Pulsed Laser Deposition (PLD)

Anne Reilly
College of William and Mary
Department of Physics

Outline
1. Thin film deposition
2. Pulsed Laser Deposition
a) Compared to other growth techniques
b) Experimental Setup
c) Advantages and Disadvantages
3. Basic Theory of PLD
4. Opportunities

Thin Film Deposition

Transfer atoms from a target to a vapor (or plasma) to a substrate

Thin Film Deposition

Transfer atoms from a target to a vapor (or plasma) to a substrate

After an atom is on surface, it diffuses according to: D=Doexp(-D/kT)

D is the activation energy for diffusion ~ 2-3 eV
kT is energy of atomic species.

Want sufficient diffusion for atoms to find best sites.

Either use energetic atoms, or heat the substrate.

Ways to deposit thin films

substrate

target

substrate
Chemical
vapor
depositionCVD

Ar+
target
Sputtering

Evaporation
(Molecular beam
epitaxy-MBE)

substrate
gas

Low energy deposition

(MBE): ~0.1 eV

High energy deposition

(Sputtering ~ 1 eV)

may get islanding unless

you pick right substrate or
heat substrate to high
temperatures

smoother films at lower

substrate temperatures, but
may get intermixing

Low energy deposition

(MBE): ~0.1 eV

High energy deposition

(Sputtering ~ 1 eV)

may get islanding unless

you pick right substrate or
heat substrate to high
temperatures

smoother films at lower

substrate temperatures, but
may get intermixing

Pulsed Laser Deposition

CCD /PMT
spectrometer

laser beam

Substrates
or Faraday

Target

cup

Pulsed Laser Deposition

CCD /PMT
spectrometer

laser beam

Substrates
or Faraday

Target

cup

Target: Just about anything! (metals, semiconductors)

Laser: Typically excimer (UV, 10 nanosecond pulses)
Vacuum: Atmospheres to ultrahigh vacuum

Advantages of PLD
Flexible, easy to implement
Growth in any environment
Exact transfer of complicated materials (YBCO)
Variable growth rate
Epitaxy at low temperature
Resonant interactions possible (i.e., plasmons in metals,
absorption peaks in dielectrics and semiconductors)
Atoms arrive in bunches, allowing for much more controlled
deposition
Greater control of growth (e.g., by varying laser parameters)

Disadvantages of PLD

Uneven coverage
High defect or particulate concentration
Not well suited for large-scale film growth
Mechanisms and dependence on parameters
not well understood

Processes in PLD

Laser pulse

Processes in PLD

eee- e- ee- ee-e- e-eeee-

Electronic excitation

Processes in PLD

lattice

eee- e- ee- ee-e- e-eeee-

Energy relaxation to lattice (~1 ps)

Processes in PLD

lattice

Heat diffusion (over microseconds)

Processes in PLD

lattice

Melting (tens of ns), Evaporation, Plasma

Formation (microseconds), Resolidification

Processes in PLD

lattice

If laser pulse is long (ns) or

repetition rate is high, laser may
continue interactions

Processes in Pulsed Laser Deposition

1. Absorption of laser pulse in material

Qab=(1-R)Ioe-L
(metals, absorption depths ~ 10 nm, depends on )
2. Relaxation of energy (~ 1 ps) (electron-phonon interaction)
3. Heat transfer, Melting and Evaporation
when electrons and lattice at thermal equilibrium (long pulses)
use heat conduction equation:
(or heat diffusion model)

T
C p
( KT ) Qab
t

Processes in Pulsed Laser Deposition

4. Plasma creation
threshold intensity:

4 x 10 4Ws1 / 2cm 2
I threshold
t pulse

goverened by Saha equation: ne ni QeQi me mi exp ion

nn

Qn me mi

kT

5. Absorption of light by plasma, ionization

(inverse Bremsstrahlung)
6. Interaction of target and ablated species with plasma
7. Cooling between pulses
(Resolidification between pulses)

Incredibly Non-Equilibrium!!!
At peak of laser pulse, temperatures on target can
reach >105 K (> 40 eV!)
Electric Fields > 105 V/cm, also high magnetic fields
Plasma Temperatures 3000-5000 K
Ablated Species with energies 1 100 eV

PLD with Ultrafast Pulses (< 1 picosecond)

see Stuart et al., Phys. Rev. B, 53 1749 (1996)
A new research area!
If the pulse width < electron lattice-relaxation time, heat diffusion, melting significantly
reduced! Means cleaner holes and cleaner ablation
Direct conversion of solid to vapor, less plasma formation
Reactive chemistry: energetic ions, ionized nitrogen, high charge states
Leads to less target damage (cleaner holes), and smoother films (less particulates)

PLD with Ultrafast Pulses (< 1 picosecond)

see Stuart et al., Phys. Rev. B, 53 1749 (1996)
A new research area!
If the pulse width < electron lattice-relaxation time, heat diffusion, melting significantly
reduced! Means cleaner holes and cleaner ablation
Direct conversion of solid to vapor, less plasma formation
Reactive chemistry: energetic ions, ionized nitrogen, high charge states
Leads to less target damage (cleaner holes), and smoother films (less particulates)

> 50 ps
Conventional melting, boiling and fracture
Threshold fluence for ablation scales as 1/2

< 10 ps
Electrons photoionized, collisional
and multiphoton ionization
Plasma formation with no melting
Deviation from 1/2 scaling

20 ns EXCIMER
Cobalt ~20 mJ/pulse, 20 ns, 308 nm,
25 Hz, 1 x 10-5 Torr

versus 1 ps TJNAF-FEL
Steel, ~20 J/pulse, 18 MHz, 3.1 micron
1 x 10-2 Torr, 60 Hz pulsed, rastered beam

FILM

(deposited on silicon)

TARGET

Less melting!

SEMs by B. Robertson, T. Wang, TJNAF

Few
particulates!
for Nb: < 1 per cm-2

Opportunities
Ultrahigh quality films
Circuit writing
Isotope Enrichment
New Materials
Nanoparticle production

Magnetic Moment of fcc Fe(111) Ultrathin Films

by Ultrafast Deposition on Cu(111)

J. Shen et al., Phys. Rev. Lett., 80, pp. 1980-1983

MBE

PLD
Higher quality films, better
magnetic properties

MICE
Direct writing of electronic components- in air!
Rapid process refinement
No masks, preforms, or long cycle times
True 3-D structure fabrication possible
Single laser does surface pretreatment, spatially selective material deposition,
surface annealing ,component trimming, ablative micromachining, dicing and
via-drilling

Isotope Enrichment in Laser-Ablation Plumes and Commensurately

Deposited Thin Films

P. P. Pronko, et al. Phys Rev. Lett., 83, pp. 2596-2599

Over twice the natural enrichment of
B10/B11, Ga69/Ga71 in BN and GaN films
Plasma centrifuge by toroidal and axial
magnetic fields of 0.6MG!

Transient States of Matter during Short Pulse Laser Ablation

K. Sokolowski-Tinten et al., Phys. Rev. Lett., 81, pp. 224-227

Fluid material state of high index of
refraction, optically flat surface

New Materials and Nanoparticles

D.B. Geohegan-ORNL

http://www.ornl.gov/~odg/#nanotubes

Study of plasma plume and deposition of carbon materials

Carbon/carbon collisonsbuckyballs

Fast carbon ionsdiamond films

References
Pulsed Laser Vaporization and Deposition, Wilmott and
Huber, Reviews of Modern Physics, Vol. 72, 315 (2000)
Pulsed Laser Deposition of Thin Films, Chrisey and
Hubler (Wiley, New York, 1994)
Laser Ablation and Desorption, Miller and Haglund
(Academic Press, San Diego, 1998)