Pulsed Laser Deposition (PLD)

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=D
o
exp(-c
D
/kT)
c
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.

target
substrate
Evaporation
(Molecular beam
epitaxy-MBE)
Ways to deposit thin films
target
substrate
Chemical
vapor
deposition-
CVD
Ar
+

substrate
gas
Sputtering
Low energy deposition
(MBE): ~0.1 eV

may get islanding unless
you pick right substrate or
heat substrate to high
temperatures





High energy deposition
(Sputtering ~ 1 eV)

smoother films at lower
substrate temperatures, but
may get intermixing
Low energy deposition
(MBE): ~0.1 eV

may get islanding unless
you pick right substrate or
heat substrate to high
temperatures





High energy deposition
(Sputtering ~ 1 eV)

smoother films at lower
substrate temperatures, but
may get intermixing
CCD /PMT
spectrometer
Target
Substrates
or Faraday
cup
laser beam
Pulsed Laser Deposition
CCD /PMT
spectrometer
Target
Substrates
or Faraday
cup
laser beam
Pulsed Laser Deposition
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


e-
e-
e-
e- e-
e-
e-
e-
e-
e-
e-
e-
e-
e-
Electronic excitation
Processes in PLD


e-
e-
e-
e- e-
e-
e-
e-
e-
e-
e-
e-
e-
e-
Energy relaxation to lattice (~1 ps)
lattice
Processes in PLD


Heat diffusion (over microseconds)
lattice
Processes in PLD


Melting (tens of ns), Evaporation, Plasma
Formation (microseconds), Resolidification
lattice
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
Q
ab
=(1-R)I
o
e
-oL

(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)



ab p
Q T K
t
T
C + V V =
c
c
) (
Processes in Pulsed Laser Deposition

4. Plasma creation

threshold intensity:

goverened by Saha equation:

5. Absorption of light by plasma, ionization
(inverse Bremsstrahlung)

6. I nteraction of target and ablated species with plasma

7. Cooling between pulses
(Resolidification between pulses)


pulse
threshold
t
cm Ws x
I
2 2 / 1 4
10 4

=
|
.
|

\
|
+

+
=
kT m m
m m
Q
Q Q
n
n n
ion
i e
i e
n
i e
n
i e
exp
Incredibly Non-Equilibrium!!!


At peak of laser pulse, temperatures on target can
reach >10
5
K (> 40 eV!)

Electric Fields > 10
5
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)




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


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




20 ns EXCIMER versus 1 ps TJNAF-FEL
Cobalt ~20 mJ/pulse, 20 ns, 308 nm,
25 Hz, 1 x 10
-5
Torr
Steel, ~20 J/pulse, 18 MHz, 3.1 micron
1 x 10
-2
Torr, 60 Hz pulsed, rastered beam
Less melting!
Few
particulates!
for Nb: < 1 per cm
-2

SEMs by B. Robertson, T. Wang, TJNAF
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
B
10
/B
11
, Ga
69
/Ga
71
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
http://www.ornl.gov/~odg/#nanotubes
New Materials and Nanoparticles
D.B. Geohegan-ORNL
Carbon/carbon collisons-
buckyballs
Fast carbon ions-
diamond films
Study of plasma plume and deposition of carbon materials
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)