THIN FILM DEPOSITION BY

PULSED LASER DEPOSITION (PLD)

Fahril Abdjan (23306001)

Departemen Teknik Fisika ITB
2006
 What is Pulsed Laser Deposition (PLD)?

Pulsed laser deposition is a technique for creating thin films.

The PLD method of thin film growth involves evaporation of a solid target in an
Ultra High Vacuum chamber by means of short and high-energy laser
pulses. In a typical PLD process, a researcher places a ceramic target
in a vacuum chamber. A pulsed laser beam vaporizes the surface of
the target, and the vapor condenses on a substrate. The main
components are a laser, optics, and a vacuum system.
PLD is conceptually simple: a laser beam vaporizes a target surface,
producing a film with the same composition as the target.
PLD is versatile: many materials can be deposited in a wide variety of
gases over a broad range of gas pressures.
PLD is cost-effective: one laser can serve many vacuum systems. fast:
high quality samples can be grown reliably in 10 or 15 minutes.
PLD is scalable: as complex oxides move toward volume production.
The technique of PLD was found to have significant benefits over
other film deposition methods, including:

1. The capability for stoichiometric transfer of material from target to

substrate, i.e. the exact chemical composition of a complex material
such as YBCO, can be reproduced in the deposited film.

2. Relatively high deposition rates, typically ~100s /min, can be

achieved at moderate laser fluences, with film thickness controlled in
real time by simply turning the laser on and off.

3. The fact that a laser is used as an external energy source results

in an extremely clean process without filaments. Thus deposition can
occur in both inert and reactive background gases.

4. The use of a carousel, housing a number of target materials,

enables multilayer films to be deposited without the need to break
vacuum when changing between materials.
 Why superconductors?
Why PLD?

12.5 kV, 1250 Amp, 3 phase

High temperature superconducting cable
YBa2Cu3O7-xcrystal structure
showing Cu coordination.

RF superconducting filter for cell phone

base stations.
What is superconductors?
Behavior of heat capacity (cv) and
resistivity () at the superconducting
phase transition
Superconductivity is a
phenomenon occurring in
certain materials at extremely
low temperatures (on the order
of negative 200 degrees
Celsius), characterized by
exactly zero electrical resistance
and the exclusion of the interior
magnetic field (the Meissner
effect )
 History of Pulsed Laser Deposition (PLD)

adalah Albert Einstein, sejak tahun 1916 telah mendalilkan

stimulated emmision process.
Oleh Theodore H.Maiman tahun 1960 menggunakan maser optic
(alat pengukur elektro magnet) yang dihubungkan dengan
menggunakan tangkai ruby sebagai medium penguat.
pada tahun 1962 , Gagang bedil salib (Laser Mirah) digunakan
untuk menguapkan exict atoms dari solid surface.
Dekade sekarang, progress laser technology sangat maju
membuat thin film yang baik sangat dimungkinkan.
salah satunya adalah Pulsed Laser Deposition High-Temperature
(Tc) superconducting film.
PLD juga telah digunakan untuk thin film dari kristal (growth)
dengan metode epitaksi. Ceramic oxide, nitride films, metallic
multi layers, and various super lattices grown.
Terbaru ; synthesis nanotubes, nanopowders, dan quantum dots,
telah dilaporkan tentang isu reproducibility, large-area scale-up
multiple-level.
 Secara garis besarnya proses Pulsed laser
Deposition (PLD) dapat berlangsung harus memiliki
empat komponen;

dari gambar ;
1. Pulsed Laser
2. UHV- Chamber
3. Target (material)
4. Substrate
 Mekanisme Pulsed Laser
Deposition
Prinsip Pulsed Laser Deposition (PLD),
sangat kontras dengan set-up sistemnya,
phenomena physical yang sangat
kompleks karena melibatkan proses
interaksi dari radiasi matrial- laser
dengan suatu target surface padatan. Hal
ini meliputi formasi plasma plume dengan
transfers energy yang besar ke surface
substrate untuk akhir proses
pertumbuhan film.

Pulsed Laser Deposition (PLD) biasanya di bagi menjadi

empat bagian;
1. Interaksi radiasi laser dengan target
2. Dinamika Ablation materials
3. Deposition dari ablation materials dengan substrate
4. Nucleation and growth dari thin film diatas surface substrate
 collisional, thermal, and
Diagram alir Mekanisme metode PLD; electronic excitation,
exfoliation , hydrodynamics

High energy
Target surface/
Laser Collision
material

Law of thermodynamics
Angle struck
Ablasi dependent
Tc tinggi
Matrial dissociated

Diameter Dm = KT ln ( R/Re)
Tebal N99 = A 1/R) 1/3 exp (-1/T

Density

Nucleation- and Thin film substrate

-Growth
Parameter yang Perlu untuk diperhatikan
pada proses PLD ;

Laser flounce (i.e. the energy per unit of area)

and wavelength
Structural and chemical composition of the
target material
Chamber pressure and the chemical
composition of the buffer gas
Substrate temperature and the distance
between the target and the substrate.
Jenis angle struck dari PLD
 Jenis Plasma plume dari Matrial

YBCO plume LSMO plume TiN plume

An intensified, gated CCD camera has been used to observe the plume
dynamics of YBa2Cu3O7-x during Pulsed Laser Deposition (PLD). One of the
manufacturing keys to incorporating high temperature superconducting YBCO
wires into new devices and designs is the ability to manufacture continuous long
lengths of superconducting wire
Langmuir probes and optical spectroscopy are used to diagnose the plasma
conditions and optical reflectometry is used to monitor the film growth
 Untuk PLD sendiri terdapat beberapa contoh
karesteristik laser;
Excimer laser

Laser medium ArF KrF XeCl XeF

Wavelength (nm) 193 nm 248 nm 308 nm 351 nm

Pulsed energy (mJ) 400 600 400 320

Average power (W) 10 16 11 8

6
Gas lifetime (10 pilse) 0.4 1 10 2
 Beberapa parameter repsentatif laser adalah;
The wave length is in the UV range
A pulse on the order of 25 ns in duration (the pulse duration,
t )
8
At power density j of 2.4 x10 W/cm2 at the target
The illuminating an area of the target (A) of typically 0.1
2
cm.
At a repetition rate(f) of 50 Hz.
2
The fluence of this typical pulse (j t ) is 6 J/cm. The
incident energy per pulse is 300 600 mJ.
8
The intantaneous power is 2.4 x 10 W, dan average power is
30 W
 Untuk material deposited yang digunakan terdapat
beberapa references; (Hans-Ulrich krebs et al).

Materials Molecules formula literature

High-temperature YBa2Cu3O7 Dijkkamp et al. (1987)
Superconductors BiSrCaCuO Guarnieri et al. (1988)
TiBaCaCuO Foster et al. (1990)
MgB2 Shinde et al. (2001)
Oxides SiO2 Fogarassy et. al (1990)
Carbides SiC Ballooch et al. (1990)
Nitrides TiN Biunno et al. (1989)
Ferroelectric materials Pb(Zr,Ti)O3 Kidoh et al. (1991)
Diamond like carbon C Martin et al. (1990)
Buckminster fullerene C6O Curl & Smalley (1991)
Polymers Polyethylene,PMMA Hansen & Robitaile (1988)
Metallic Systems 30 alloys/multilayer Krebs and Bremert (1993)
FeNdB Geurtsen et al. (1996
 TYPICAL PROPERTIES
OF SINGLE CRYSTAL SUBSTRATES
Lattice Lattice
TE Loss
Crystal Const. Const. Density M Pt Dielectric
Material coef Tangent @
Type A A (g/cm3) Celsius Constant
10^-6 10GHz
a c
Al203 Hex 4.758 12.991 3.97 2030 7.5 9.3 9x10^-3
MgO Cubic 4.216 3.58 2800 12.8 9.8
MgAl204 Cubic 8.083 3.6 2130 7.45
ZnO Hex 3.252 5.213 5.605 1975 2.9
SrTiO3 Cubic 3.905 5.12 2080 10.3 300 2 x 10^-2
LaAlO3 Rhom 3.79 13.11 6.51 2180 9.2 24.5
NdGaO3 Ortho 5.43 7.71 7.57 1600 4.5 20 3 x 10^-3
SrLaALO3 Tetrag 3.756 12.63 1348 4.65 16.8 6 x 10^-4
SrLaGaO3 Tetrag 3.84 12.68 1238 6 300
YtAlO3 Ortho 5.176 5.815 6.1 1870 5.59 16-20 10 x 10^-4
YSZ Cubic 5.41 5.8 2500 10.3 27
(LaAlO3).3-
(Sr2AlTaO8). 3.868 6.74 1840 10 22
7
 TYPICAL PROPERTIES CRYSTAL
SUBSTRATES superconductors
crystal Structure /lattice Density Thermo- Dialectric Lattice Growth tech
constan(A) M.POC g/c m3 Expands constant mismatch & max size
6 to YBCO
X10

LSAT Cubic, a= 3,868 1840 6.74 10 22 0.82% CZ.2

LaALO a=3.790 c=13 2100 6.51 9.2 24.5 2.8% CZ.3

3

MgO Cubic, a=4.21 2852 3.58 12.8 9.80 7.9% Arc melt 2"

NdCaAlO Tetrag. a=3.685 c=12 1850 5.56 12.0 19.5 5.5% CZ 35mm
4 .12

NdGaO Orthor. a=5.43 b=5.50 1600 7.57 7.80 25 1.1% CZ, 2"
3 c=7.71
SrTiO Cubic, a=3.905 2080 5.12 10.4 300 0.12% vernuil
3 30mm
SrLaAlO Tetrag. a=3.756 1650 5.92 10.5 16.8 3.7% CZ, 1"
4 c=12.63
SrLaGaO Orthor. a=5.176 1600 4.88 2 ~ 10 16~20 5.7% CZ, 1"
4 b=5.307 c=7.355
YSZ Cubic, a=5.125 ~2500 5.80 10.3 27 31% Arc melt 2"
 Typical Properties of Single Crystals Substrates
for III-V Nitride Films

Crystal Structur Lattice Constant A TE Coeff. Lattice Wafer

e a b c (10- mismatc Max Size
ºK ) h to GaN
Al2O3 Hexag. 4.758 ---- 12.99 7.50 14% 6" dia
<0001>

MgO Cubic 4.216 ---- ---- 12.8 13% <111> 3" dia

MgAl2O4 Cubic 8.083 ---- ---- 7.45 9% 1.5" dia

<111>

ZnO Hexag. 3.252 ---- 5.213 2.90 2.2% 10x10mm

<0001>

SiC(6H) Hexag. 3.08 ---- 15.12 10.3 3.5% 10x10mm

<0001>

LiAlO2 Tantra 5.17 ---- 6.26 ---- 1.4% <100> 30mm dia

LiGaO2 Orthor. 5.406 5.012 6.379 ---- 0.2% <100 30mm dia
>

NiAl (new) Cubic 2.880 ---- ---- ---- 10% <100> 20mm dia
 Properties of Single Crystal Substrate
ANTHANUM ALUMINATE - LaAl03
Twinning boundaries parallel to pseudo cubic
cell. Grown czochralski method the most
widely used substrate for high frequency,
microwave applications on (100) orientation.
Available any size up to 3" diameter.

SAPPHIRE - Al2O3
Twin free and defect free. Al2O3 is
available up to 10" diameter. Sapphire is
used for a number of applications and is
grown several different methods. We offer
a high quality grade specifically for HTSC
film growth. Boules are accurately oriented,
precision wafered, and epitaxially
polished. Standard orientation is (0001) C-
plane. Also available are A-plane (1120), R-
plane (1102) and M-plane (1100).
 Bulk vs. thin film synthesis
Flux-grown YBCO bicrystal
-simple growth
-very good stoichiometry
-very good crystallinity
-difficulty in controlling structure
PLD-grown YBCO bicrystal
-growth in a vacuum chamber
-can control stoichiometry
-can control crystallinity
-well-defined final structure.
 Thin film growth techniques

evaporation/ MBE
sputtering
vacuum
pulsed laser deposition -one step
epitaxy
CVD (chemical vapour deposition)

electrochemical
bulk techniques
sol-gel -post-anneal needed for epitaxy
spin-coating
spray pyrolysis
1. Island growth (Volmer-Weber)
form three dimensional islands
film atoms more strongly bound to each other than to substrate
and/or slow diffusion

2. Layer by layer growth (Frank -van derMerwe)

generally highest crystalline quality
film atoms more strongly bound to substrate than to each other
and/or fast diffusion

3. Mixed growth (Stranski-Krastanov)

initially layer by layer, then forms three dimensional islands
 Film growth issues:

1. Stoichiometry: chemical composition of the film.

2. Epitaxy: the film is single crystal, and is related to the substrate crystal
orientation. Achieved by heating the substrate, so the film atoms have
energy to relax into a crystal structure commensuratewith the substrate.

3. Impurities: at high temperatures, the substrate and film atoms can

interdiffuse. Other impurity sources: target holders, walls etc.

4. Strain: the crystal spacing of film and substrate material is usually not the
same. This means the film has intrinsic strain,which can lead to defects, film
roughness, delamination.

5. Second phases: the film may phase-separate into different regions, with
different properties.
Contoh; ilustrasi dari interaksi substrate

Dari diagram; terlihat bahwa energetic

species memercik sebagian ke surface
atoms dan terbentuk collision region yang
baik diantara incident flow dan sputtered
atoms. Maka Film grows terbentuk di
thermalized region (collision region) .
Daerah tersebut berfungsi sebagai sebuah
source for condensation of particles.
Manakala tingkat condensation lebih
tinggi di banding particles supplied by the
sputtering, maka akan tercapai thermal
equilibrium condition dengan cepat film
grows akan menempel pada substrate
surface diikuti oleh terjadinya the direct
flow of the ablation particles.
Evaporation/ MolecularBeam Epitaxy

Each target atomic species

has its own effusion cell.

Each type of target is

vaporized independently by
i) heat, ii) e-beam, iii) laser.

Rate control is the big challenge.

UHV MBE system for GaAs

etc.
 Sputtering

A sputtering gas is used to excite a charged plasma which coats the

substrate.
Each type of atom has a different sputtering energy.
Controlling the charged plasma, and preventing resputtering from the
substrate are the challenges here.
Pulsed Laser Ablation

A high-power excimerlaser is
focused on the target.

The target is ablated to

form a plume of atoms, molecules
and chunks.

The advantage of PLD is that

complex materials can be easily
ablated.

The challenge is minimizing

chunks, and maintaining
stoichometry.
 Pulsed Laser Ablation PLD;
Dapat juga digunakan pada Ceramic oxide, nitride films, metallic multi
layers, and various super lattices grown.

In the PLD technique, a laser beam

(frequently an excimer laser) is directed
at a solid target. The interaction of the
pulsed laser beam with the target
produces a plume of material that is
transported toward a heated substrate
placed directly in the line of the plume.
Multiple targets can be loaded inside the
chamber on a rotating holder, which can
be used to sequentially expose different
targets to the laser beam, thereby
enabling the in-situ growth of
heterostructures and superlattices with
relatively clean interfaces.
In a PLD Chamber a target is vapourised by an intense pulsed laser to
create a plasma plume and the material is deposited on a substrate.
This method is most useful for oxides and other compounds such as
YBa2Cu3O7, (La0.7S0.3)MnO3, EuS and Heusler Alloy.
 Chamber

Laser + optics

gas handling
Figure 1); A photograph of vacuum chamber used in pulsed laser deposition.
The target was oriented at 45 degrees to the axis of laser beam
 Goal: Understanding electromagnetic transport
across low angle grain boundaries (LAGBs).

In YBa2Cu3O7-xbicrystals, the zero

field Jc across the grain boundary
drops rapidly with misorientation
angle, .

Dimos, Chaudhari, Mannhart, LeGoues,

PRL,61, 219 (1988); PRB, 41, 4038 (1990).

Zero field Jb/Jcvs. at 77 K decreases Heinig et al., Appl. Phys. Lett.,

rapidly with increasing . 69, 577, (1996).
 What do PLD grown films look like?

FESEM image of 7 o YBa2Cu3O7 HRTEM image of 10o YBa2Cu3O-

 High magnetic field, nV sensitive transport
data show progressive change with

Log(V) -log(I) show

increasing GB
influence, at low and
high voltage,
as increases.

77 K, H||c
 Different 7othin film bicrystals can have very
different extended V-I characteristics.

In one bicrystal, there is little evidence

The other bicrystal shows evidence
of the GB in the V-I characteristic.
of weak coupling and flux flow along the
GB at higher V.
 HRTEM image of a supersaturated
Fe(Ag) lm showing
TEM image of a polycarbonate a dislocation loop and dislocations
lm with nanocrystalline Ag grains (enlarged in the insets)
Change of the Permalloy thin lm texture, depending on the Ar gas
pressure during PLD at room temperature
 Experiment by; Monica Vendan
Iowa State University, Ames, Iowa 2006

Scanning electron micrograph of the morphology

of SiC film deposited on Si by
a). fs-PLD at 500C substrate temperature; and
b) CVD at 1360oC
 Experimental Detail By Monica Vendan

Silicon wafers substrate with (1 0 0) ukuran 250 mm thickness,

and 25 mm diameter dibersihkan dengan HF
acid,deionized,aseton dan methanol dan diletakkan dalam
UHV standard .
Target Polished Teflon sheet 22 mm 2diletakkan dengan jarak
40 mm dari substrate.
The chamber diberi tekanan 10 -6Torr dengan turbo molecular
pump pada tekanan 0,5 mbar .
Substrate di panaskan 300 oC dengan resistance heather.
Menggunakan teknik (CPA) sistym tekan.suatu amplifier
regenarative ( pump Nd: YLF laser) dan sebuah compresor
.laser memancarkan 120 fs pulses secara linier, cahaya
dipolarisasi didalam Gaussian beam (M = 1:5 ) panjang
gelombang 800 nm (photon energy = 1:55eV) diameter beam
6 mm,
 o
Laser pada frekfensi 1 kHz di focuskan pada2lensa 45
pada surface target untuk spot size 50 mm digunakan pulse
energy 0,01s/d 0.5 mJ. (energy fluence 25 J/cm )
Target dan substrate diputar selama proses PLD agar tejadi
uniform cratering target dan deposition film.dan dipanaskan
pada 500oC selama 10 menit.
Di dinginkan dengan kecepatan pendinginan 5o C/m untuk
peningkatan morphology thin film.
dua silicon subrate yang mengandung PTFE hasil selama
15 dan 45 menit ditandai dan di baca hasilnya dengan
AFM, SEM, FT-IR spectroscopy dan X-ray . Hasilnya
dibandingkan dengan Exremer PLD .
 Comparison of nanosecond and femtosecond pulsed laser ablation
Characteristic Nanosecond pulsed Femtosecond pulsed
excimer laser ablation Ti:Sapphire laser ablation

Lasermaterial interaction Single-photon Multi-photon absorption

absorption
Energy absorption depth Few tens of nanometers Near vicinity of the target

Congruent evaporation Less More

Energy of plasma species Low High

Deposition rate Low High

Target degradation High Low

Particulate density High Low

Thermal diffusion effects More Less

Proses lanjut Thin film dari PLd

Photolithography is a six step

process. Photoresist is spun
onto a thin film which is then
exposed to UV light through a
mask. The development step
then removes the exposed
photoresist ad the pattern is
etched. The remaining
photoresist is then removed
with a solvent.
 Advantages and Disadvantages of PLD
Advantages:
1. New technique.
2. Simple (fast, and easiest to study new chemical systems).
3. Compatible with oxygen and other reactive gases.
4. Cost-effective: one laser beam can be split into multiple
beams that can serve many vacuum systems.
5. Scalable: technology can be extended to high-volume
production through multiple targets and beams.
Disadvantages:
1. Particulates.
2. Target degradation
3. Composition and thickness depend on deposition conditions.
Difficult scale-up to large wafers?
 Low angle [001] tilt YBa2Cu3O7-xbicrystals
were grown by laser ablation, and
characterized by FESEM,TEM,and zero and
high magnetic field transport.
A progression from strongly coupled, flux-
pinning limited transport behavior to weakly
coupled, Josephson behavior was seen
between 3oand 15o.
Variation between bicrystals with the same
shows that extrinsic factors modify the GB
transition region.
PEMBATAS