Silicon carbide thin films for EUV

application deposited by means of

Pulsed Laser Deposition (PLD)
Gianni Monaco LUXOR-IFN Laboratory
COST meeting Krakow, May 2010
COST-STSM-MP0601-05393 Report
gmonaco@dei.unipd.it
 Outline

❑ SiC Carbides in the EUV;

❑ PLD systems;

❑ SiC thin films deposited at IOP-WAT

Warsaw with Excimer laser;
❑ Analysis of the films;

❑ Some SiC thin film deposited at LUXOR

with Nd-YAG.
Gianni Monaco COST meeting Krakow, 26 may 2010 2/24
 List of pubblications on SiC and PLD materials
@LUXOR lab.

❑ P. Nicolosi, D. Garoli, M. G. Pelizzo, V. Rigato, A. Patelli, and F. Rigato, “VUV reflectance

measurements and optical constants of SiC thin films” J. Electron Spectrosc. Relat.
Phenom. 144–147, (2005).
❑ D. Garoli, G. Monaco, F. Frassetto, M.G. Pelizzo, P. Nicolosi, L. Armelao, V. Matterello, V.
Rigato “Thin film and multilayer coating development for the extreme ultraviolet
spectral region” “Radiation Physics and Chemistry”, 75 (11), p.1966-1971, Nov 2006
❑ G. Monaco, D. Garoli, R. Frison, V. Mattarello, P. Nicolosi, M. G. Pelizzo, V. Rigato, L.
Armelao, A. Giglia, S. Nannarone, “Optical constants in the EUV soft x-ray (5÷152 nm)
spectral range of B4C thin films deposited by different deposition techniques”,
Proceedings SPIE, 6317, (2006).
❑ D.Garoli, F. Frassetto, G. Monaco, P. Nicolosi, M.-G. Pelizzo, F. Rigato, V. Rigato, A. Giglia,
S. Nannarone, “Reflectance measurements and optical constants in the extreme
ultraviolet-vacuum ultraviolet regions for SiC with a different C/Si ratio” Appl. Opt.
45(22) (2006) 5642-5650.
❑ Gianni Monaco, M. Gastaldi, P. Nicolosi, M.G. Pelizzo, E. Gilioli, S. Rampino, S. Agnoli, G.
Granozzi and N. Manuzzato, “Silicon carbide thin films for EUV and soft X-ray
application” Eur. Phys. J. ST 169-1 (2009).
❑ Gianni Monaco, M. Suman, M. G. Pelizzo, P. Nicolosi, “Optical constants of silicon
carbide deposited with emerging PVD techniques”, Proc. SPIE Vol. 7360 (2009).
Gianni Monaco COST meeting Krakow, 26 may 2010 3/24
 Carbides material

Hot-
pressed
material B 4C
CVD SiC Mo Al Si Zerodur®
properties

Density, ρ (kg m–3 ) x 10-3 3.21 2.52 10.3 2.7 1.85 2.55

Coefficient of thermal expansion, α

2.4 5.6 5.4 25.0 11.4 0.15
(K–1x10–6)

Specific heat, C (J kg –1 K–1) 700 950 250 899 1880 820

Termic conductivity, κ (W m–1 K–1) 200 30 - 42 134 237 216 6.0

Young's Modulus , E (GPa) 466 450-470 250 76 303 90

Hardness KH (kg mm-2) 2480 275

•low density
•high melting point
•low expansion coefficient
•can be polished to lower roughness than metals
Gianni Monaco COST meeting Krakow, 26 may 2010 4/24
 Reflecting materials for EUV
200 nm 105 nm 30 nm 0.2 nm
❑ Presence of a great number of VUV
VUV
atomic resonance EUV
EUV (reflective
(reflective optics)
optics)
❑ →radiation absorbed on very Soft X-ray (ML’s
Soft X-ray (ML’s optics)
optics)
short distances
❑ complex refractive index:
n=1-+ik (n=1- )
0.9

❑ Fresnel normal incidence 0.8

Al+MgF2
reflectance: R=(1-n)/(1+n)2 0.7 Au

=(2 + k 2 )/4 0.6

Pt
Ir
❑ Below 30 nm (Soft X-ray) , k Reflectivity 0.5
CVD SiC

«1
=>R < 10-4 0.4

❑ → optics must be used at 0.3

grazing incidence in order to 0.2

take advantage of total 0.1
reflection
0
❑ → Multilayers optics (ML’s) 20 40 60 80 100 120 140 160 180 200 220 240
wavelength (nm)

Gianni Monaco COST meeting Krakow, 26 may 2010 5/24

 Deposition of Silicon Carbide thin films for EUV

• CVD-techniques Si atom
• monocrystalline β-SiC with T≈ 1400°C C atom
• high normal incidence reflectance
• (R > 40% for λ < 60nm)
• good stability 3.08Å
Fernandez-Perea et al. Proc. SPIE
6317, (2006)
• Sputtering techniques
(Ion beam, or magnetron)
• worse performances than CVD-SiC
• only amorphous SiC Larruquert et al.,Appl. Opt. 39
• Suitable for multilayer (2000);
• lower temperature J. B. Kortright and D. L. Windt
Appl. Opt. 27, 2841–2846 (1988)
• lower cost
• Reflectivity degradation

Gianni Monaco COST meeting Krakow, 26 may 2010 6/24

 SiC deposition techniques/2

❑ HOW TO OBTAIN HIGH REFLECTIVE SiC AT LOWER

TEMPERATURE THAN CVD PROCESS?
❑Plasma Enhanced-CVD
(R.A.M. Keski-Kuha, Appl. Opt. 27 (1988).
❑With Pulsed Laser Deposition at around 800 °C is
possible to obtain a crystalline SiC. Pelt et al. Thin
Solid Films, 371 (2000).
Let’s try Pulsed
deposition techniques
(as PLD)!

Gianni Monaco COST meeting Krakow, 26 may 2010 7/24

 PLD deposition systems

Features:
❑Very high heating rate of the target surface (108 K/s ).
❑deposition of crystalline film demands a much lower substrate
temperature
❑stoichiometry of the target can be retained

laser beam
AR window

substrate
holder
Particulate generation substrate

❑ can be connected to two macroscopic processes: exfoliational and

hydrodynamical-sputtering.
❑ Related to the laser parameters: wavelength, fluence and pulse duration
❑ The particulate content
target decreases with the wavelength
Vacuum chamber

Gianni Monaco COST meeting Krakow, 26 may 2010 8/24

PLD Deposition facility at the MUT

Gianni Monaco COST meeting Krakow, 26 may 2010 9/24

 Experimental Set-up

❑Silicon Carbide β-SiC (crystalline) target

❑Substrates
❑ Single Crystal Sapphire orientated on the 0001 C-plane
(for heteroepytaxial grow)
❑Si (111) (for for heteroepytaxial grow)
❑Si (100) (for further analysis)

Gianni Monaco COST meeting Krakow, 26 may 2010 10/24

 Deposited samples
Sample Substrate Temp (°C) RF etching Base pressure Fluence Freq (Hz) Laser Distance (mm) Atmosphere Time (min)
(min) (torr) (J/cm2) energy
1 Si RT 15 2.07x10-5 1.3 1 133.5 mJ - Vacuum 30
2 Si RT 15 2.07x10-5 1.3 1 133.5 mJ - Vacuum 30

❑3 Frequency:
Si evenRTif an higher 15 repetition rate would
2.9 x10-5 2 have
1 resulted
200 in -an higher deposition
Vacuum 60rate,
4 we chose Sap a rateRT of 1 Hz for 15
all the deposition.
2.9 x10 -5
2Our goal 1 was 200to get a -crystalline,Vacuum
hence 60
15 3 x10 -5
5 Si RT 3 1 120 74 (ca) Vacuum 90
6
organized,
Si
structure
RT
and15this could 3be x10
better 3accomplished
-5
1
if the atoms
120 74 (ca)
on theVacuum
substrate 90
7
surface Si
have longer
538
time No intervals in
1x10order
-4 to organize
1.3 1
themselves.
137 74 (ca) Vacuum 90
❑8 Laser fluence:
Sapp laser
538 fluence No was chosen 1x10 -4
very low.
1.3 The1 deposition
137 threshold
74 (ca) of Vacuum
Silicon Carbide
90
9 with excimer
Si laser
800 @192 nm is 1 J/cm and we
10 min 1x10 2 -4
1.3choose 1 to be around80that valueVacuum
135.6 to get less 45
-2
(10 mbar Ar)
10
particulate
Si
and give
900
raise to a slower
30 min 1x10 crystallization
-4
1.3(ca)
process.
1 148
The two 80
deposition carried75at 3
Vacuum
2
J/cm (sample 5 and 6) where used to locate the plume position and direction inside the
(10 -2
mbar Ar)
11 chamber.Sapp 900 30 min 4.5x10 -1x10 -5 -4
1.3(ca) 1 148 80 Vacuum 75
-2
(10 mbar Ar)
❑12 Substrates:
Sapp Silicon 930 (111)30and min Sapphire
-2
4.5x10 were
-1x10-5
used
1.3 for1two reasons:
-4
138 they
80 have low lattice 120
Vacuum
(10 mbar Ar)
13
mismatchSapp
with 3C-SiC
930
and can be suitable
30 min 3.5x10 -8x10
for 1.3
-5 heteroepitaxial
-5
1 138
growth80(3C-SiC has 4.36 Å,120
Vacuum
Sapphire 4.75 Å on its face [0001],
-2
(10 mbar Ar) Si (111) has 9.23 Å) , while Silicon (100) (cubic, lattice
14 constant 5,43 Å) is mainly
Si(111) 930 used as a test sample
30 min 3.5x10 -8x10 -5
1.77 for successive
-5
1 185 characterization
80 such as 120
Vacuum film
-2
(10 mbar Ar)
15 thickness
Sappand composition.
930 30 min 3.5x10 -8x10 -5 -5
1.77 1 185 80 Vacuum 120
❑16 Temperature:
-2

Sapp
the930
temperature
(10 mbar Ar)
30 min
is another
3.5x10 -8x10
crucial
-5 -5
1.77
parameter
1 185
in our process.
80
As said in the
previous document in which
(10 mbarthe
-2 Ar) project has been exposed, the crystalline CVDVacuum 120
silicon carbide
17 is obtained
Si(111) at a 930
temperature 30 min as high as-6x10
3.5x10 1400 °C,
-5
1.45 but 1with PLD
-5
148 we are 80 trying toVacuum
demonstrate 90
-2
(10 mbar Ar)
18
that it is possible930to obtain
Sapp 30 minthe same structure
3.5x10 -6x10-5 -5
1.45
at lower
1
temperature.
148 80
We plannedVacuum
to keep90
the
deposition temperature(10around mbar Ar) 900° C for all the samples to help the crystalline growth.
-2

-5 -5
30 min 3.5x10 -6x10
❑ For the last three samples
19 Sapp 930
20,Ar)21, 22 we tried1.45
-2
(10 mbar to help1 film crystallization
148 80
by useVacuum
of Ar 90
20 bombardment
Sapp keeping
ca 650 a30 mild
min temperature
5x10 -5
of1.7650° C.1 185 43 Ar (6x10-3 120
(10-2 mbar Ar)
torr)
21 Sapp ca 650 30 min 5x10-5 1.7 1 185 43 Ar (6x10-3 120
(10-2 mbar Ar)
torr)
22 Si(111) ca 650 30 min 5x10-5 1.7 1 185 43 Ar (6x10-3 120
Gianni
(10 -2 Monaco COST
mbar Ar) meeting Krakow, 26 may 2010 11/24 torr)
 AFM analysis of the deposited samples

Sapphire substrate Sample n°4 Sample n°5

Sample n°8 Sample n°15 Sample n°18

Gianni Monaco COST meeting Krakow, 26 may 2010 12/24

 Samples thicknesses

❑ Silicon Carbide has an absorption dip centered at 795 cm−1 that could be
ascribed to TO-phonon mode of SiC in its cubic or hexagonal phase

880 cm-1

825 cm-1

Gianni Monaco COST meeting Krakow, 26 may 2010 13/24

 Samples thicknesses

Profilometer measurements of the step height

1500
1400
1300
1200
1100 sample6
1000
sample5
step height (Å)

900
800
700
600
500
400
300
200
100
0
-100 0 200 400 600 800 1000 1200 1400
position on the profilometer stage (µm)

Samples number 5 and 6 (high fluence=of 3 J/cm2 90 min @RT)

Gianni Monaco COST meeting Krakow, 26 may 2010 14/24
 SEM images

Sample n°8 Sample n°19

Gianni Monaco COST meeting Krakow, 26 may 2010 15/24
 XRD spectra of the samples

Sapphire 1 1 -2 0

Sapphire 006
Sapphire 003

❑Peak @ 43° 21° and 38° are due to the Sapphire substrate.
❑3 spectra show different features: SiC8, SiC12 and SiC19 (Sapphire peaks disappear)
The feature of these spectra, as retrieved in the Instrument database (ICCD-JCPDS),
cannot be attributed to any of the SiC crystalline structure.

Gianni Monaco COST meeting Krakow, 26 may 2010 16/24

 EUV Reflectance measurements

❑ Source: hollow cathode or spectral lamps (40-500 nm)

❑ Monochromator: Johnson Onaka – normal incidence
❑ Detector: Channel Electron Multiplier or photomultiplier
❑ Sample and detector on manual stages
❑ Polarization factor known (from 121.6 to 40 nm)
Gianni Monaco COST meeting Krakow, 26 may 2010 17/24
 EUV Reflectance

Reflectance @10° SiC sample vs Sapphire substrate

0.35

0.3
584 919
0.25 1048
744
0.2 1216
R%

0.15

0.1 sapphire
461
sic sample
0.05
304
0
250 350 450 550 650 750 850 950 1050 1150 1250 1350
wavelength (Å)

Gianni Monaco COST meeting Krakow, 26 may 2010 18/24

 EUV Reflectance /2

0.7 0.7

0.6 sap_1216 SiC_1216 0.6 Sap_1048 SiC_1048

0.5 0.5

Reflectance
Reflectance

0.4 0.4

0.3 0.3

0.2 0.2

0.1 0.1
0 0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
incidence angle (degree) incidence angle (degree)
0.8 0.8
0.7 sap_919 sic_919 0.7 sap_584 sic_584
0.6 0.6

Reflectance
Reflectance

0.5 0.5
0.4 0.4
0.3 0.3
0.2 0.2
0.1 0.1
0 0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
incidence angle (degree) incidence angle (degree)

Gianni Monaco COST meeting Krakow, 26 may 2010 19/24

 Conclusions of the STSM

❑ Hard to find evidences of 3C-Silicon Carbide!

I. The films are crystalline but are simply too thin to be revealed with the utilized
techniques. This could sound strange if we think that we placed the substrates in
the position of the sample n°5 which was demonstrated to have a thickness of 60
nm. Since we have kept the same target-substrate distance, the explanation surely
lies in the laser fluence which is three times higher compared to the other
samples.
II. The samples are not crystalline, films are too thin and we cannot see any film by
the utilized techniques (such as IR which is not sensitive to amorphous structure).
III. Contamination of the surface, due to the residual atmosphere and to the clamp
(made in stainless steel) prevails with respect to deposited films. Hence, it is
difficult to see the IR absorption and the XRD spectra since the crystalline structure
has not been formed, or some other structure have been formed instead
crystalline SiC.
❑ A TEM analysis could probably help to solve the first and the second uncertainties,
while an XPS could be helpful for the third uncertainties. Nevertheless, with the
results we obtain we can exclude the third supposition since the reflectance it is
not affected by the presence of absorbing elements, such as Oxygen, that would
lower the Reflectance yield compared to the substrate.
Gianni Monaco COST meeting Krakow, 26 may 2010 20/24
 Appendix: further deposition@ LUXOR

• Laser: Nd:YAG (λ = 1064 nm)

with variable repetition rate
and 6ns Permanent magnet

• Incidence angle of 45° on

the target
• P ≈ 8.7 x 10-7 mbar 2 1
3
• Magnetic field intensity 5
4
on target: 100 – 200 Gauss
• Variable target-permanent
magnet distance substrates
• Can guest more than one target
• Ceramic heater (up to 1500 °C depending by the vacuum)
• Five samples deposited (different position relative to the
target)
Gianni Monaco COST meeting Krakow, 26 may 2010 21/24
Appendix: further deposition@ LUXOR/2

Si (111) Si(100) Sapphire

Fluence 1.4 J/cm2, T=650°C,
10 Hz or 2 Hz Repetition rate
Gianni Monaco COST meeting Krakow, 26 may 2010 22/24
Appendix: further deposition@ LUXOR/3

Sapphire
SiC_Sap_1_90
SiC_Sap_4_45
3C-SiC (111)

3C-SiC (222)
30 35 40 45 50 55 60 65 70 75 80
Angle (2theta)

Gianni Monaco COST meeting Krakow, 26 may 2010 23/24

 Acknowledgments

❑ Institute of Optoelectronics
Prof Henryk Fiedorowicz , Dr. Waldemar Mróz, Artur
Prokopiuk, Michael L. Korwin-Pawlowski and Sylwia
Burdyńska, BoguslawBudner
❑ LUXOR-INF Laboratory
Prof. Piergiorgio Nicolosi, Dr. Suman Michele, Dr.
Maria G. Pelizzo, Dr. Zuppella Paola
❑ Dr. Garoli Denis and Dr. Natali Marco
for SEM and XRD measurements
❑ COST project
❑ Thank you for your attention!

Gianni Monaco COST meeting Krakow, 26 may 2010 24/24