ion-beam induced surface chemical effects metal oxides & nitrides 1989-2001
DESCRIPTION
Ion-beam Induced Surface Chemical Effects Metal Oxides & Nitrides 1989-2001. Imre Bertóti Institute of Materials and Environmental Chemistry Chemical Research Center, Hungarian Academy of Sciences [email protected] 2003. september. MTA KK AKI – Nanoréteg Kémiai Laboratórium Tóth András * - PowerPoint PPT PresentationTRANSCRIPT
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Ion-beam Induced Surface Chemical Effects
Metal Oxides & Nitrides 1989-2001
Imre Bertóti Institute of Materials and Environmental Chemistry
Chemical Research Center, Hungarian Academy of [email protected]
2003. september
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RÉSZTVEVŐK - EGYÜTTMŰKÖDŐK
MTA KK AKI – Nanoréteg Kémiai Laboratórium
• Tóth András*• Mohai Miklós Gulyás László techn.• Ujvári Tamás• Kereszturi Klára
Hazai partnereink: Külföldi együttműködők:
• Gyulai József T. Bell Prof. † • Menyhárd Miklós R. Kelly• Radnóczi György G. Marletta Prof. • Sulyok Attila J. Sullivan Prof.• Sáfrán György• Geszti Olga• Szedlacsek Katalin• Ferenc Kárpát• Szörényi Tamás >65 közlemény• Sokan Mások ... >300 hivatkozás
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• 1. Tárgya és eszköze a tudományos kutatásnak
• 1.1. A kutatás tárgya• Porlasztás, nem-egyensúlyi rendszerek • Ionsugarak okozta kémiai változások• 1.2. A kutatás eszköze• Szekunder-ion tömegspektroszkópia (SIMS)• Ion-porlasztásos mélységi analizis (XPS, AES, SNMS)• Ion-reflexiós felületanalizis (ISS)• 2. Eszköze technológiai feladatok
megodásának• 2.1. Ion-porlasztásos rétegnövesztés• Mikroelektronika, Napelemek, Optika, Tribológia• 2.2. Ionimplantáció• Mikroelektronika, Kopásállóság, Korrózióállóság • 2.3. Ionsugaras felületkezelés• Elektromos tulajdonságok, Adhézió, Nedvesedés
Gyorsított ionok kölcsönhatása szilárdtestekkel
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MaterialsAl2O3 single crystal (0112) B2O3 fused sheet
TiO2 single crystal (100) SiO2 s. cryst., glass
ZrO2 single crystal (100) GeO2 pelleted powder
V2O5 single crystal (010) Nb2O5 pelleted powder
Cr-O-Si cermet film, Si-O-Si-org. polymer
TiN, ZrN, CrN single/poly cryst. films
Ion BombardmentKratos MacroBeam ion gun1-5 keV Ar, He, N2, O2, N2O, H2
typical current density: ~10-6 A/cm2
fluence for steady state: ~1017 ions/cm2
XPS AnalysisKratos XSAM 800 spectrometerMg K radiation (1253.6 eV)Kratos Vision and XPS MultiQuant software
Experimental
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Primary ion
Secondary ions/neutrals
0
5
5D
ep
th
(Å)
-Surface
-Contamination
Ion
bombardment:
Ar+, He+, N2+, O2
+, N2O+
Ep = 1.0 - 5 keV
Id = 1 - 10 μA/cm2
Collision cascade (˜10-16 s)
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B.E.
I
Ion gun
Electron energy analyzer
X-ray gun
UHV system
Sample lock
Data acquisition and processing
Electron detector
X-ray Photoelectr
on Spectromet
er
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TiO2 single crystal Ar+-O2+-N2
+
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V2O5 single crystal Ar+-N2+
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Nb2O5 bombarded by Ar+
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0.0
0.5
1.0
1.5
2.0
2.5
0 20 40 60 80
Ion bombardment time (min)
Ato
mic
rat
ioO Si N O+N
SiO2 (glass) Ar+-N2+-Ar+
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0
0.5
1
1.5
2
2.5
3
3.5
0 20 40 60 80 100
Ion Bombadrment Time (min)
Ato
mic
Ra
tio
O
N
B
N+O
B2O3 Ar+-N2+-Ar+
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0
0.5
1
1.5
2
2.5
0 20 40 60 80 100 120
Ion Bombadrment Time (min)
Ato
mic
Ra
tio
O
Ti
N
N+O
TiO2 single cryst. Ar+-O2+-N2
+-O2+
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N1s peak shape recorded
on different oxides after N2
+ bombardment
(1989-90)
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410 405 400 395
N2
+ 5.0 KeV
N2
+ 3.5 KeV
N2
+ 2.0 KeV
N2
+ 1.0 KeV
N2
+ 0.5 KeV
403.4 eV 396.35 eV
N1sIn
tensity (
a.u
.)
85 80 75 70 65
N2
+ 5.0 KeV
N2
+ 3.5 KeV
N2
+ 2.0 KeV
N2
+ 1.0 KeV
N2
+ 0.5 KeV
original
Al2p
Inte
nsity (
a.u
.)
Binding Energy (eV)
545 540 535 530 525
N2
+ 5.0 KeV
N2
+ 3.5 KeV
N2
+ 2.0 KeV
N2
+ 1.0 KeV
N2
+ 0.5 KeV
original
O1s
Inte
nsity (
a.u
.)
Al2O3 single crystal bombarded by N2
+
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0 1 2 3 4 50,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1,1
1,2
1,3
1,4
1,5
1,6
1,7
Inte
nsi
ty R
atio
(XP
S)
ion energy (keV)
O/Al N/Al
Al2O3 single crystal bombarded by N2
+
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540 535 530 525 520
0
10000
20000
30000
40000
50000
Energy reference: O1s at 531.0Normalizado al area del Al2p
O1s sph49, O2+ 2 kV 45 min
sph50, N2+ 0.5 kV 30 min
sph51, N2+ 1 kV 30 min
sph52, N2+ 2 kV 30 min
sph54, N2+ 3.5 kV 30 min
sph55, N2+ 5 kV 30 min
Inte
nsity
(a.
u.)
Binding Energy (eV)
Al2O3 single crystal bombarded by N2
+
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85 80 75 70 65
0
2000
4000
6000
8000
Energy reference: O1s at 531.0
Normalizado al area del Al2p
Al2p sph49, O2+ 2 kV 45 min
sph50, N2+ 0.5 kV 30 min
sph51, N
Inte
nsity
(a.
u.)
Binding Energy (eV)
Al2O3 single crystal bombarded by N2
+
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415 410 405 400 395 390 385
2000
3000
4000
5000
6000
7000
8000
9000
10000
402.9 eV 395.85 eV
Energy reference: O1s at 531.0
Normalizado al area del Al2poriginal treatment: O2
+ 2 kV, 45 min
N1s sph50,N2
+ 0.5 kV, 30 min sph51,N2
+ 1 kV, 30 min sph52,N2
+ 2 kV, 30 min sph54,N2
+ 3.5 kV, 30 min sph55,N2
+ 5 kV, 30 min
Inte
nsity
(a.
u.)
Binding Energy (eV)
Al2O3 single crystal bombarded by N2
+
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0 100 200 300 400 500 600 7000,2
0,4
1,2
1,4
1,6
Heating under vacuum Temperature (ºC)
O/Al N/Al
Inte
nsity
Rat
Al2O3 single crystal
Heat treatmentafter 5 keV N2
+
bombardment
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410 405 400 395 390
Vacuum at 650ºC
Vacuum at 550ºC
Vacuum at 450ºC
N2
+ 5 kV
Binding Energy (eV)
N1s
Al2O3 single crystal heat treated after N2
+
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TRIM calculation of the ranges and energy deposition parameters at N bombardment of Al2O3
*Taken as a sum of the mean projected range and the longitudinal straggling
r{O2-} = 1.32 Å - 2/3 octahedral sites occupied by Al, 1/3 is empty
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Kérdések• Mitől függ a redukció mértéke Ar+ esetén
• Miért nagyobb az oxigén-hiány N2+ esetén
• Miért alakul ki 1:1 arányu N – O helyettesítés
SiO2 Si—O—Si
Si
Si3N4 Si—N—Si
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O loss at N2+ bombardment
0
10
20
30
40
50
60
0.00 0.50 1.00 1.50 2.00 2.50ΔHoxid-ΔHnitrid eV
O l
os
s %
Loss of oxygen in % of stoichiometric state
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Cr-Si-O thin film Ar+-He+-Ar+-N2+ bombardment
Cr:Si:O=0.9:1:1.1 (RBS) Heat treated at 400 0C
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Si-O compounds bombarded by Ar+
SiO2
SiO1.3
Cr-O-SiSi2p
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Si4+
Si3+
Si1+
Si0
SiO1.3
Si2+
Cr-O-Si
Si-O compounds bombarded by Ar+
(CrOSi) → SiOx + CrSiy
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PVTMS
PMSSO
Auger parameter plot of Si compounds
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0
1
2
3
4
0 5 10 15 20
Fluence (x1016 ion/cm2)
Ato
mic
ra
tio
O/Si
Cr/Si
1
2
34
56
7
8
He+ He+Ar+ Ar+
Cr-O-Si cermet layer bombarded by He+ and Ar+
Cr - O - Si =0.9 : 1.1 : 1
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The maximum energy transferred from the projectile to the Cr:O:Si target
Etmax / Ep = 4 Mp Mt / (Mp+Mt)2
─────────────────────────────────────
Ion O Cr Si────────────────────────────────
─────
He+ 0.64 0.26 0.44Ar+ 0.82 0.98 0.97
─────────────────────────────────────
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Results of TRIM calculation and average energy-deposition to
Cr:Si:O=1:1:1
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Konkluziók Ar+ ionbombázás hatására az oxigén bizonyos hányada preferáltan távozik
minden (vizsgált) oxidból. A metastabilis oxigén-hiányos állapot kb. 1017 ions/cm2 dózisnál alakul ki és nem csökken tovább a dózis növelésével. O2
+ bombázással az eredeti O/M arány megközelítőleg visszaállítható.
N2+ bombázás hatására az O/M arány tovább csökkethető és nitrogén építhető
be, a megfelelő nitridekre jellemző N-M kötések kialakulásával, annak ellenére, hogy az oxidok TD stabilitása a nitridekénél nagyobb.
Ar+ ionbombázás hatására létrejött O/M arány megegyezik a N2+ bombázás
hatására kialakuló O+N/M aránnyal.
Nitrid típusu nitrogén beépülése az oxid rácsba csak ‘további’ oxigén eltávolításakor lehetséges (második oxigén vakancia helyére). Minnél kevésbé gátolt termodinamikailag az oxid-nitrid átalakulás (ΔHoxid-ΔHnitrid), annál nagyobb a beépülő nitrogén mennyisége.
A relaxáció folyamatának kémiai meghatározottságát a Cr-Si-O esetében a N2
+ bombázáskor is észleltük, amikor kimutattuk, hogy az Ar+ ionokkal keltett Cr-Cr, Si-Si és Cr-Si kötéseknél stabilisabb Cr-N és Si-N kötések alakulnak ki.
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Ion bombardment of metal and carbon nitrides
TiN, ZrN, CrN, CNx
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TiN single cryst.film Ar+ and N2+ bombardment
Ti2p
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Ion bombardment of titanium nitride
N1s
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Ar+
N2+
Difference
5.8 eV
TiN-1
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TiN-1
Ar+ N2+
Difference
Subsequent Ar+ and N2+ bombardment
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ZrN bombarded by Ar+-N2+- Ar+
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ZrN
Difference
Ar+
N2+
Effect of subsequent Ar+ and N2+
bombardment
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N1s line-shape of various nitrides
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Conclusions
XPS can be applied as a simple tool for complex characterization of nitride coatings
In addition to determination of composition, chemical state identification is straightforward (CrN, Cr2N)
Minor compositional and chemical state changes can be detected and unambiguously interpreted also for nano- and amorphous phases
Data obtained on Ti N1+x and ZrN1+x coatings, besides of supporting earlier results, evidencing the existence of new compounds (Ti3N4, Zr3N4) with ionic Ti-N and Zr-N bonds
Delineation of stoichiometry changes may help to develop optimum deposition conditions of coatings with pre-determined composition and structure