Formation of transient layers after ion irradiation of TiO2/SiO2/Si...
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Formation of transient layers after ion irradiation of TiO 2 /SiO 2 /Si multilayer system Kulik M. 1,2 Asgerov E.B. 1,3 , Madadzada A.I. 1,3 , Kołodynska D. 4 and Pyszniak K. 2 1) Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna, Russia 2) Institure of Physics, Maria Curie-Sklodowska University, Lublin, Poland 3) Department of Neutron Physics, National Nuclear Research Centre JSC, Baku, Azerbaijan 4) Chemistry Department Maria Curie-Sklodowska University, Lublin, Poland
Transcript of Formation of transient layers after ion irradiation of TiO2/SiO2/Si...
Formation of transient layers after ion irradiation of TiO2/SiO2/Si
multilayer system
Kulik M. 1,2 Asgerov E.B. 1,3, Madadzada A.I. 1,3, Kołodynska D. 4 and Pyszniak K. 2
1) Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna, Russia 2) Institure of Physics, Maria Curie-Sklodowska University, Lublin, Poland 3) Department of Neutron Physics, National Nuclear Research Centre JSC, Baku, Azerbaijan 4) Chemistry Department Maria Curie-Sklodowska University, Lublin, Poland
Outline
1. few remarks about TiO2/SiO2/Si 2. Ion implantation Ne, Ar, Kr, Xe ions 3. The results of research and discussion 4. summary
Titanium dioxide, also known as titanium(IV) oxide or titania, is the naturally occurring oxide of titanium, chemical formula TiO2. Generally, it is sourced from ilmenite, rutile and anatase. It has a wide range of applications, including paint, sunscreen and food coloring.
few remarks about TiO2
Titanium dioxide occurs in nature as the well-known minerals rutile anatase Crystal system ------ Tetragonal brookite
Some information about the TiO2 and its application Titanium dioxide (TiO2) is the most widely used white pigment, for example in paints. It has high brightness and a very high refractive index. The light passes through the crystal slowly and its path is substantially altered compared to air. If you have many small particles orientated in different directions, a high refractive index will lead to the scattering of light as not much light passes through. In lenses, high refractive index means high clarity and high polarising power. Titanium dioxide has a higher refractive index than diamond and there are only a few other substances that have a higher refractive index. Almost every sunscreen contains titanium dioxide. It is a physical blocker for UVA (ultraviolet light with wavelength of 315–400 nm) and UVB (ultraviolet light with wavelength of 280–315 nm) radiation. It is chemically stable and will not become decolourised under UV light.
TiO2 multilayer systems and the application of research results
Some information about previous studies Ion implantation
1) M. Kulik, A.P. Kobzev, D. Jaworska, J. Zuk, J. Filiks, Vacuum, 81 1124 (2007). 2)F.F. Komarov, L. Vlasukova, O. Milchanin, A. Mudryi, J. Zuk, K. Pyszniak, M. Kulik, Acta Phys. Pol. A 120, 204 (2011). 3) M. Kulik, D. Kołodyńska, J. Zuk, F.F. Komarov and J. Filiks, Acta Phys. Pol. A 123, 943 (2013).
*M. Kulik, J. Zuk, A. Drozdziel, et al: Materials Science and Engineering B-Advanced Functional Solid-State Materials, 176, 340 (2011). *T. Lohner, P. Petrik, O. Polga, N. Q. Khánh, M. Fried and J. Gyulai, Vacuum 50, 487 (1998). *M. Erman, J.B. Theeten, P. CHambo, S.M. Kelso and D.E. Aspnes, J. Appl. Phys.56, 2664 (1984) *MOo Danq, HE Xingfe, Chinese Phys. Lett., 3, 229 (1986), •J.R.Adams and N.M.Bashara, Surf.Sci.49 441 (1975), • M.Erman and J.B.Theeten, Surface and Interface Analysis 4. 98 (1982).
--Dadong Shao, Jiaxing Li ,Xiaoli Tan,Zhongshi Yang,Kenji Okuno, , Yasuhisa Oya Jouranl Of Nuclear Materials 457, 118 (2015). M. J. Vasile, A. B. Emerson, F. A. Baiocchi „The characterization of titanium nitride by x-ray photoelectron spectroscopy and Rutherford backscattering” J. Vac. Sci. Technol. A 8 (1990) 99. M. Kulik, S.O. Said, J. Liśkiewicz, Nucleonika 44, 167 (1999). D. Pjević, T. Marinković, J. Savić, N. Bundaleski, M. Obradović, M. Milosavljević, M. Kulik, Thin Solid Films 591, 224 (2015). M. Kulik, D. Kołodyńska, A.P. Kobzev, F.F. Komarov, Z. Hubicki, K. Pyszniak Thin Solid Films 616, 55 (2016).
Logical layout for an XPS Instrument
ellipsometer
RBS method and JINR in Dubna
Basic Physical Processes
Conservation of energy and conservation of momentum parallel and perpendicular to the direction of incidence are expressed by the equations
Eliminating f first and then v2, one finds
For M1 < M2 the plus sign holds. We now define the ratio of the projectile energy after the elastic collision to that before the collision as the kinematic factor K
The disorder of multilayer structure is created during the process of implantation [1,2]. The changes in the atomic composition refraction and extinction indices of implanted layers [3,4].
[1] Gyulai J, Paszti F, Lohner T. and Battistig G, Ion Beam Analysis, Proceedings of the Eleventh International Conference on Ion Beam Analysis, Balatonfured, Hungary, 1993;July:5. [2] Kulik M, Rzodkiewicz W. and Pyszniak K, Physica Status Solid C, 2011;8:1315. [3] Kulik M, Komarov F.F. and Maczka D, Vacuum, 2001; 63:755.
[4] Kulik M, Zuk J, Drozdziel A, Pyszniak K, Komarov F.F. and Rzadkiewicz W, Material Science and Enegineering B, 2011;176:340.
Ion implantation MOTIVATION
The information about the preparation of the samples and methods of their research
In this study we investigated the changes in depth distributions of atomic compositions in multilayer structures TiO2/SiO2/Si after ion implantation. Depth profiles of elements in the samples were analyzed by the Rutherford Backscattering Spectrometry (RBS) method. It was found that transition layer existed between the TiO2 and SiO2 layers. The thickness of transition layers were increased with the growing of energy as well as the atomic mass of the implanted ions. The chemical compositions of the near-surface layers was investigated using the X-ray Photoelectron Spectroscopy (XPS) method. It was observed that the concentration of Ti, TiO, Ti2O3 was increased while the concentration of TiO2 was decreased as results of displacement of atoms during implantation process.
The results of research and discussion
The samples have been irradiated with the ions at the same fluency 1*1016 (ions/cm2). The ion implantation process was performed on the UNIMAS ion implanter of the Maria Curie-Skłodowska University [1]. In additional, the chemical composition of the near surface layers was have been investigated using with the X-ray photoelectron spectroscopy (XPS) method [5]. The XPS spectra for all samples were registered in the energy ranges 450 - 462 eV. The energy range were referred to the binding energy of Ti 2p electrons. [1] M. Turek, S. Prucnal, A. Drozdziel, K. Pyszniak, Versatile plasma ion source with an internal evaporator, Nucl. Instrum. Methods Phys. Res. B 269 (2011) 700.
The results of research and discussion
thickness of transition layers between TiO2 and SiO2 ------ 15-10 15 -- 20-10 15 cm-2 as well as SiO2 and TiO2 ------ 10x10 15 -- 25x10 15 cm-2
-Atomic depth distribution of the elements in the samples before and after irradiation were investigated using the RBS method [2]. The RBS experiments were carried out on the EG-5 accelerator at the Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research [3]. The accelerator produced a monoenergetic beam of He+ ion at energy 1.5 MeV. The beam was directed to the sample under the incident angle 𝛼𝛼 = 600 respect to the normal of the sample surface. A semiconductor which has energy resolution 15 keV was located at the scattering angle 𝜃𝜃 = 1700 in order to record the backscattered ions from the near surface layers of samples. The element composition, their content and depth distribution were calculation using SIMNRA code [4].
[2]W.K. Chu, J.W. Mayer, M.A. Nicolet, Backscattering Spectrometry, Academic Press, New York San Francisco London, 1978. [3] Tran Van Phuc, M. Kulik, A. P. Kobzev, Le Hong Khiem, Study of mos structures using nuclear analytical methods, Communications in Physics, Vol. 27, No. 4 (2017), pp. 279- 289. [4] W. Olovsson, T. Marten, E. Holmatstron, B. Johansson, I. Abrikosov, First principle calculations of core-level binding energy and auger kinetic energy shifts in metallic solids, J. Electron Spectrosc. Relat. Phenom. 178 (2010) 88. [5] M. Mayer, SIMNRA User's Guide, Report IPP 9/113, Max-Planck-Institut für Plasmaphysik, Garching, Germany, 1997.
The results of research and discussion
300 400 500 600 700 800 900 10000
10000
20000
Si in SiO2 the fir st layer
Si sample substrate
TiYie
ld [c
ount
s]
channel
total O, Si Ti, Xe experimental
XeEXe+=100 keV
O
EHe+ = 1500 keV
α= 55o, θ=170o
300 600 9000
10000
20000
the bands SiO2 and TiO2 do not overlap
Yield
[cou
nts]
channel
TiO2- 5 laySiO2- 4 laySisub.
simulated O Si Ti experimental
α=55o, θ=170οEHe+= 1500 keV
first and second "band of scattered α particles " on nuclei of Ti in TiO2 first, second maximum - after implantation
300 600 9000
10000
20000
30000
Ti
EHe+ = 1500 keV
α= 60o, θ=170o
Yiel
d [c
ount
]
channel
simulated O Si Ti Xe experimental
O
The results of research and discussion
600 650 7000
5000
10000
α=60o, θ=170ο
EHe+= 1500 keV
TiO2- 5 laySiO2- 4 laySisub.
simulated O Si Ti exper imental
Yie
ld [c
ount
s]
channel
600 650 700 7500
5000
10000
the bands SiO2 and TiO2 do not over lap
Yie
ld [c
ount
s]
channel
TiO2- 5 laySiO2- 4 laySisub.
simulated O Si Ti exper imental
α=55o, θ=170ο
EHe+= 1500 keV
600 6500
5000
10000
the beginning of the overlap process
α=65o, θ=170ο
EHe+= 1500 keV
TiO2- 5 laySiO2- 4 laySisub.
simulated O Si Ti exper imental
Yie
ld [c
ount
s]
channel
600 6500
5000
10000
process of covering the bands SiO2 and TiO2 began
α=70o, θ=170ο
EHe+= 1500 keV
TiO2- 5 laySiO2- 4 laySisub.
simulated O Si Ti exper imental
Yie
ld [c
ount
s]
channel
The results of research and discussion
TiO2 thickness of about 40.0 nm ±2 .0nm – form SE
SiO2 thickness of about 34 nm ± 2.0 nm --- from SE
400 600 800 10000
10000
20000
Yield
[cou
nt]
channel
simulated O Si Ti
600 900 1200
third layer --- SiO2
Si substrate
Ti
Eα=1500 keVα = 55o, θ = 170o
exp.
Energy [keV]
O
TiO2-five layersSiO2-five layers
dashed line - after implantation Xe + E = 100 keV
0 50 1000
1x1021
2x1021
3x1021
SRIM
atom
ic d
ensi
ty X
e [1
/cm
3 ]
Depth [nm]
TiO2
RBS
TiO2
SiO2
atomic density TiO2 --- 9.564x1022 atoms/cm3
SiO2 --- 6.975x1022 atoms/cm3
the width of the transfer layer
solid lines---borders
The results of research and discussion
Xe Value Standard Error Intercept 0.18728 0.02479 B1 -0.00251 3.04809E-4 B2 1.24846E-5 8.6386E-7
Kr Value Standard Error Intercept 0.16054 0.08952 B1 -0.00221 0.0011 B2 1.03655E-5 3.11901E-6
Ar Value Standard Error Intercept 0.13162 0.03793 B1 -0.00181 4.6635E-4 B2 7.87422E-6 1.3217E-6
Ne Value Standard Error Intercept 0.07621 0.03804 B1 -0.001 4.67662E-4 B2 4.04458E-6 1.3254E-6
100 150 200 250
-0.2
0.0
0.2
0.4
Re
lative
chan
ging o
f thi
ckne
ss [a
.u]
Energy [keV]
TiO2
Transition layer SiO2
100 150 200 250-0.5
0.0
0.5
1.0
1.5
2.0
2.5
Rel
ativ
e ch
angi
ng o
f thi
ckne
ss [a
.u]
Energy [KeV]
TiO2
Transition layer SiO2
The relative changing thickness of the TiO2, transition and SiO2 layers of two samples in group 2 that implanted with Ne+ (a) and Xe+ (b) ions. The thickness of the all layers were obtained on the basics of the RBS measurement.
a
b
ellipsometry
• Polarized light is reflected at an oblique angle to a surface
• The change to or from a generally elliptical polarization is measured.
• From these measurements, the complex index of refraction and/or the thickness of the material can be obtained.
SE --- method
maybe an interesting mention
upset beetles
The results of research and discussion --SE
452 454 456 458 460 462 464
100
200
300
Inte
nsity
[a.u
.]
Binding energy [eV]
sample unimpl TiO2
Total norma Ti 2p
Ti TiO Ti2O3
TiO2
GB Measured
Results SE
Wavelength (nm)200 400 600 800 1000
∆ in
deg
rees
0
30
60
90
120
150
180
TiO2 --70 degTiO2 -fi 69TiO2 -fi 68TiO2 fi 67TiO2 fi 66TiO2 fi 65
Results SE
Wavelength (nm)200 400 600 800 1000
Ψ in
deg
rees
0
3
6
9
12
15
18 TiO2 --70 degTiO2 -fi 69TiO2 -fi 68TiO2 fi 67TiO2 fi 66TiO2 fi 65
SiO2 =0.00
Wavelength (nm)200 400 600 800 1000
Ψ in
deg
rees
20.4
20.7
21.0
21.3
21.6
21.9
SiO2 fi 70
450 455 460
100
150
200
250
300
350
100-keV Ne+In
tens
ity [c
onun
ts]
Binding energy [eV]
Total Ti TiO Ti2O3 TiO2 Background Measured
452 456 460 464
100
150
200
250
300 150-keV Ne+
Inte
nsity
[con
unts]
Binding energy [eV]
Total Ti TiO Ti2O3
TiO2
Background Measured
452 456 460 464
100
150
200
250
300
350Virgin sample
Inte
nsity
[con
unts]
Binding energy [eV]
Total Ti TiO Ti2O3 TiO2 Background Measured
448 452 456 460 464
100
150
200
250
Inte
nsity
[con
unts]
Binding energy [eV]
Total Ti TiO Ti2O3 TiO2 Background Measured
200-keV Ne+
452 456 460 464
100
150
200
Inte
nsity
[con
unts]
Binding energy [eV]
Total Ti TiO Ti2O3 TiO2 Background Measured
250-keV Ne+
100 150 200 250
0
5
10
15
20
25R
elat
ive
conc
entr
atio
n [a
.u]
Energy [keV]
Ti TiO Ti2O3
100 150 200 250-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
Rel
ativ
e co
ncen
trat
ion
[a.u
]
Energy [keV]
TiO2
The relative changing concentration of compounds in the transient layers as a
function of energy of Ne+ ions.
Summary and conclusions
the thickness of the transition layer increases
the mass and energy of implanted ions corresponds to the increase
the refractive index and extinction coefficient of the transition layer increase --- the result of implantation
increase in reflectance of the multilayer structure, the reason for ion implantation, and displacement of atoms
Thank you for your attention
