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RADIATION DEFECTS AND OXIDATION STATE OF nl- IONS IN NON-STOICHIOMETRICAL OXIDES
Nicolay A. Kulagin
Kharkiv National University for Radio Electronics, av. Shakespeare 6-48, Kharkiv 61045, Ukraine. E-mail: [email protected] , kulagin@´kture.kharkov.ua
Szczecin May, 7 2007
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Outline of the talk
- Radiation stimulated by X rays, gamma, electrons and particles charges transfer in oxides: sapphire, garnets, perovskites; - Optical absorption, luminescence, EPR and TSL-TSC spectra of irradiative oxides doped with nd- and nf- ions;- X Ray spectra and oxidation state of component and doped nl- ions; - Ab initio energy calculations for doped and radiation clusters and unit defects;- Electronic state stability of doped nl- ions under radiation of oxides;- Change of oxides surface under plasma treatment: quasi-ordered nano-scale structures;- Shot summary
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Growth and Treatment
The main methods of crystallization of the oxide single crystals
• Czochralsky - Cz; Verneuil - V;
• Method of horizontal and vertical crystallization - DC;
• Stepanov – S, etc.
Mixtures of different quality and different concentration - C of accidental impurities were used for oxides crystals growth:
* super- pure (C <10-5 wt %),
* pure (C <10-3 wt %), and
* standard one ((C <10-2 wt %)
Thermal treatments and co-doping by Ca, Mg
• O2, 1200 <T <1800 K;
• CO2, 1500 <T <1800 K;
• vacuum, 10-5 Torr, 1500 <T <1900 K;
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Pure Sapphire – Al2O3
Optical absorption of sapphire grown by different methods
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TABLE. Spectral parameters of the sapphire grown by different techniques
Sample Abs.edge nm
OpticalBands, nm
AA bands nm
TL, 320-420 nm
TSC peaks T, K
TL bands nm
V 195 206*, 225*,260*, 400* 570
206, 225,280, 475
- 388, 578 690
Vp 142 175, 206,230, 400*
206, 225,280, 475*
4 385, 560507
320, 690690
Vsp 142 185*,206*, 230* No AA 0.1 430, 507*560
420, -690
DC 145 175, 206*235*
206, 230 no TL 398*, 507* -
DCr 142 175, 206,235
206, 230280*, 470*
8 373,506, 565
320, 420690
Czr 143 180*, 206 206, 475 2 430,580
320, 420420, 690
Cr 142 198, 225* No AA no TL 387*, 426*485*
--
Sr 142 175, 206230
206, 230 1 390,418, 430, 506*
420-
Pure Sapphire – Al2O3
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Ruby – Radiation Effect
Optical absorption of ruby: Al2O3:Cr
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Structure and Defects
Simplified garnet structure
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Pure Garnet
• Optical absorption of pure YAG crystals grown by Chochralsky – 1 and HDC – methods
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Optics of Y3Al5O12:Nd:Cr Garnets – Radiation Effect
Optical absorption of YAG before and after irradiation
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TSL – TSC spectra for YAG pure and doped with Cr:Nd
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ESR of Cr+3 ion in Garnet
EPR spectra of Cr*3 ions in YAG crystals
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Optics of GSGG and GSAG Garnets doped with Cr and Ca
OAS of doped garnets before and after thermal treatment
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Optics of YAG:V+3 – Thermal Treatment
OAS spectra of V*3 ions in YAG crystals
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Theoretical Results - Cr+3:[O-2]6 Cluster under Pressure
Table 2. Theoretical values of radial integrals for Cr+3 ions in
Cr+3:[O-2]6 clusters for different R
Integral Free ion / R = 2.1
1.96 1.9 1.8 1.5
Configuration 3d3
F2(3d,3d), cm-1
87080 72010 58644 50932 45863 44795
F4(3d,3d), cm-1 54582 42380 35644 30881 27796 29599
(3d), cm-1 290.9 245.1 220.2 194.8 167.5 74.9
(3d|r|3d ), a.u. 1.093 1.351 1.561 1.721 1.839 2.100
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Theoretical Results - Cr+3:[O-2]6 Cluster, Ruby and YAG
RCr-O(Å)\ Level 2E 2T14T2
2T24T1(t2
2e) 4T1(t2e2)
Theory R = 2.0 Å 14850 15652 16500 22171 24229 37661
1.96 14220 14969 18100 21538 25811 40324
1.9 12500 13113 20500 19392 27659 44176
Ruby
Experiment 14433 15087 18133 21318 24767 39067
Semiempirical 14354 14989 18108 21355 24843 39362
Table1. Dependence of Cr+3 ions energy levels on R Cr-O (cm-1)
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Theoretical Results - Cr+3:[O-2]6
• Table 3. Semiempirical and theoretical data for B, C and Dq for Cr+3 ions in different crystals (cm-1)
DqDqIntegral -Al2O3 Y3Al5O12 Gd3Sc5O12 Gd3Sc2Ga3O12 Cr+3:[O-2]6
B 682 725 740 740 789
C 3120 3373 3578 3578 2829
Dq 1787 1650 1500 1500 1750
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Theoretical Results - 3d2 configuration of Cr+4:[O-2]6
2S+1Γ(t,e) – level Energy, cm-1 2S+1Γ(t,e)- level Energy,cm-1
3T1(t2
2) 0 1T2(t2e) 34909
1E(t22) 15002 3A2(e
2) 38391
1T2(t2
2) 15618 1T1(t2e) 38391
3T2(t2e) 18045 1E(e2) 54429
1A1(t2
2) 30962 1A1(e2) 75683
3T1(t2e) 31939
Table 4. Theoretical level scheme for ion Cr+4 in ruby (Dq = 1990 cm-1, B = 1050 cm-1 and C = 3873 cm-1)
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Optics of Garnets – Cr+4 Energy Levels Schemes
TABLE 10. Energy levels of Cr4+:[O2-]4
cluster
Y3Al5O12 Gd3Sc2Ga3O12
2S+1Γ λtheor, nm λexp, nm λtheor, nm λexp, nm
3A2 - - - -
1E 10950 11000 847 - 3T2 964 964 1052 1052
3T1 640 640 661 600
1A1 627 - 507 504
1T2 517 - 475 504
1T1 453 - 407 410
3T1 410 - 410 410
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Perovskites – ABO3
• LiNbO3:Cr ->
A - Li+, B – Nb+5
• YAlO3:Cr/Nd ->
A – Y+3, B – Al+3
• SrTiO3:V, Mn, Fe, Co, Ni / Pr, Nd, Sm, Tm
A – Sr+2 (RE+2, +3),
B – Ti+4 (Me+2, +3, +4)
• Simplified structure of perovskite
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Perovskite - YAlO3:Cr:Nd
OAS spectra of Cr*3 ions in YAlO3 crystals
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Perovskite SrTiO3 Optical Absorption
Optical absorption of SrTiO3 crystals.
Pure (1) and blue sample (2) – a, crystals doped with RE – b (1 - Sm, 2 – Pr, 3 – Nd, 4 – Tm)
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Dielecrical Properties of SrTiO3
0 50 100 150 200 250 300
0.0015
0.0020
0.0025
0.0030
0.0035
0.0040
0.0045
0.0050
3
2
1
0-1
T[K]
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Dielecrical Properties of SrTiO3
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Structure and Defects in SrTiO3
• Energy zones of a wide – band gap crystal with different transitions and local levels
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X Ray Lines of nlN Ions
X Ray lines: Kα1: 1s1/2 2p3/2 transition
n’l-1nlN- Lα1: 2p3/2 3d5/2 transitionconfigurations
nl- level nlJ- spin-orbit level 3d --------------------- 3d5/2
============= --------------------- 3d3/2
--------------------- 2p3/2
2p =============
--------------------- 2p1/2
1s
============= ============= 1s1/2
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X Ray Microanalysor
N
ln
N
lnx ll EEE ''''
1 Nx
Nxx EEE
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CrKα- Line Valency Shift for Irradiated Ruby and Garnet
%, 100 E
E )C(Cr
theorx
expx4
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Perovskite SrTiO3 X Ray
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Energy of X Ray of RE and AC ions
RE E (K1 ) E(K1) E(L1)
Nd 2+ 37337,290 42250,942 5370,471
Nd 3+ 37336,610 42248,875 5369,708
Nd 4+ 37335,741 42246,471 5368,449
Eu2+ 40071,174 45371,500 5852,357
Eu3+ 40070,420 45369,567 5848,793
Eu4+ 40069,405 45367,192 5847,622
Gd2+ 42921,661 48620,131 6062,622
Gd2+ 42920,521 48618,235 6063,971
Gd2+ 42920,118 48615,998 6060,614
Yb2+ 52156,939 58580,850 7421,563
Yb3+ 52155,897 58578,564 7426,668
Yb4+ 52155,007 58576,031 7429,100
U2+ 95912,345 108809,007 13639,793
U3+ 95912,037 108808,394 13639,528
U4+ 95911,663 108807,659 13639,200
Np2+ 98307,960 111517,588 13970,953
Np3+ 98307,642 111516,963 13970,674
Np4+ 98307,262 111516,221 13970,346
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K1- line L1- line
Ion E0 a -b E0 a -b
Ac 88951.080 0.431 0.070 12671,789 0,424 0.052
Th 91233.519 0.467 0.034 12989,542 0,326 0.032
Pa 93553.072 0.540 0.034 13311,565 0,479 0.030
U 95910.145 0.605 0.033 13637,868 0,539 0.029
Np 98305.122 0.659 0.032 13968,481 0,580 0.028
Pu 100738,542 0,691 0,031 14303,356 0,640 0.027
Am 103210,648 0,724 0,030 14641,226 0,682 0.026
Cm 105721,613 0,767 0,028 14986,249 0,711 0.025
Bk 108272,134 0,826 0,026 15334,323 0,728 0.023
Cf 110862,572 0,882 0,025 15686,806 0,740 0.021
Es 113493,397 0,920 0,024 16043,560 0,784 0.021
Fm 116165,234 0,935 0,023 16405,048 0,790 0.020
Md 118877,847 0,977 0,022 16770,396 0,851 0.020
No 124428,762 1,035 0,021 17140,694 0,875 0.019
320 NcNbNaEEx
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SEM Picture after SrTiO3:Sm Plasma Treatment
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SEM Picture after SrTiO3:Tm Plasma Treatment
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SEM Picture after SrTiO3:Nd Plasma Treatment
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3D- AFM Picture after SrTiO3:Sm Plasma Treatment
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3D-AFM Picture after SrTiO3: Ni Plasma Treatment
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Energy Levels Scheme Parametrization of nl(f)- Ions
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Theoretical Foundations
Free IonsHFP approach
Doped CrystalsHL-SCF for Clusters
),()(),(),()( int RrRERrRrHrH lllfree
)|(),|(),(
),(),(),(
11
22
22211112
221111
GlnYRrlnAPGln
GlnGlnGlnln
iii Niii
Niii
Niii
NNNN A
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Theoretical Foundations – Ions and Hamiltonians
ji
jiji
iji i
iifree )s1(r/1r/Z2/1H
jimn
mjnijimn
nimjni ji
jini srrZH,,,,
int )1(/1/2/1
Ion – nlN: Me – 3dN, RE - 4fN, AC - 5fN => ME The main configurations: nlN and nlNn’l’N’ Cluster: ME+n: [L]k. Ligand – O-2, F-, Cl- etc
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Theoretical Foundations – Energy of Cluster
)EEE(kkEE)]L[:ME(E excZ'
1freekn
,
,
,)(YB)nl()J,SLSL(
)nl,nl(F)LS,l(fE)LSJ|(nlE
i,q,kiikqkq
''
kk
'Nk0
'Nfree
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Theoretical Foundations – Radial Integrals
''1
''21
2
''21
2
,)'|''()|''()|''()|()'',(
,)|''()|()'',(
,)|()|(),(
drdrrlnPrlnPr
rrlnPrnlPlnnlG
drdrrlnPr
rrnlPlnnlF
drdrrnlPr
rrnlPDnlnlF
k
kk
k
kk
k
k
kk
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Theoretical Results - 3d24p configuration of Cr+3 in Cr+3:[O-2]6
Integral Free / R(Å) = 2.1 1.96 1.9 1.8 1.5
Configuration 3d24p
F0(3d,4p), cm-1 91284 65490 69606 71629 74294
F2(3d,4p), cm-1 22295 9455 12485 14705 21010
G1(3d,4p), cm-1 7778 2513 4924 7046 14430
G3(3d,4p),cm-1 7193 2001 3838 5471 11135
(3d), cm-1 331.9 322.1 303.8 288.7 238.1
(4p), cm-1 642.0 97.6 129.6 153.3 198.8
(3d|r|3d) a.u. 1.018 1.064 1.148 1.219 1.474
(4p|r|4p) a.u. 2.734 3.538 3.314 3.210 3.045
(4p|r|4p) a.u. 2.734 3.538 3.314 3.210 3.045
ΔE(3d3–3d24p), eV 17.8 21.8 16.1 9.9 11.6
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42
Self Consistent Field Equations for nl-Ions in Solids
nnlnnl rlnPrnlXrnlP
r
llrnlY
rdr
d
'
' ),|()|()|()1(
)|(2 ''
2'
2
2
'l'n,1k,k
'1kk
1kk'll
''''1kk
1kk'll
)]r|'ln,nl(Yb)r|ln,ln(Ya[2/r)r|nl(Y
''
1
1
1
1'
,,
'''' )|(])|,([)|(lnkk
kkllkk
kk
llrlnPrrlnnlYrnlX l
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43
''''''121
'' 21
1)|()|(),()|,( drrrlnPrnlP
Rr
kkkrlnnlYk
k
k
kk
)||)(|(
*)|()()||(
'2
'11221
'12
'21
'''2
;1
11221
'22'
22
'11
'22
'22
'11
1'
mmrmmmm
mmOOvSSAmmrmmOOvam m
mm
mm
mm
mmmmmm
kk
ll
m
mm
mm
mm
kk
llmmrmmmmOOSSAvb )||)(|()( ''
11
12'21
'21
'' '
22
11'11
1'
Self-Consistent Potential for nl-Ions in Solids
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44
m
mmmm
kk
llmmrmmOOSSAv ,)||()( '
1'2
11221
'''22
'11
1'
mZ
mm
mmmmmmkkll
mrmmmOOmmOR
vZ )'||)(|()[|(
'2
11212
'11
22
'11'11
;11'22
'
Self Consistent Field Equations for nl-Ions in Solids
Boundary conditions: P(nl|r)| r →∞ → 0 - for unit center or impurity ionWigner-Zeits conditions: ∂P(nl|r)/∂r | r→R → 0 for cluster and crystal
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7
SCF Potential and Radial Wave Functions for nf- Ions
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46
Short Summary
Ab initio study of the electronic structure of ME+n:[L]k-clusters and energy of X-ray lines is a powerful and effective method of investigation of foundations of doped materials. This method and optical spectra of nl- ions in oxides - on the one hand and study of the influence of irradiation or thermal treatment to crystals doped with d- or/and f ions on the other hand allow to explain of the nature of radiation defects into doped oxides and draw the simple conclusion that stability of the oxidation state of ions in crystals is determined relation of energy of ionization of ME+n ion – I Me
and Madelung's constant αM = - ΣZi/ri for the cation site.
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47
Concluding Remarks
• Crystals growth method determines the main defects of the oxides through crystals stoichiometry
• Crystals stoichiometry determines electronic state and ions valency and properties of the oxide single crystals, too
• Relation A/O changes:- for simple oxides up 0.95 to 0.99- for garnet crystals A/B changes up 0.9 to 0.98- for perovskites - 0.8 – 0.98 (A1-xB1-yO3-z)
• Value of A/O and A/B is determined by possibility of the regular nd and nf ions to change their valency. We can used non-stoichiometry oxides for expansion of area of employment of the pure and doped single crystals