Ion implantation doping of perovskites and

related oxides
Ulrich Wahl
Instituto Tecnológico e Nuclear (ITN), Sacavém, Portugal

Collaborators:
João Guilherme Correia (Senior Res., ITN & CERN)
Eduardo Alves (Senior Res., ITN)
Ana Claudia Marques (PhD student, U Lisbon & CERN)
Carlos Pedro Marques (PhD student, U Lisbon)
Karl Johnston (Post-Doc, U Saarbrücken & CERN)
João Pedro Araújo (Prof., U Porto)
Lino Pereira (PhD student, U Porto)
 Outline
• Motivation for implantation studies in perovskites
• Objectives and work plan
• Implantation damage annealing in SrTiO3:
– RBS/C, 89Sr emission channeling, PL
• Fe in SrTiO3:
– emission channeling lattice location,
– magnetic moments (SQUID)
• 67Cu and 111Ag emission channeling in SrTiO3
• Rare earth 169Yb in SrTiO3
• Conclusions
• Outlook
 What are perovskites?

Perovskites are metal oxides of the form ABO3

A forms a simple cubic lattice
B forms a simple cubic lattice
A and B together form a bcc lattice
O occupies the faces of the cube

Best studied
perovskite: SrTiO3

Perovskites are ionic compounds:e.g. Sr2+Ti4+O23

 Perovskites and doping
• Perovskites (SrTiO3, CaTiO3, BaTiO3, KTaO3, ...) are
multifunctional materials...

• ...whose electrical, magnetic and optical properties can

be drastically changed by doping

• Many possible applications of perovskites rely on doping

these materials.
 SrTiO3: great variety of possible dopants

• Possible electrical dopants But little is known about ion

implantation doping:
• Some magnetic dopants
lattice sites ?
• Some optical dopants damage annealing ?
Motivation: ion implantation in perovskites

Amorphization threshold temperature [K]

Trecrystallization
 In short:
• perovskites are hard to amorphize and...
• ...recrystallize at moderate temperatures
 should be attractive systems for ion
implantation
 Major objectives of this project:
• investigate basic possibilities for ion implantation doping
of perovskite oxides and related materials in order to
modify their optical, magnetic and electrical properties
• implantation of magnetic impurities such as Fe or Mn,
optically active dopants such as rare earth elements, and
prospective electrically active donor and acceptor
impurities
• study lattice location of impurities and annealing of
implantation damage using nuclear techniques
• complementary characterization of optical, magnetic and
electrical properties for certain implanted impurities
 Secondary objectives:
• promoting the use of nuclear techniques in the production
and characterization of novel materials in the
technologically relevant fields of microelectronics,
optoelectronics and spintronics
• transfer of know-how in the application of nuclear
techniques to the other participants of the Coordinated
Research Project
• training and formation of PhD and undergraduate students
on a national level in materials science and in the
application of nuclear techniques
 Work plan:
• Year 1 (2005-06): lattice location and damage
annealing studies in SrTiO3, first measurements of
optical and magnetic properties
• Year 2 (2006-07): lattice location and damage
annealing studies extended to other perovskites,
e.g. KTaO3, measurements of optical and magnetic
properties under optimized conditions (dose,
annealing…)
• Year 3 (2007-08): set priorities for the study of
those systems where, according to outcome of
research in years 1+2, best results were obtained
 Foreseen methods of study
• stable and radioactive ion implantation

• nuclear methods using radioactive isotopes

- Emission Channeling (EC) lattice location
- Perturbed Angular Correlation (PAC)
- Photoluminescence (PL)

• Rutherford Backscattering / Channeling (RBS/C)

• conventional Photoluminescence (PL)
• macroscopic magnetic moments by means of SQUID

...work in progress, presentation includes several

experiments that are not yet fully analyzed!
 Annealing of radiation damage: RBS/C
1.00
<100> 51015 cm2 Fe <100> 11015 cm2 Fe
0.95
<110> 51015 cm2 Fe <110> 11015 cm2 Fe
0.90 <111> 51015 cm2 Fe <111> 11015 cm2 Fe

<100> virgin crystal

RBS minimum yield min

0.85
<110> virgin crystal
<111> virgin crystal
0.80

0.75

0.20

0.15

0.10

0.05

0.00
0 200 400 600 800 1000 1200
annealing temperature TA [°C]

• SrTiO3 implanted with 56Fe at doses of 151015 cm2

• 2 MeV 4He+ RBS/C minimum yield min measured as function of TA
 only for TA>1000°C remaining damage reaches values similar to a virgin
crystal
 Annealing of radiation damage: 89Sr emission channeling
 analysis of experiment still in progress! <211> following TA=1000°C
Conversion electron emission channeling with 30 mm x 30 mm Si pad4 detector:

1.7 "on-line" display: template C:\ORIGIN\PADSPEC4.OTP read with script file C:\ORIGIN\CHANRED4.SCR


2 1 0 -1 -2

+ M2:- M2:

- z:  

<100> -10 -10

1.6 max ~ substitutional fraction

cnterclwclockw

6.6E3 -- 7E3
<111>
max of electron channeling

-5 -5

rel. Z-coordinate [mm]

6.2E3 -- 6.6E3

<110>
5.8E3 -- 6.2E3

1.5 0 0 5.4E3 -- 5.8E3

<211> 5E3 -- 5.4E3

4.6E3 -- 5E3
5 5

1.4 <411> 4.2E3 -- 4.6E3

counts raw data
3.8E3 -- 4.2E3
10 10 the plot shows the crystal as

it is viewn from the detector

+ z:
1.3
 U. Wahl, ITN

 2 1 0 -1 -2
+ M1:  rel. M1-angle [deg] - M1: 

1.2 SSr STi

1.1

1.0
0 100 200 300 400 500 600 700 800 900 1000 1100
annealing temperature TA [°C]

 as was expected, 89Sr (60 keV, 81014 cm2) occupies mainly Sr sites
 broad damage recovery stage 2001000°C
 annealing probably not yet finished at 1000°C
 information on rms displacement of Sr atoms as function of TA could not be
derived (problem of angular resolution, mosaicity of implanted sample!)
 Annealing of radiation damage: PL

• Sample implanted with 89Sr at a dose of ~1014 cm2

• PL with 325nm excitation (above band edge 387 nm = 3.2 eV ) measured
at 1.6 K as function of TA
 near-band edge luminescence restored only for TA>800°C
Motivation: SrTiO3 in the focus as...

... dilute magnetic

semiconductor
(room-temperature
ferromagnetism?)
 Fe in SrTiO3
• As 3d transition metal element, Fe is a candidate for
magnetic doping of SrTiO3 (cf Mn)

• which lattice site does Fe occupy following ion

implantation?

 study by means of  emission channeling using the

radioactive isotope 59Fe (t1/2=44 d)
low dose implantations (60 keV, 51012  11013 cm2)

• What are the magnetic properties of Fe-implanted SrTiO3?

 study by means of SQUID

high dose implantations (60 keV, 1015  1016 cm2)
Emission channeling lattice location:
basic principle
The cubic perovskite lattice of SrTiO3

u1(Sr)=.077 Å
u1(Ti)=.061 Å
u1(Sr)=.085 Å
 59
Fe lattice sites in SrTiO3 as function of TA

 as-implanted: octahedral interstitial I8 prominent + substitutional Ti

 Fe on I8 decreases fast
 no damage recovery stage
 no (or little) Fe on Sr sites
 Fe prefers <100> displaced Ti sites (0.4-0.8 Å) + Ti sites
  emission channeling patterns, 59Fe 60 keV 1013 cm2 in SrTiO3, as-impl.

{1
experiment best fit STi + STiSO + Oi <100> displ. STi I8 sites
00 -2 -1 0 1 2 3 -2 -1 0 1 2 3
} (e) <100>
2
(a) simulation STi sites simulation STiSsimulation
1.72 - 1.85 O sites SSr sites simulation Oi sites
1 -2 -1 0 1 2
1.59 - 1.72
-2 -1 0 1 -22 -1 0 1 2 -2 -1 0 1 2
(a) <100> 1.46 - 1.59
(a) <100> (e) <100> (e) <100>
{110} 0 1.53 - 1.64 1.33 - 1.46 1.18 - 1.25 1.34 - 1.42 2.63 - 2.90
1.42 - 1.53 1.12 - 1.18 1.27 - 1.34 2.37 - 2.63
-1 1.19 - 1.33
1.31 - 1.42 1.05 - 1.12 1.19 - 1.27 2.10 - 2.37
1.06 - 1.19 1.12 - 1.19 1.83 - 2.10
{2

1.19 - 1.31 0.98 - 1.05

-2 0.93 - 1.06
11

1.08 - 1.19 0.91 - 0.98 1.04 - 1.12 1.56 - 1.83

0.80 - 0.93
}

0.97 - 1.08 0.85 - 0.91 0.96 - 1.04 1.30 - 1.56

{1
1 1} 3 0.86 - 0.97
0.75 - 0.86
(f) <110> 0.78 - 0.85
0.71 - 0.78
0.89 - 0.96
0.81 - 0.89
1.03 - 1.30
0.76 - 1.03
1.54 - 1.64
(b) 2 (b) <110> 1.44 - 1.54 (b) <110> (f) <110> (f) <110>
2.81 - 3.10 1.35 - 1.44 1.20 - 1.27 1.24 - 1.29 1.55 - 1.65
1 2.52 - 2.81 1.25 - 1.35 1.14 - 1.20 1.18 - 1.24 1.44 - 1.55
2.23 - 2.52 1.08 - 1.14 1.13 - 1.18 1.34 - 1.44
{110} 0 1.15 - 1.25
1.93 - 2.23 1.01 - 1.08 1.08 - 1.13 1.24 - 1.34
1.64 - 1.93
1.06 - 1.15 0.95 - 1.01 1.02 - 1.08 1.14 - 1.24
-1 1.35 - 1.64 0.96 - 1.06 0.88 - 0.95 0.97 - 1.02 1.03 - 1.14
{2 0.86 - 0.96
10 1.06 - 1.35 0.82 - 0.88 0.91 - 0.97 0.93 - 1.03
} 0.77 - 1.06 0.75 - 0.82 0.86 - 0.91 0.83 - 0.93
2 (g) <211>
(c) <211> (c) <211> (g) <211> (g) <211>
(c) 1.93 - 2.10
1.30 - 1.37
2.08 - 2.26 1.14 - 1.19 1.25 - 1.31
1 1.23 - 1.30
1.77 - 1.93 1.90 - 2.08 1.10 - 1.14 1.18 - 1.25
1.60 - 1.77 1.16 - 1.23 1.72 - 1.90 1.05 - 1.10 1.12 - 1.18
{110} 0 1.43 - 1.60 1.10 - 1.16 1.54 - 1.72 1.00 - 1.05 1.05 - 1.12
1.27 - 1.43 1.03 - 1.10 1.36 - 1.54 0.96 - 1.00 0.99 - 1.05
-1
1.10 - 1.27 0.96 - 1.03 1.18 - 1.36 0.91 - 0.96 0.92 - 0.99
0.94 - 1.10 0.89 - 0.96 1.00 - 1.18 0.87 - 0.91 0.86 - 0.92
-2
0.77 - 0.94 0.82 - 0.89 0.82 - 1.00 0.82 - 0.87 0.79 - 0.86
(d) <111> (d) <111> (h) <111> (h) <111>
(d) 2 1.09 - 1.13
(h) <111> 1.09 - 1.13 1.18 - 1.22 1.20 - 1.24
1.05 - 1.09 1.21 - 1.25 1.05 - 1.09 1.14 - 1.18 1.15 - 1.20
1 1.00 - 1.05 1.16 - 1.21 1.00 - 1.05 1.10 - 1.14 1.11 - 1.15
0.96 - 1.00 1.12 - 1.16 0.96 - 1.00 1.06 - 1.10 1.06 - 1.11
{110} 0 0.92 - 0.96 1.08 - 1.12 0.92 - 0.96 1.02 - 1.06 1.02 - 1.06
0.88 - 0.92 0.88 - 0.92 0.98 - 1.02 0.97 - 1.02
1.04 - 1.08
-1 0.83 - 0.88
1.00 - 1.04
0.83 - 0.88 0.94 - 0.98 0.93 - 0.97
0.79 - 0.83 0.79 - 0.83 0.90 - 0.94 0.88 - 0.93
-2 -2 -1 0.95
0 -11.002 -2 -1 0 1 -22 -1[deg]
0 1 2 -2 -1 0 1 2 [deg]
} 0.91 - 0.95
{2 11
-2 -1 0 1 2 -2 -1 0 1 2 [deg]
  emission channeling patterns, 59Fe 60 keV 1013 cm2 in SrTiO3, TA=900°C
{1
00
}
experiment best fit STi + STiSO <100> displ. STi ideal STi sites
-2 -1 0 1 2 -2 -1 0 1 2
(a) 2 (e) <100>
simulation S sites simulation STiSO sites
1.30Ti- 1.37
simulation STi sites simulation STiSO sites
1 -2 -1 0 1
1.24 - 1.302 -2 -1 0 1 2 -2 -1 0 1 2 -2 -1 0 1 2
(a) <100> 1.17 - 1.24 (e) <100> (a) <100> (
{110} 0 1.53 - 1.64 1.10 - 1.17 1.34 - 1.42 1.53 - 1.64
1.42 - 1.53 1.27 - 1.34 1.42 - 1.53
-1 1.03 - 1.10
1.31 - 1.42 1.19 - 1.27 1.31 - 1.42
0.97 - 1.03
{2

1.19 - 1.31 1.12 - 1.19 1.19 - 1.31

11

-2 1.08 - 1.19
0.90 - 0.97 1.04 - 1.12 1.08 - 1.19
}

0.97 - 1.08 0.83 - 0.90 0.96 - 1.04 0.97 - 1.08

{1 0.86 - 0.97 (f) <110> 0.89 - 0.96 0.86 - 0.97
11 2
} 0.75 - 0.86
1.64 - 1.75
0.81 - 0.89 0.75 - 0.86

(b) 1 (b) <110> 1.53 - 1.64

(f) <110> (b) <110> (
2.81 - 3.10 1.42 - 1.53 1.24 - 1.29 2.81 - 3.10
{110} 0 2.52 - 2.81
1.32 - 1.42
1.18 - 1.24 2.52 - 2.81
2.23 - 2.52 1.13 - 1.18 2.23 - 2.52
-1 1.21 - 1.32
1.93 - 2.23 1.08 - 1.13 1.93 - 2.23
1.64 - 1.93 1.10 - 1.21 1.02 - 1.08 1.64 - 1.93
{2 -2
10 1.35 - 1.64 0.99 - 1.10 0.97 - 1.02 1.35 - 1.64
} 1.06 - 1.35 0.88 - 0.99 0.91 - 0.97 1.06 - 1.35
0.77 - 1.06 0.86 - 0.91 0.77 - 1.06
2 (g) <211>
(c) (c) <211> (g) <211> (c) <211> (
1.29 - 1.36
1 1.93 - 2.10
1.23 - 1.29
1.14 - 1.19 1.93 - 2.10
1.77 - 1.93 1.10 - 1.14 1.77 - 1.93
1.16 - 1.23
{110} 0 1.60 - 1.77 1.05 - 1.10 1.60 - 1.77
1.43 - 1.60 1.10 - 1.16 1.00 - 1.05 1.43 - 1.60
-1 1.27 - 1.43 1.03 - 1.10 0.96 - 1.00 1.27 - 1.43
1.10 - 1.27 0.97 - 1.03 0.91 - 0.96 1.10 - 1.27
-2 0.94 - 1.10 0.91 - 0.97 0.87 - 0.91 0.94 - 1.10
0.77 - 0.94 0.84 - 0.91 0.82 - 0.87 0.77 - 0.94
(d) <111> (h) <111> (d) <111> (
2 (h) <111>
(d) 1.09 - 1.13
1.16 - 1.20
1.18 - 1.22 1.09 - 1.13
1.05 - 1.09 1.14 - 1.18 1.05 - 1.09
1 1.12 - 1.16
1.00 - 1.05 1.10 - 1.14 1.00 - 1.05
{110} 0 0.96 - 1.00 1.08 - 1.12 1.06 - 1.10 0.96 - 1.00
0.92 - 0.96 1.04 - 1.08 1.02 - 1.06 0.92 - 0.96
0.88 - 0.92 0.98 - 1.02 0.88 - 0.92
-1 0.99 - 1.04
0.83 - 0.88 0.94 - 0.98 0.83 - 0.88
0.95 - 0.99
0.79 - 0.83 0.90 - 0.94 0.79 - 0.83
-2 -2 -1 0.91
0 -10.952 -2 -1 0 1 2 [deg] -2 -1 0 1 2 -2 -1 0 1 2 [d
1}
{21
0.87 - 0.91
-2 -1 0 1 2 -2 -1 0 1 2 [deg]
  emission channeling patterns, 59Fe 60 keV 1013 cm2 in SrTiO3, TA=900°C
{1
00
}
experiment best fit STi + STiSO <100> displ. STi ideal STi ideal SSr
-2 -1 0 1 2 -2 -1 0 1 2
(a) 2 (e) <100>
simulation STi sites simulation STiSO sites simulation STi sites simulation STisimulation
SO sites SSr sites
1.30 - 1.37
-2 -1 0 1 2 -2 -1 0 1 2 -2 -1 0 1 2 -2 -1 0 1 -2 2 -1 0 1 2
1 1.24 - 1.30
(a) <100> (e) <100> (a) <100> (a) <100> (e) <100>
1.17 - 1.24
{110} 0 1.53 - 1.64
1.10 - 1.17
1.34 - 1.42
1.27 - 1.34
1.53 - 1.64 1.18 - 1.25 1.34 - 1.42
1.27 - 1.34
1.42 - 1.53 1.42 - 1.53 1.12 - 1.18

-1 1.31 - 1.42 1.03 - 1.10 1.19 - 1.27 1.31 - 1.42 1.05 - 1.12 1.19 - 1.27
1.19 - 1.31 1.12 - 1.19 1.19 - 1.31 0.98 - 1.05 1.12 - 1.19
0.97 - 1.03
{2

1.08 - 1.19 1.04 - 1.12 1.08 - 1.19 0.91 - 0.98 1.04 - 1.12
11

-2 0.97 - 1.08
0.90 - 0.97 0.96 - 1.04 0.97 - 1.08 0.85 - 0.91 0.96 - 1.04
}

0.86 - 0.97 0.83 - 0.90 0.89 - 0.96 0.86 - 0.97 0.78 - 0.85 0.89 - 0.96
{1 0.75 - 0.86
(f) <110> 0.81 - 0.89 0.75 - 0.86 0.71 - 0.78 0.81 - 0.89
11 2 (b) <110> (f) <110> (b) <110> (b) <110> (f) <110>
} 1.64 - 1.75
(b) 1 2.81 - 3.10
2.52 - 2.81 1.53 - 1.64
1.24 - 1.29
1.18 - 1.24
2.81 - 3.10
2.52 - 2.81
1.20 - 1.27
1.14 - 1.20
1.24 - 1.29
1.18 - 1.24
2.23 - 2.52 1.42 - 1.53 1.13 - 1.18 2.23 - 2.52 1.08 - 1.14 1.13 - 1.18
{110} 0 1.93 - 2.23 1.32 - 1.42 1.08 - 1.13 1.93 - 2.23 1.01 - 1.08 1.08 - 1.13
1.64 - 1.93 1.02 - 1.08 1.64 - 1.93 0.95 - 1.01 1.02 - 1.08
-1 1.35 - 1.64
1.21 - 1.32 0.97 - 1.02 1.35 - 1.64 0.88 - 0.95 0.97 - 1.02
1.06 - 1.35 1.10 - 1.21 0.91 - 0.97 1.06 - 1.35 0.82 - 0.88 0.91 - 0.97
{2 -2
10 0.77 - 1.06 0.99 - 1.10 0.86 - 0.91 0.77 - 1.06 0.75 - 0.82 0.86 - 0.91
} (c) <211> 0.88 - 0.99 (g) <211> (c) <211> (c) <211> (g) <211>
2
1.93 - 2.10
(g) <211> 1.14 - 1.19 1.93 - 2.10
1.77 - 1.93
2.08 - 2.26
1.90 - 2.08
1.14 - 1.19
1.10 - 1.14
(c) 1.77 - 1.93
1.60 - 1.77 1.29 - 1.36
1.10 - 1.14
1.05 - 1.10 1.60 - 1.77 1.72 - 1.90 1.05 - 1.10
1 1.43 - 1.60 1.23 - 1.29 1.00 - 1.05 1.43 - 1.60 1.54 - 1.72 1.00 - 1.05
1.27 - 1.43 0.96 - 1.00 1.27 - 1.43 1.36 - 1.54 0.96 - 1.00
1.16 - 1.23
{110} 0 1.10 - 1.27 0.91 - 0.96 1.10 - 1.27 1.18 - 1.36 0.91 - 0.96
0.94 - 1.10 1.10 - 1.16 0.87 - 0.91 0.94 - 1.10 1.00 - 1.18 0.87 - 0.91
-1 0.77 - 0.94 1.03 - 1.10 0.82 - 0.87 0.77 - 0.94 0.82 - 1.00 0.82 - 0.87
(d) <111> 0.97 - 1.03 (h) <111> (d) <111> (d) <111> (h) <111>
-2 1.09 - 1.13 0.91 - 0.97 1.18 - 1.22 1.09 - 1.13 1.09 - 1.13 1.18 - 1.22
1.05 - 1.09 0.84 - 0.91 1.14 - 1.18 1.05 - 1.09 1.05 - 1.09 1.14 - 1.18
1.00 - 1.05 1.10 - 1.14 1.00 - 1.05 1.00 - 1.05 1.10 - 1.14
2 0.96 - 1.00 (h) <111> 1.06 - 1.10 0.96 - 1.00 0.96 - 1.00 1.06 - 1.10
(d) 0.92 - 0.96
1.16 - 1.20
1.02 - 1.06 0.92 - 0.96 0.92 - 0.96 1.02 - 1.06
0.88 - 0.92 0.98 - 1.02 0.88 - 0.92 0.88 - 0.92 0.98 - 1.02
1 0.83 - 0.88 1.12 - 1.16 0.94 - 0.98 0.83 - 0.88 0.83 - 0.88 0.94 - 0.98
0.79 - 0.83 1.08 - 1.12 0.90 - 0.94 0.79 - 0.83 0.79 - 0.83 0.90 - 0.94
{110} 0 -2 -1 0 1 2 -2 -1 0 1 2 [deg] -2 -1 0 1 2 -2 -1 0 1 -2 2 -1 [deg]
0 1 2
1.04 - 1.08
-1 0.99 - 1.04
0.95 - 0.99
-2 0.91 - 0.95
1}
{21
0.87 - 0.91
-2 -1 0 1 2 -2 -1 0 1 2 [deg]
 SQUID magnetic moment of SrTiO3:Fe (H)

• Fe 60 keV 51015 cm2, TA=900°C, SQUID measurement at 10 K

56

• Diamagnetism of SrTiO3 substrate

• Weak paramagnetism of implanted Fe and contaminants (0.5 ppm Cu2+?)
• Ferromagnetism of implanted Fe
 SQUID magnetic moment of SrTiO3:Fe (T)

• Paramagnetic component becomes obvious from temperature

dependence:
1/T Brillouin paramagnetic vs constant diamagnetic + ferromagnetic
 SQUID results for different Fe fluences
magnetization of 51015 cm2 Fe
small ferromagnetic signals
implanted SrTiO3
from
 7.5 B -3

/m [em u g ]
2 x1 0
virgin SrTiO3

-1
11015 cm2 Fe implanted
-3
1 x1 0

ferromagnetic
0
signature
-1x1 0
4
-5 x1 0
3
0 5 x1 0
3
1 x1 0
4

H [O e]

-3
-1 x1 0
0 .0002

15
S T O _ 2 5 6 (5 ´1 0 )
15
S T O _ 2 5 7 (1 ´1 0 )
-3 S T O _ v irg in
-2 x1 0

0 .0000

 Note: 60 keV 11015 cm2 corresponds to

[Fe]max = 1.8% /unit cell -0.0002

-10 00 -50 0 0 5 00 1000

 implanted Fe exhibits ferromagnetism in SrTiO3

Sources of magnetism in Fe-implanted SrTiO3
 Cu and Ag in SrTiO3
• As group Ib elements, Cu and Ag on Sr sites are candidates
for p-type (acceptor) doping of SrTiO3

• which lattice site do they occupy following ion implantation?

 study by means of  emission channeling using the

radioactive isotopes 67Cu (t1/2=63 h) and 111Ag (7.5 d)

• Note: low dose implantations (60 keV, 51012  11013 cm2)

 Cu and 111Ag lattice sites in SrTiO3 as function of TA
67

1.0
sum of all fractions
0.9
0.8
f(I8) octahedral interst. 111
Ag
f(Sr)
0.7
f(Ti)
67
Cu
Cu fractions f

0.6
0.5
0.4
0.3
67

0.2
0.1
0.0
0 200 400 600 800 1000
annealing temperature TA [°C]

 as-implanted: substitutional + octahedral interstitial I8 sites

 Cu and Ag on I8 disappears fast
 broad recovery stage of damage 300-900°C,
 Cu and Ag are both amphoteric (found on both Sr and Ti sites)
 Cu prefers Ti sites while Ag prefers Sr sites!

Possible explanation: ionic radii

Sr2+ 1.13 Å Cu1+ 0.96 Å Ag1+ 1.26 Å
Ti4+ 0.68 Å Cu2+ 0.69 Å Ag2+ 1.08 Å
 Motivation: SrTiO3 in the focus as...

... red phosphor material

flat panel displays
  emission channeling patterns, 169Yb 1014 cm2 in SrTiO3, TA=900°C
SSr STi
{1 experiment simulation best fit Sr sites Ti sites
00
} -2 -1 0 1 2 -2 -1 0 1 2 -2 -1 0 1 2 -2 -1 0 1 2
(a) 2 1.67 - 1.83 (f) <100> (a) <100> 2 (e) <100>
1.52 - 1.67 1.41 - 1.53 1.87 - 2.05
1 1.36 - 1.52 1.30 - 1.41 1 1.68 - 1.87
1.21 - 1.36 1.18 - 1.30 1.50 - 1.68
{110} 0 1.07 - 1.18 0 1.32 - 1.50
1.05 - 1.21
0.95 - 1.07 1.14 - 1.32
-1 0.89 - 1.05 0.83 - 0.95 -1 0.96 - 1.14
0.74 - 0.89 0.72 - 0.83 0.77 - 0.96
-2 0.58 - 0.74 0.60 - 0.72
-2 0.59 - 0.77

(b) 2 2.09 - 2.28 (g) <110> (b) <110> 2 (f) <110>

1.90 - 2.09 1.31 - 1.40 3.40 - 3.80
1 1.71 - 1.90 1.22 - 1.31 1 3.00 - 3.40
1.12 - 1.22 2.60 - 3.00
{110} 0 1.52 - 1.71
1.03 - 1.12 0 2.19 - 2.60
1.33 - 1.52 1.79 - 2.19
0.94 - 1.03
-1 1.14 - 1.33 0.85 - 0.94
-1 1.39 - 1.79
0.95 - 1.14 0.99 - 1.39
-2 0.76 - 0.95
0.75 - 0.85
0.66 - 0.75
-2 0.59 - 0.99

(c) 2 2.06 - 2.25 (h) <211> (c) <211> 2 (g) <211>

1.86 - 2.06 2.94 - 3.27 2.89 - 3.21
1 1.67 - 1.86 2.62 - 2.94 1 2.56 - 2.89
1.48 - 1.67 2.29 - 2.62 2.24 - 2.56
{110} 0 1.97 - 2.29
0 1.92 - 2.24
1.28 - 1.48
1.59 - 1.92
-1 1.09 - 1.28
1.64 - 1.97
1.31 - 1.64
-1 1.27 - 1.59
0.89 - 1.09
-2 0.99 - 1.31 -2 0.94 - 1.27
0.70 - 0.89 0.66 - 0.99 0.62 - 0.94

(d) 2 1.79 - 1.94 (i) <411> (d) <411> 2 (h) <411>

1.63 - 1.79 2.06 - 2.26 2.16 - 2.38
1 1.48 - 1.63 1.86 - 2.06
1 1.93 - 2.16
{110} 0 1.33 - 1.48 1.66 - 1.86 1.71 - 1.93
1.47 - 1.66
0 1.49 - 1.71
1.17 - 1.33
-1 1.02 - 1.17 1.27 - 1.47 -1 1.26 - 1.49
1.04 - 1.26
1.07 - 1.27
0.86 - 1.02
-2 0.87 - 1.07 -2 0.81 - 1.04
0.71 - 0.86 0.67 - 0.87 0.59 - 0.81

1.30 - 1.39 -3 -2 -1 0 1 -3 -2 -1 0 1 [deg]

(e) 2 (j) <111>
1.21 - 1.30
1 1.12 - 1.21
1.03 - 1.12
{110} 0 0.94 - 1.03
-1 0.85 - 0.94
0.76 - 0.85
-2 0.67 - 0.76
-2 -1 0 1 2 -2 -1 0 1 2 [deg]
 169
Yb lattice sites in SrTiO3 as function of TA

 no octahedral interstitial I8 sites (in contrast to TMs Fe, Cu, Ag)

 also broad recovery stage of damage 300-900°C,
 Yb is also amphoteric (found on both Sr and Ti sites)
 Yb prefers Ti sites
 Overview: SrTiO3 emission channeling
lattice location experiments

• Electrical dopants  Emission channeling lattice location

• Magnetic dopants experiments undertaken so far
Experiments foreseen or possible
• Optical dopants Experiments attempted
 Conclusions
 SrTiO3 relatively resistant against implantation
damage
 damage annealing starts above 200-300°C...
• but is only complete at ~1000-1100°C
 annealing is less efficient than expected
• lattice location experiments in SrTiO 3 difficult to
analyze:
– Cu, Ag, Yb are amphoteric impurities: multiple sites
– Fe also shows site distribution: <100> diplaced Ti + Ti
 generally doping is complicated by amphoteric
nature
• Ag more promising Sr-site acceptor than Cu,
• Fe was shown to act as ferromagnetic dopant
 Performance against original work plan:

 Year 1 (2005-06): lattice location and damage

annealing studies in SrTiO3, first measurements of
optical and magnetic properties
• Year 2 (2006-07): lattice location and damage
annealing studies extended to other perovskites,
e.g. KTaO3 (samples have now been bought), measurements
of optical and magnetic properties under
optimized conditions (dose, annealing…) 
• Year 3 (2007-08): set priorities for the study of
those systems where, according to outcome of
research in years 1+2, best results were obtained