Thesis 19 06 2008 Final Version

Instituut voor
Kern- en Stralingsfysica
Departement Natuurkunde KATHOLIEKE UNIVERSITEIT
Faculteit Wetenschappen
Defect characterization of Europium

implanted Gallium Nitride
Promotor: Proefschrift ingediend tot

Prof. Dr. André Vantomme het behalen van de graad van
doctor in de wetenschappen
door
Vasco Miguel Matias Serrão
Leuven 2008
“People are like crystals. It is the defects in them that make them interesting.”
Sir F. Charles Frank
“Perfection has one grave defect: it is apt to be dull! ”

William Somerset Maugham
Acknowledgments
Finally here it is, my PhD thesis! So much work, ups and downs, a lot of
pleasure, some less good moments, and somehow I managed to get to the
end of it after all...
However, this is also a bit some other people’s work as well. Without
them I would have never been able to get this far. Not just scientifically
but also personally.
During this period, not only I learned the ways of science, developed my
problem solving skills and learned how to autonomously work, but also grew
up as a person. I came out of my “safe” family environment, left my friends,
my roots and my culture to begin a scary but exciting new adventure: living
in Belgium. Soon I found myself thinking: “my God, what have I done?”.
All my references were gone and suddenly I was just one more foreigner in
a strange country. I had a hard time to adapt: people were “colder”, their
habits were weird and my sun and blue sky had abandoned me.
Little by little things started to get better. I met people in the same
situation as I was and Leuven started to become my home away from home.
I’ve met a lot of people during my PhD. Some of them stayed colleagues,
some of them became friends. A few of them, real friends. I would like to
take this chance to thank all of the people that helped me getting to this
point today.
I couldn’t start by nobody else than my promotor André Vantomme.
He encouraged me to come to Leuven and start a PhD in his group. Helped
me through all the paper work and once I was here he gave me guidance
and made sure I was on the right tracks. He was a good mentor during my
PhD. He was always available to discuss results and provide precious hints
on how to tackle certain problems. Furthermore, with him I learned how
to autonomously work. Bedankt voor al uw geduld, uw steun en uw advies.
Vooral bedankt voor uw hulp met mijn thesis.
Next I would like to thank the jury members: Professors Guido Lan-
gouche, Kristiaan Temst, Gustaaf Borghs, André Stesmans, Kevin O’Donnell
and F. D. Auret for their effort in reading my thesis, their comments, cor-
rections and the very pleasant discussion during the preliminary defense.
I would equally like to thank the RENiBEl network colleagues for the
precious collaboration, interesting discussions and workshops and the pleas-
ant moments of companionship. In particular I would like to thank Katha-
rina Lorenz, Emilio Nogales, Iman Roqan and Thomasz Wojtowicz.
This work would have never been possible without the help of some
fantastic people I’ve met in Pretoria, South Africa. Baaie dank Johan,
Jackie, Hannes, Sérgio, Gunther, Michael, Claude and everyone else that
helped me during my stay there. I’ve learned a lot with you. You guys are
great!
I would also like to thank my colleagues at the IKS. First of all, Bert
Pipeleers for his patience and tutorship. Thanks for helping me with the
implanter and RBS. You were a great colleague. Thank you Bart De Vries
for the interesting discussions and computer tips. Thanks Stefan Decoster
for the companionship and understanding when the machines were giving
me a bad time. Thanks Zhao for fixing the Pelletron time and again.
Annemie and Willy, thank you for your help with the implanter - eventually
I managed to get the hang of it. A big thank you to all the other colleagues
that were on the same boat and made this journey so pleasant. Thank you
Kristof, Dries, Annelies, Koen, Doru, Zhou, and all the other people I’m
forgetting to mention.
On the personal level, I would like to thank the people I’ve met during
my PhD and became more than just collegues. Thank you Marisia, Sarah,
Katia, Sally, Thomas, Nick and of course Ester. You kept me going when
things were becoming too heavy. Thanks for your precious friendship, your
humor, complicity, understanding and sincerity. It means a lot to me.
I would like to thank my family. This PhD changed a lot of things in
our lives. However, even though I’m 2000 Km away, you have been with
me all along the way. Gave me strength to go on. Believed in me. Mãe
e mana obrigado por tudo. Eu adoro-vos. E mesmo apesar da distância
vocês estarão sempre comigo no meu coração.
Ik zou ook graag mijn belgische familië willen bedanken. Bedankt om
me binnen bij jullie te laten. Met jullie heb ik veel geleerd. Vooral dat
belgen toch warme mensen kunnen zijn. Dankzij jullie voel ik me niet meer
nog een vreemdeling meer tussen veel. Ik heb jullie cultuur en gewoonten
leren accepteren en kunnen beseffen dat ookal zijn er oppervlakkige ver-
schillen, het woord familie in het nederlands betekent juist hetzelfde als
in het portugees: daar voor elkaar zijn wanneer het het meest nodig is -
Hartelijk bedankt.
Tenslotte kon ik niet eindigen zonder mijn toekomstige echtgenoot mijn
grootste dank te zeggen. Ik heb jou in het begin van mijn doctoraat leren
kennen en je hebt alles kunnen volgen. Alles wat goed of minder goed ging,
je hebt het allemaal gehoord. Ook al had je geen verstand van fysika je had
altijd fijne woorden voor mij, en veel geduld. Vooral tegen het eind toen
alles heel zwaar begon te worden. Al jouw steun, sterkte, geduld, liefde,
vriendschap... je bent ongeloofelijk. Echt. Ik zou je nooit genoeg kunnen
bedanken. Bruno je bent een held. Mijn held. Ik hou veel van jou.
Vasco Matias
Contents
Introduction v
1 Properties of III-nitrides and RE in GaN 1

1.1 III-nitrides historical background and their applications . . 1
1.2 Growth of crystalline III-nitrides . . . . . . . . . . . . . . . 4
1.2.1 Nitride growth techniques . . . . . . . . . . . . . . . 5
1.2.2 Buffer layer . . . . . . . . . . . . . . . . . . . . . . . 6
1.3 Brief overview of III-nitride properties . . . . . . . . . . . . 8
1.3.1 Structural properties . . . . . . . . . . . . . . . . . . 8
1.3.2 Thermal properties . . . . . . . . . . . . . . . . . . . 8
1.3.3 Optical properties and band structure . . . . . . . . 9
1.3.4 Electrical properties . . . . . . . . . . . . . . . . . . 11
1.4 Rare-earth elements . . . . . . . . . . . . . . . . . . . . . . 12
1.4.1 Properties of rare-earths . . . . . . . . . . . . . . . . 13
1.4.2 RE in GaN for luminescence emission . . . . . . . . 13
2 Energy band structure of semiconductors 19

2.1 Band structure in solids . . . . . . . . . . . . . . . . . . . . 19
2.1.1 Electrons in semiconductors . . . . . . . . . . . . . . 20
2.2 Electronic conduction in semiconductors . . . . . . . . . . . 26
2.3 Optical emission . . . . . . . . . . . . . . . . . . . . . . . . 27
2.4 Intrinsic and extrinsic semiconductors . . . . . . . . . . . . 28
2.4.1 Intrinsic semiconductor . . . . . . . . . . . . . . . . 29
2.4.2 Extrinsic semiconductor . . . . . . . . . . . . . . . . 29
i
2.5 Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.5.1 Electrical doping . . . . . . . . . . . . . . . . . . . . 33
2.5.2 Magnetic doping . . . . . . . . . . . . . . . . . . . . 35
2.5.3 Optical doping . . . . . . . . . . . . . . . . . . . . . 36
3 Defects in semiconductors 41
3.1 Structural defects classification . . . . . . . . . . . . . . . . 41
3.2 Point defects . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.3 Line and surface defects . . . . . . . . . . . . . . . . . . . . 45
3.4 Volume defects . . . . . . . . . . . . . . . . . . . . . . . . . 47
4 Deep Level Transient Spectroscopy 51

4.1 Schottky barrier and depletion layer . . . . . . . . . . . . . 52
4.2 DLTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.2.1 Capacitance transient . . . . . . . . . . . . . . . . . 58
4.2.2 Emission rate window . . . . . . . . . . . . . . . . . 60
4.3 DLTS instrumentation . . . . . . . . . . . . . . . . . . . . . 68
4.4 DLTS signature temperature dependence . . . . . . . . . . 69
4.5 DLTS limitations . . . . . . . . . . . . . . . . . . . . . . . . 71
5 Ion beams for materials modification and characterization 73

5.1 Fundamentals of ion beam-solid interactions . . . . . . . . . 73
5.2 Ion implantation . . . . . . . . . . . . . . . . . . . . . . . . 80
5.3 Parameters influencing implantation damage . . . . . . . . 87
5.4 RBS\C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
6 Structural characterization of Eu-implanted GaN 109

6.1 Experimental details . . . . . . . . . . . . . . . . . . . . . . 109
6.2 Structural damage due to ion implantation . . . . . . . . . 113
6.3 Fluence dependence . . . . . . . . . . . . . . . . . . . . . . 121
6.4 Implantation direction . . . . . . . . . . . . . . . . . . . . . 128
6.5 Temperature dependence . . . . . . . . . . . . . . . . . . . 137
6.6 AlN protective layer . . . . . . . . . . . . . . . . . . . . . . 159
6.7 Substrate composition . . . . . . . . . . . . . . . . . . . . . 164
6.8 Energy dependence . . . . . . . . . . . . . . . . . . . . . . . 181
6.9 Ion mass dependence . . . . . . . . . . . . . . . . . . . . . . 189
6.10 Beyond the limitations of RBS/C . . . . . . . . . . . . . . . 194
6.11 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
7 Electrical characterization of Eu-implanted GaN 205

7.1 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . 207
7.2 DLTS measurements at ENSICAEN . . . . . . . . . . . . . 208
7.3 DLTS at the University of Pretoria . . . . . . . . . . . . . . 214
7.3.1 Current- and capacitance-voltage measurements . . 214
7.3.2 Deep level transient spectroscopy . . . . . . . . . . . 218
7.4 DLTS results summary and conclusions . . . . . . . . . . . 256
8 Conclusions 261
A Rutherford Backscattering and Channeling Spectrometry

(RBS/C) 267
A.1 Basic concepts . . . . . . . . . . . . . . . . . . . . . . . . . 268
A.2 Physical background . . . . . . . . . . . . . . . . . . . . . . 269
A.2.1 Kinematic factor K . . . . . . . . . . . . . . . . . . . 269
A.2.2 Stopping cross section ² . . . . . . . . . . . . . . . . 270
A.2.3 Scattering cross section σ(θ) . . . . . . . . . . . . . 272
A.3 RBS/Channeling . . . . . . . . . . . . . . . . . . . . . . . . 273
B High Resolution X-ray Diffraction (HRXRD) 279
Nederlandstalige samenvatting 283
References 291
Publications 309
iv
Introduction
Gallium nitride and related semiconducting materials are in the center

of one of the most important breakthroughs in electronics and optoelec-
tronics of the last decade. Since the development of the first blue (450
nm), blue/green, violet and ultra-violet GaN-based light emitting devices
by Shuji Nakamura in the early years of the 1990’s, worldwide attention
has turned to these nitride compound semiconductors. With a brightness
up to 100 times stronger than SiC based emitting devices, soon the nitrides
found applications in several areas ranging from traffic lights, through out-
door displays, to medical applications. In fact, GaN-based violet lasers are
the base technology within the new generation of optical data storage and
entertainment systems, such as the Blu-ray Disc system. This new format
allowed expanding the standard DVD capacity from 4.7 Gb to about 54 Gb
(double layer) of information on a disc. Other technologically relevant ap-
plications of GaN are found in the domains of high temperature, high power
and fast electronics, being high electron mobility transistors (HEMT) an
example of such applications.
Besides these direct applications, the physical properties of GaN kept
attracting attention of research groups to explore other capabilities of this
interesting material. Due to its resistance to radiation damage, its thermal
stability and direct band gap, GaN and related materials are very suitable
hosts for optical dopants. Among such dopants, rare-earth (RE) ions have
long been employed in phosphors to produce bright luminescence in a wide
range of colors of the visible spectrum. RE-luminescence has its origin
on the intra-4f shell electronic transitions resulting in sharp luminescence
v
vi Introduction
emission lines with wavelengths virtually independent of the host material.

However, despite the fact that the wavelength is host-independent, the in-
tensity of RE-luminescence depends very strongly on the host material.
Classical semiconductors such as Si and GaAs are characterized by rela-
tively narrow band gaps (1.1 and 1.4 eV). Such materials normally present
good optical behavior at low temperatures, however at higher temperatures
the luminescence output is often considerably quenched. Favennec et al.[1]
empirically observed that the the thermal quenching of RE-luminescence
decreases with increasing host semiconductor band gap. As such, with its
wide direct band gap (3.4 eV) GaN became an interesting host for rare-
earth optical dopants.
Despite the fact that GaN proved its efficiency as a host, several prob-
lems were encountered while attempting to optimize the properties of the
rare-earth-GaN optical system. Both the most common techniques to in-
troduce dopants in semiconductors present advantages and disadvantages.
Doping during growth, employing for example molecular beam epitaxy, does
not allow to control the dopant distribution and thus local doping is not
possible. Furthermore, possibly the most important disadvantage of this
doping method is the solubility limit of the dopant in the host material.
On the other hand, ion implantation allows solving both of those prob-
lems. By steering the beam, it is possible to control the local dopant dis-
tribution and even more than one dopant species can be introduced in
the same region, paving way to color-mixing. Another strong advantage
of this technique is the fact that the solubility limit can be overcome, as
implantation is a non-equilibrium doping method. However the ion im-
plantation technique presents a very important disadvantage: structural
damage brought to the crystal lattice during dopant introduction can seri-
ously hinder the optical outcome.
The work summarized in this thesis is performed in the context of

the RENiBEl Research Training network, from the European Commis-
sion’s 5th Framework Improving Human Potential program. The RENi-
BEl acronym stands for Rare E arth doped Ni trides for high B rightness
vii
El ectroluminescent emitters. The main goal of this network was to under-

stand the fundamental optical interactions of RE-ions in GaN-based semi-
conductors in order to improve light emission efficiency and device perfor-
mance. RE doping of the nitride host employing ion implantation was an
essential tool in order to accomplish RENiBEl’s objectives. Furthermore,
the driving force for the research work presented here was to relate the
structural, optical and electrical properties of Eu-implanted GaN in order
to improve the understanding of the energy transfer mechanism between
the nitride host and the rare-earth ions, responsible for the characteristic
light emission.
viii Introduction
Chapter 1
Properties of III-nitrides
and RE in GaN
1.1 III-nitrides historical background and their

applications
The past decade has seen a strong interest in wide band gap semiconduc-
tors, in particular, gallium nitride (GaN) and related compounds. The need
for devices operating at higher temperature and/or higher power has been
the motor for this quest. Due to their properties, namely wide and direct
band gap, group III-nitrides are expected to operate at higher temperatures,
have larger breakdown fields, higher electron saturated drift velocity and
better thermal conductivity as compared to more common semiconductors
such as silicon and gallium arsenide [2, 3]. Another important character-
istic of these III-nitride semiconductors is the ability they show to form
alloys. In fact, aluminium nitride (AlN) and GaN have a continuous solid
solubility and despite the fact that indium nitride (InN) has limited solu-
bility in GaN, obtaining ternary alloys of Alx Ga1−x N and Inx Ga1−x N is
possible. Controlling the concentrations on these alloys allows engineering
the material band gap ranging from 0.7 eV (infrared) for pure InN to about
6.2 eV (ultraviolet) for AlN, covering the entire visible spectrum. For this
reason GaN-based semiconductors became interesting for employment in
1
2 Properties of III-nitrides and RE in GaN
optoelectronic devices operating in this energy region.

Despite this recent interest, GaN and related semiconductors are known
for a long time now. In fact, in the beginning of the 20th century there
were already studies on AlN powder. In the early 1930s a study [6] has
been performed on the nitrogen compounds of gallium, namely GaN, also
in powder form. The step from powder form to single-crystalline nitrides
was taken in the 1960s when Maruska and Tietjen [7] employed the hydride
vapor phase epitaxy (HVPE) technique to grow GaN layers on sapphire, as
they had previously done with GaAs. The quality of the obtained layers was
suitable for preliminary studies of a variety of important semiconductors
physical properties. However, even when not intentionally doped, these
films had a high residual n-type background due to defects and impurities
introduced during growth. Hydrogen in particular, has an important role on
the passivation of acceptor doping, a mechanism that at the time was not
understood. This fact made p-type doping of GaN virtually impossible,
explaining the interruption of interest in the development of III-nitrides
semiconductors.
The interest in the III-nitrides was only recovered almost 30 years later
when other growth techniques became available. Efforts were focused on the
growth of these nitrides with less defects and impurities. Since bulk mate-
rial for GaN substrates was not available and is still nowadays difficult and
expensive to grow, heteroepitaxial growth of these films on sapphire or SiC
substrates with buffer AlN or GaN layers became a widespread alternative.
In 1986 H. Amano et al. [8] employed atmospheric pressure metalorganic
vapor phase epitaxy (MOVPE) to grow high quality GaN thin films on
sapphire (0001) substrates with AlN buffer layers. These films still had
elevated dislocation densities (many orders of magnitude higher than the
values found for GaAs, for example) due to the large lattice mismatch and
thermal expansion coefficients of film and substrate. The following years
were accompanied by efforts to reduce unintentional contamination and de-
fect density of the films. Optimizing of growth techniques was accomplished
through detailed studies of the influence of temperature and gas flow rates
on the film quality. With this, the residual n-type doping was brought to
1.1 III-nitrides historical background and their applications 3
the present level of 1017 cm−3 [9]. The breakthrough that brought GaN
and related materials again to the spotlight came in 1989 when Amano and
collaborators announced [10] they obtained p-type doped material after ir-
radiating a MOVPE grown Mg doped GaN wafer with an electron beam
of 10 keV (well below the subthreshold energy necessary for atom displace-
ment). They demonstrated the efficiency of hole injection from the p-type
GaN:Mg into the undoped n-type film by fabricating a GaN UV-LED with
a p-n junction.
In 1991, Nakamura et al. obtained low resistivity p-type GaN:Mg by post-
growth thermal annealing in N2 at temperatures ≥ 700o C. They con-
cluded that the reason why p-type dopant activation was so difficult to
achieve was the elevated levels of hydrogen introduced in the film during
its growth. In fact H is present in most of the precursors employed for
GaN growth, such as (CH3 )3 Ga and N H3 in metalorganic chemical vapor
deposition (MOCVD) growth. The presence of H leads to the passivation
of the acceptor dopant. Nakamura and his collaborators have observed that
this reaction can be driven in the reverse direction by either annealing the
samples or injecting minority carriers (electrons) using low energy electron
beam irradiation [11, 12].
Since the first GaN p-n junction, intensive efforts have been put on the
improvement of growth processes to obtain better quality material. Also,
GaN-based devices became more complex and efficient, covering a wide
range of applications from transistors, through ultrahigh power switches,
to laser diodes. AlGaN/GaN-based electronics have demonstrated [13, 2]
superior characteristics. Obtaining GaN-based light emitting devices oper-
ating in the blue and ultraviolet region of the spectrum was one of the driv-
ing forces of III-nitride research. Again, at the end of 1995 Nakamura and
collaborators were on the front line of development of this technology with
their InGaN multi-quantum-well (MQW) active region laser diode [14]. In
July 2002, Sumitomo Electric Industries [15], announced the development
of a growth technique that allows reducing the density of dislocations in
GaN to about 1 × 106 /cm2 . The Dislocation Elimination by Epitaxial
growth with inverse-pyramidal Pits (DEEP) technique allows reducing dis-
locations by forming inverse-pyramidal pits on the surface of the grown

material. This low dislocation material can be used to fabricate blue-violet
lasers with superior lifetime performances. Operating in the violet-blue
region of the spectrum (380-450 nm), this laser came to replace the red-
infrared (650-780 nm) GaAs-based existing lasers. Since the density of
information recorded on optical media increases with the inverse squared
of the laser wavelength, the violet-blue laser diodes allow increasing the
storage capacity on a disc, from the actual 4.7 Gbytes of a red laser device
to about 27 Gbytes (54 Gb double layered). In fact, GaN-based lasers were
very recently in the center of a battle to establish the format of the next
generation of optical data storage [16]. Both Blu-Ray (from Sony) and HD-
DVD (from Toshiba and NEC) drives are equipped with blue-violet GaN
lasers diodes operating at 405 nm.
Also in the field of wireless communications GaN has proven to be a
reliable alternative to Si. Giant of electronics, Fujitsu [17] has developed
GaN high electron mobility transistors (HEMT) with high output powers,
higher breakdown voltages and cut-off frequencies.
These examples evidence well the technological relevance of GaN and
its related compounds and why these materials are and will continue to be
the subject of an active research field.
1.2 Growth of crystalline III-nitrides

In the previous section, several nitrides growth techniques were mentioned
along with the improvements each of it introduced to the crystalline quality
of the grown layers. A common problem to all of those techniques is the
choice of an adequate substrate. Throughout the years, due to the non-
existence of good quality, affordable and easy to obtain GaN substrates,
heteroepitaxial growth of GaN films was performed on several more avail-
able substrates. Among some of the most common substrates used to grow
nitride films upon are Si, GaAs, SiC, ZnO and sapphire. From this list,
SiC offers the best conditions for heteroepitaxial growth since its lattice
presents a mismatch of only 3.5% to the one of GaN and its thermal ex-
1.2 Growth of crystalline III-nitrides 5
pansion coefficients are the closest to the ones of GaN. However sapphire
substrates became the most popular due to their wide availability, hexag-
onal symmetry, ease of handling, simple pre-growth cleaning requirements
and high temperature (required during film growth) stability. Nevertheless
the lattice and thermal mismatches between sapphire and GaN (about 16%
of lattice mismatch) are responsible for the considerable amount of strain
on the material after post-growth cooling [3].
1.2.1 Nitride growth techniques

Presently mainly two techniques are employed to grow high quality III-
nitride films. In metalorganic chemical vapor deposition (MOCVD), also
known as MOVPE, metalorganic gases such as tri-methylX - (CH3 )3 X - or
tri-ethylX - (C2 H5 )3 X - with X being Ga, Al or In, transport these metals
onto the substrate. Simultaneously N is introduced through a flow of am-
monia (N H3 ). Both reactant gases, diluted with H2 , are introduced in a
reactor chamber through a nozzle directing the flow onto a high temperature
(∼ 1000 o C) heated substrate. The reaction of both gases at the substrate
yields a deposited film of Ga, In, or AlN. The disadvantage of this method
resides at the elevated substrate temperature necessary to decompose N H3 .
In fact, due to the thermal mismatch with the substrate, postgrowth cool-
ing introduces significant amounts of strain and structural defects into the
nitride film. Also, at these high temperatures residual contaminants can be
introduced in the film and III-metal desorption, diffusion and segregation
can occur. An alternative growth technique that allows reducing the sub-
strate temperature is molecular beam epitaxy (MBE). With this technique,
N supplied by microwave plasma excitation reacts with Ga vapor from an
effusion cell when both are directed toward a heated substrate. The pro-
cess is usually performed in an ultra-high vacuum environment to reduce
contamination. The main disadvantages of MBE while III-nitride growth
technique are related to the growth rate. This rate is limited by the avail-
able flux of low kinetic energy reactive nitrogen ions. While attempting to
increase this rate Ga droplets are observed to form on the surface. Also,
when microwave power is increased, more energetic ions are created. These
more energetic ions are in general detrimental to crystal quality since they
can introduce point defects.
1.2.2 Buffer layer

Since in both growth methods sapphire is the most commonly used sub-
strate, a buffer layer is usually required to minimize the effects of lat-
tice and thermal mismatch. Usually AlN or GaN buffer layers are em-
ployed. The vast majority of the films employed in this study were grown
by MOCVD at the semiconductor group from the university of Montpellier
(GES-Montpellier), a partner institution of the RENiBEl network. Their
III-nitride growth method is composed by several steps performed at at-
mospheric pressure. The process begins with a nitridation of the substrate
at about 1100 o C under a N H3 flow to remove impurities from the surface.
During this step, a thin layer (20-50 Å) of AlN is formed as N from the am-
monia reacts with Al from the sapphire. The temperature is then brought
down to about 550 o C to deposit a thin (∼ 250 Å) GaN buffer layer. It
has been observed that the buffer layer thickness has a strong influence on
the quality of the grown film. This low growth temperature causes this
buffer layer to be amorphous. By annealing the wafer at a temperature of
∼ 1070o C during a few minutes, the buffer layer will crystallize, resulting
on a highly defective crystalline template layer that allows reducing the
lattice mismatch for epitaxy.
The second phase of the process starts by reducing the temperature
to about 980 o C. At this point the reactant gases are allowed to react
at the buffer layer surface. A large number of nucleation sites begins to
form and will evolve to the shape of isolated monocrystalline islands on
top of the buffer layer. These islands will grow laterally and will start
to coalesce and the nitride film is grown. This process is schematically
represented in figure 1.1. It is possible that during growth, these islands
will have slightly different crystalline orientations and, as a consequence,
at the coalescence boundaries between islands, a considerable amount of
extended defects might form. This has a direct impact on the crystalline
quality since after coalescence, the growth will continue upwards and the
1.2 Growth of crystalline III-nitrides 7
Fig. 1.1: MOCVD growth steps of III-nitrides [18]
stacking faults formed at boundaries will proceed up to the film surface.

The grown film is said to exhibit mosaicity. This situation is depicted in
figure 1.2. As will be discussed in chapter 2 these structural defects will
influence the electrical and optical properties of the nitride film.
Fig. 1.2: Mosaic growth of the III-nitride film

1.3 Brief overview of III-nitride properties

As mentioned in section 1.1, nitrides structural, electrical and optical prop-
erties attracted the attention of semiconductor industry to these materials.
In this section, a brief overview of III-nitrides’ most relevant properties
for the present work will be given, with particular emphasis on the prop-
erties of GaN. For a more comprehensive description of the properties of
III-nitrides, the reader is referred to references [19, 20, 21, 22].
1.3.1 Structural properties

The III-nitrides can crystallize in two structures, namely wurtzite and
zincblende. However, the zincblende structure is thermodynamically meta-
stable and thereby less common. In this study, wurtzite GaN films have
been employed. For such structure, each of the group-III atoms (Ga,In or
Al) is located at the center of a tetrahedron on whose vertices N atoms
are found. In the same way, each N atom is surrounded by four group-III
atoms. The Bravais lattice of wurtzite can be seen as two inter-penetrating
hexagonal close packed sublattices, one with the group-III atoms and the
other with N atoms. This structure is illustrated on figure 1.3. This struc-
ture is characterized by lattice parameters a and c, as well as by a u-value
given by u=b/c where b is a bond length in the direction perpendicular to
the hexagons. This direction is commonly referred to as the crystal c-axis.
The ideal wurtzite structure is characterized by ratios c/a = 1.633 and
u = 0.375. The parameters of wurtzite GaN are quite close to those ideal
values, with c = 5.1850(5) Å, a = 3.1892(9) Å and u = 0.377(1)[19]. The
space group symmetry of wurtzite III-nitrides is C6v4 (P 6 mc) with a C
3 6v
(6mm) point group symmetry.
1.3.2 Thermal properties

GaN is a robust material with demonstrated superior thermal stability.
It has an elevated melting point of 2500 o C, thermal conductivity of 1.3
W cm−1 o C −1 and a Debye temperature of 600K. Maruska and Tietjen
[7] have studied the lattice parameters of wurtzite GaN as a function of
1.3 Brief overview of III-nitride properties 9
Fig. 1.3: Wurtzite structure of group III nitrides
temperature for the range of 300-900 K. They found a mean coefficient

of thermal expansion for the a direction of ∆a/a=5.59 × 10−6 /K for the
entire temperature range, and a superlinear temperature dependence for the
c direction with mean coefficients ∆c/c=3.17×10−6 /K and 7.75×10−6 /K
for the regions between 300-700 K and 700-900 K, respectively. These values
differ considerably from the values of the sapphire substrate: ∆a/a=7.5 ×
10−6 /K and ∆c/c=8.5 × 10−6 /K. This difference is responsible for the
appearance of strain between substrate and GaN film after post-growth
cooling. Strain release leads to cracks and other structural defects that
influence the electrical and optical properties of the film.
1.3.3 Optical properties and band structure
One of the reasons why III-nitrides are so interesting for optoelectronic ap-
plications resides in the fact that these semiconductors have a direct wide
energy band gap. Optical emission from interband electron-hole recombi-
nation in the III-nitrides and their ternary alloys covers an important part
of the electromagnetic spectrum, ranging from the infra-red, through the
entire visible spectrum, to the ultra-violet region (Fig.1.4).
The band gap characteristics of a semiconducting material are respon-
sible for a wide range of its properties. Figure 1.5 illustrates the main
features of the band structure of wurtzite GaN, as calculated by Suzuki et
Fig. 1.4: Band gap energy versus lattice constant of III-nitride semiconductors at
room temperature [23].
al. in reference [25]. As can be seen, the top of the valence band is split
into three states. This splitting is a direct consequence of the fact that
the Ga 3d core-level energies are resonant with the N2s -like lower valence
band states. Due to this resonance, the 3d Ga electrons hybridise strongly
with both the upper- and lower-valence band s and p levels. With a band
gap energy of 3.39 eV, GaN inter-band luminescence is located at the UV
region of the spectrum, as shown on figure 1.4.
1.3 Brief overview of III-nitride properties 11
Fig. 1.5: Band structure of wurtzite GaN [24].
1.3.4 Electrical properties
As discussed in section 1.1, as-grown heteroepitaxial wurtzite GaN has an

elevated intrinsic electron concentration, being the material unintentionally
n-type doped. In 1995, BogusÃlawski et al. [26] have attributed this fact
to the high density of structural defects introduced during growth, such
as nitrogen vacancies, as confirmed by ab initio molecular dynamics cal-
culations. In their study, these authors concluded that such native defects
introduce energy available states in the band gap.
In more recent studies (2004), Van de Walle and Neugebauer [27] have
employed more advanced computational methods to investigate the un-
intentional n-type conductivity of GaN. From their work the authors con-
cluded that such property of as-grown GaN cannot be attributed to nitrogen
vacancies, but is more probably due to the unintentional incorporation of
O and Si impurities during material growth. In the same manner as struc-
tural defects do, those impurities lead to the formation of energy states in
the band gap. Those levels interact with the free charge carriers and can
GaN AlN InN

Lattice parameter a [Å] 3.189 3.112 3.548
Lattice parameter c [Å] 5.185 4.982 5.760
Therm. exp. ∆a/a [/K] 5.59 × 10−6 4.2 × 10−6 4 × 10−6
Therm. exp. ∆c/c [/K] 3.17 × 10−6 5.3 × 10−6 3 × 10−6
Therm. conduc. [W/cm K] 1.3 2 0.8
Atomic density [at/cm3 ] 8.76 × 1022 9.58 × 1022 6.35 × 1022
Density [g/cm3 ] 6.15 3.23 6.81
TDebye [K] 600 1150 660
Melting temp. [o C] 2500 3000 1100
Brkdown field [V/cm] 5 × 106 1.2 − 1.8 × 106 −
e mob. [cm2 V −1 s−1 ] ≤ 1000 300 3200
h mob. [cm2 V −1 s−1 ] ≤ 200 14 −
Dielec. const. (static) 9 8.5 15
Dielec. const. (hi. freq.) 5.35 4.68 − 4.84 8.4
Refract. index n 2.29 2.1 − 2.2 2.56 − 3.12
Energy gap [eV] 3.39 6.2 0.7 − 1.9[4][5]
Table 1.1: Basic properties of Ga, Al and InN at 300 K [3, 19].
thereby have a strong influence on the electronic properties of GaN, such

as carrier mobilities and diffusion coefficients.
A resume of the basic structural, electrical, thermal and optical prop-
erties of GaN, AlN and InN is given in table 1.1.
1.4 Rare-earth elements
The elements of the periodic table constituting the lanthanide series, rang-
ing from cerium (Ce - atomic number 58) to ytterbium (Yb - atomic number
70), are often known as the rare earth (RE) elements (Fig. 1.6). The term
Fig. 1.6: The rare-earth elements

1.4 Rare-earth elements 13
rare earth was proposed due to the fact that when the first RE were discov-
ered they were thought to exist in the earth crust only in small amounts and
because they had to be extracted from materials known as “earths”, such
as lime and alumina. Today it is known that each of them is more common
than platinum, gold or silver. RE are never found as free metals in the
earth’s crust but rather in compounds of various RE and non-metals. They
are all chemically very similar, a fact that makes their complete isolation
and classification very difficult.
1.4.1 Properties of rare-earths
The rare earth elements are metals presenting high lustre and electrical
conductivity. Their bulk color is often silver, silvery-white or grey. RE
rapidly react with oxygen in air, forming oxides. They all have elevated
melting points (≥ 800 o C) and tend to form ionic compounds. Most RE-ions
are trivalent, with samarium, europium, thulium and ytterbium also having
valence +2 and cerium, praseodymium and terbium +4. Their electronic
configuration is [Xe]4fn 5d0 6s2 with n varying from 1 (Ce) to 14 (Yb).
1.4.2 RE in GaN for luminescence emission
It is their electronic charge distribution that makes RE very interesting for

optoelectronic applications. As illustrated in figure 1.7, the partially filled
4f electronic-energy levels are located quite close to the nucleus and are
shielded from external fields by 5s2 and 5p6 outer-shell electrons. For this
last reason, the intra 4fn shell electronic transitions result in very sharp
optical emission [29] at wavelengths ranging from the ultraviolet to the
infra-red. It should be emphasized that the nature of this RE-luminescence
is different from that originating from the intrinsic inter-band electron-hole
recombination in the host semiconductor, which depends on the material
band gap. The wavelength of the RE emitted light is determined solely
by the energy of the transition between the 4f states and is thereby rel-
atively independent of the host material. However, in the free (isolated)
RE3+ state, those transitions would be forbidden due to parity conservation
Fig. 1.7: Approximate charge distributions of electrons in 4f, 5s, 5p, 5d, 6s and 6p
orbitals, evidencing the shielding of the 4f electrons by the outer-shell electrons
[28].
[29]. When the RE3+ is integrated in the matrix of a III-V semiconductor,

the crystalline electric field around the RE-ion will produce the splitting
of the energy levels - known as Stark splitting. Depending on the total
angular momentum quantum numbers of the initial and final 4f levels, the
wavelength of the radiation, and properties of the host material such as its
refractive index and absorption coefficient, certain transitions are predom-
inant, leading to the observed emission.
Figure 1.8 shows the allowed transitions of europium, erbium and thulium
in GaN. Steckl et al. [31] have reported photoemission from RE-doped GaN
covering the entire visible spectrum: red (from Eu at 621 nm and Pr at 650
nm), green (Er at 537/558 nm) and blue (Tm at 477 nm). Apart from the
pure RBG colors, these authors obtained mixed colors by co-doping GaN
films with combinations of RE ions.
Fig. 1.8: Simplified energy diagram of the 4f levels of Eu, Er and Tm in GaN[30]
Despite the fact that the host material has little influence on the wave-
length of the emitted luminescence, it does have a strong effect on the
photoemission intensity (radiative transition probability) of that lumines-
cence. The intense light emission obtained from RE-doped GaN can be
partially attributed to the ability of GaN to incorporate considerable con-
centrations of optically active RE species. In conventional semiconductor
hosts such as Si or GaAs, elevated RE concentrations result in emission
quenching due to degradation of the host material and RE precipitation
[32]. Another advantage of using GaN (and wide direct band gap semi-
conductors, in general) as a host for RE-luminescence is that luminescence
intensity does not quench with increasing of temperature until values well
above room temperature [31]. This is in good agreement with the empirical
studies of Favennec et al. [1], as previously mentioned. Due to these prop-
erties, luminescence obtained from RE-doped III-nitrides is in competition
with inter-band luminescence obtained from Alx Ga1−x N and Inx Ga1−x N
alloys, as described in section 1.1.
Luminescence from RE-doped III-nitrides requires the introduction of
these dopants in the host semiconductor. This can be accomplished by
three processes, namely diffusion doping, in situ doping during growth or
by ion implantation. The first method has limited use since RE’s have low
diffusivity and III-nitrides have relatively low decomposition temperatures

[29]. In situ doping is currently the most frequently used method to obtain
light emitting devices based on RE-doped III-nitrides [33, 34]. However,
this method of introducing RE dopants has quite some important restric-
tions. The limited solubility of RE’s in the host material as well as RE
cluster formation, restrain the incorporation of RE in sufficiently high con-
centrations to reach intense emissions. The introduction of contaminants
along with RE might also be a limiting factor. Patterning for lateral color
integration, for example, is difficulty to achieve by in-situ doping due to
lack of control on the dopant lateral disposition.
The samples investigated in this study were prepared by means of ion
implantation. This method allows overcoming the limitations of in situ
doping. By employing this non-equilibrium process the dopant solubility
constraints are much more relaxed. Ion implantation allows to introduce
elevated dopant concentrations before precipitation starts to play a role.
Also, due to the possibility of introducing mass separation, contaminants
are eliminated and isotopically pure dopant beams can be used. Further-
more, the implantation technique offers the advantage of exact control of
the dopant concentration and depth distribution, as well as the possibility
of lateral patterning. However, the strongest disadvantage of this doping
technique is the fact that it leads to the introduction of radiation damage
in the crystalline lattice. Such structural defects generate non-radiative
carrier recombination centers that hinder the material luminescence. Post-
implantation thermal treatment steps are frequently employed in order to
reduce the radiation-induced damage.
In this chapter, an overview of the fundamental properties of III-nitride
materials, with special emphasis on GaN, was given. Such properties allow
explaining the increasing interest in choosing these materials as hosts for
RE-ion doping, with potential interesting applications in the electrolumi-
nescent device industry.
As discussed in the introductory chapter, the main objective of the
RENiBel network was to understand the fundamentals of the interaction
between RE-dopants and III-nitride hosts. To accomplish that goal it is
necessary to deepen this discussion into the electronic band structure of

the material.
Chapter 2
Energy band structure of

semiconductors
2.1 Band structure in solids
A great variety of semiconductors properties are fundamentally explained

by means of their electronic structure. This structure depends on how
atoms composing the material are arranged in space and the type of bonds
established among them.
Let us consider two free atoms initially separated by an infinite distance.
As they progressively approach each other, increasing-strength interactions
between electrons and nuclei on both atoms start to manifest. The wave
functions of electrons on both atoms begin to overlap having this a direct
influence on the electronic states, namely a split in energy, as can been seen
in figure 2.1 a). Increasing the number of atoms in the material results on
the denser distribution of the electronic states as seen in figure 2.1 b) for a
system containing N atoms. Further increasing N to the limit found in real
macroscopic systems will result in more compact distributions of electronic
states that can than be regarded as continuous distributions, also referred
to as bands. These bands have their origin in the orbitals of the more
external electrons since the ones closest to the nuclei have very localized
wavefunctions that will not overlap.
19
20 Energy band structure of semiconductors
Fig. 2.1: Split of energy of electronic states [35]
2.1.1 Electrons in semiconductors
To understand how the band structure appears in semiconductors we start

from a simple system - an electron moving in space without the influence
of any potential. In such case, by solving the Schrödinger equation for the
system, it is possible to describe the set of energy states E accessible to the
electron, as a function of its momentum p(k) = ~k, schematically illustrated
in figure 2.2. Here, ~ is the reduced Planck constant and k is the module
−
→
of the electron wave-vector k =| k |= 2πλ , being λ the wavelength associated
to the electron. A more formal treatment of the quantum mechanical for-
malism describing the movement of a free electron in space can be found
in elementary physics text books, such as reference [36].
However, when an atomic nucleus of charge +Ze is placed somewhere
in space, it will induce a well of potential energy capable of localizing the
electron. In fact, if the well is infinitely deep and wide, there will exist wave
functions limited to the nuclear vicinity, called bound states, as illustrated
in figure 2.3. These bound states will be of energy inferior to the one of a
free electron with zero kinetic energy.
These two situations - free and bound electrons - are opposite extreme
2.1 Band structure in solids 21
Fig. 2.2: Set of points representing the states of a free particle of mass m.
Fig. 2.3: Wave-functions of electrons in a nuclear potential well.

Fig. 2.4: Periodic potential of a lattice of atomic nuclei.
cases of what happens to electrons in semiconductors, however, the inter-

mediate cases are the relevant ones to our purpose.
Let’s consider now, for the sake of simplicity, that the electron is con-
fined inside a 1-dimensional semiconductor of size L. Its wave-function can
only have certain wavelengths λ=2L, 2L 2L 2L 2π
2 , 3 , ... n , or since k = λ , it can
2π π 2π 3π
only have certain wave-vectors k = 2L = L , L , L , ..., nπ
L . Furthermore, an
electron in a semiconductor will no longer only have kinetic energy, but it
will move under the influence of a periodic potential built by the lattice
of atoms composing the material. In our one-dimensional semiconductor
model, this periodical potential will appear when the atomic nuclei are
arranged periodically along the linear segment L with periodicity a, as de-
picted on figure 2.4.
Considering that the periodic potential is weak and that fluctuations are
sufficiently small, the electron will encounter an average potential Vaverage
(figure2.4). This average weak potential can be considered as a small per-
turbation to the electron’s wave-function. The influence of this potential on
the electron is small and we speak of the nearly-free electron approximation
[37, 39]. In fact, neither the shape of the wave-function nor the electron
energy will be drastically affected by the presence of such potential.
The assumption that the periodic potential has little effect on outer
electrons is validated by two facts: - on one hand, the nuclear force has a
short range for interaction and Pauli exclusion principle forbids outer elec-
trons to enter the totally filled inner orbitals; on the other hand, electrons
from the inner shells contribute to significantly reduce the amplitude of the
nuclear charge experienced at the site of outer electrons.
The effect of such periodic potential on the electron wave-function was
described by Felix Bloch (see for example, reference [39]), as being the mod-
ulation of the wave-function by a function having the potential periodicity.
The closer to the nuclei electrons are, the stronger the influence of the peri-
odic potential, and the more localized those electrons will be. At the limit,
these electrons become bound to an individual ion and will not participate
in electric conduction.
In the case of outer electrons, with generic k wave-vectors as previously
indicated, for which the periodic potential is weak, the electron energy
2
E is still essentially a parabolic function of k : E = ~k 2m . For electrons
with such k -values the crystal will be transparent, and they are “free” to
move through the material. However, there will be some special values of
k for which the perturbation cannot be considered small, independently
of the potential intensity. This happens when the condition nλ=2a, or
k= 2π π
λ = n a is satisfied. Note the analogy with Bragg’s law for diffraction of
electromagnetic radiation on a lattice with periodicity a (appendix B). At
such k -values electrons are diffracted. The amplitude of the incident wave
will strongly decay, losing its intensity to the diffracted wave. However,
since the diffracted wave also satisfies the Bragg condition (same k -value),
a stationary wave is obtained. These special values of k = ±n πa where
dispersion occurs receive the name of Brillouin zone boundary and the
regions therein comprised are called the Brillouin zones. Depending on the
value of n, they are called first Brillouin zone (n = 1), second Brillouin zone
(n = 2), etc.
It can be demonstrated ([37]) that at each Brillouin zone boundary,
the electron wave-function Ψk will have two values, Ψ+ −
k and Ψk , to which
two eigenvalues of energy will be associated: Ek+ = Ek + Vk and Ek− =
Ek − Vk , respectively. In the E/k diagram this appears as a discontinuity
at the Brillouin zone boundaries as seen in figure 2.5 b). Due to the crystal
periodicity, from the point of view of translation operations, k and k ±
n 2π
a are equivalent. As such, the electron states can be represented in the
Fig. 2.5: Extended zone schemes. a) represents the E/k diagram for a free elec-
tron, b) the equivalent diagram for an electron in a crystal with atoms displayed
with a periodicity a, c) the reduced zone scheme and d) the repeated zone scheme.
[38]
Fig. 2.6: Energy gaps (white areas) between three energy bands (grey areas).
reduced E /k diagram of figure 2.5 c). The energy discontinuity at the

borders of the Brillouin zone, as represented in figures 2.5 b), c) and d) is
responsible for the appearance of zones of forbidden electronic energy states.
Such a region is commonly known as energy gap. Figure 2.6 illustrates the
appearance of energy gaps between continuum bands of electron accessible
energy states. A schematic representation of the band structure of GaN
has already been shown in figure 1.5.
The population of the electron states starts from the levels of lowest
energies, following the exclusion principle of Pauli and the Fermi-Dirac dis-
tribution function. The inner electrons, also known as core electrons, are
found in completely filled bands with an even amount of electrons. This
follows up until the valence electrons. The number of valence electrons
per unit cell determines whether the last energy bands are partly or to-
tally filled. This directly determines the substance electrical properties. In
fact, this allows distinguishing between conducting or insulating (or semi-
conducting) materials. A simple metal is, by definition, a substance with
odd number of electrons per primitive cell, yielding at least a partly filled
energy band. In an insulator, or semiconductor, the last completely filled
energy band is separated from the next empty band by an energy gap.
Fig. 2.7: Band scheme for metals, semiconductors and insulators.
2.2 Electronic conduction in semiconductors
At this point, it is important to mention two special energy bands often

mentioned in semiconductors terminology. The valence band (VB) is the
band of states occupied by the valence electrons of a material. A band of
states that will never be completely filled with electrons - where there will
always be free states available - is known as the conduction band (CB). A
semiconductor is a particular case of an insulating material, with a small
energy gap between the completely filled VB and the next completely empty
(at T=0 K) band of states (CB), as illustrated on figure 2.7.
Due to the fact that at T=0 K the VB is completely filled and the CB
empty there will be no electrical current and the semiconductor behaves
as an insulator. For temperatures T>0 K, some electrons from the top of
the valence band can be thermally excited to the bottom of the conduction
band following the Fermi-Dirac distribution function. The electrons excited
to the CB leave empty states in the VB so that both bands will be partly
filled and both will thereby contribute to electrical conduction. The empty
states at an almost filled VB, also known as holes, are often seen as counter
particles with positive charge, for the electrons excited to the CB. In fact,
holes behave as a positively charged particle when under the influence of
an electric field. With this in mind, it is valid to state that, in a semicon-
ductor, the current is carried by electrons at the bottom of the CB and by
positively charged holes at the top of the VB. Due to the nature of their
2.3 Optical emission 27
Fig. 2.8: Charge carriers under the influence of an electric field E.
charge, electrons and holes are accelerated in opposite directions, under the
influence of an electric field. Both types of charge carriers will contribute to
the total current. In fact, the total current density will be the sum of two
contributions with the same sign: Je = n(−e)vd,e and Jh = pevd,h , where
e is the electron charge, n and p are the density (/cm3 ) of electrons in the
CB and holes in the VB, respectively and vd is the carrier drift velocity.
Since vd,e has an opposite sign to the applied electric field, Je will be in the
same direction of E, so that it has the same sign as Jh as shown in figure
2.8.
2.3 Optical emission
The optical properties of a semiconductor are dominated by the inter-band

transitions. An electron in the VB can be excited across the band-gap
into a state in the CB. This excitation can have different causes, such as
thermal excitation, absorption of a sufficiently energetic photon, etc. As a
consequence of the electron promotion to the CB, a hole is left in the VB,
and after a certain period of time the system will minimize its energy by
recombining the electron-hole pair. This happens when the electron emits
its excess of energy and returns to the initial state in the VB, annihilating
the hole. For both situations (upwards - excitation - or downwards - relax-
ation) transitions between two quantum states occur with conservation of
energy and crystalline momentum:

½
EV (k 0 ) − EC (k) = hν
(2.1)
k 0 − k = kγ .
In this example, an excited electron filling a state (EC , k) in the CB,

released its excess energy as a photon of energy hν and momentum kγ and
recombined with a hole in a state (EV , k 0 ) in the VB. However, typical
energies of de-excitation are of the order of a few eV, implying wavelengths
of emitted electromagnetic radiation of the order of 1 µm, so that kγ is of
the order of 10−3 Å. Comparing this with the typical crystalline momenta,
such as the border of Brillouin zone at 2π a ∼ 1 Å
−1 with a ∼ 1 Å, we
conclude that kγ is negligible. As such, k 0 − k ' 0, or k 0 ' k, meaning

that electronic transitions occur for the same value of k. As a consequence,
since the most probable transitions are the ones occurring between the top
of the VB to the bottom of the CB, in a material where these two points
occur at different k -values, no transitions between those two values will be
allowed. A material for which the maximum of the VB and the minimum
of the CB occur at the same k -value is said to have a direct band-gap.
GaN, InN and AlN are examples of direct band-gap semiconductors. Si,
BN and GaP are indirect band-gap semiconductors. For indirect band-
gap semiconductors, inter-band transitions are still possible, though less
probable. These transitions must however, be aided by a phonon. Phonons
are lattice vibrations and as opposed to photons, they have high crystalline
momenta and negligible energy. So in these transitions, the photon will
supply the needed energy (vertical transition component) and the phonon
will contribute to the necessary momentum change (horizontal transition
component). Indirect band-gap transitions are less probable and depend
on the temperature since T controls the phonon population in a material.
2.4 Intrinsic and extrinsic semiconductors

A semiconductor is said to be intrinsic when electrical conduction occurs
only due to thermal excitation through the energy gap. This can be changed
by incorporation of impurities and/or defects present in the material.
2.4 Intrinsic and extrinsic semiconductors 29
2.4.1 Intrinsic semiconductor

The number of occupied states in the CB is given by (ref. [39])
Z ∞
n= ge (E) < n(E) > dE, (2.2)
EC
with ge (E) the density of states in the conduction band and < n(E) >
the average state occupation number given by the Fermi-Dirac distribution
function:
1
< n(E) >= E−εF , (2.3)
e kB T + 1
where εF is the Fermi energy, the energy of the highest occupied quantum
state at T = 0K and kB is the Boltzmann constant. Equivalently, the
number of empty states, or holes in the valence band is,
Z EV
p= gh (E)[1− < n(E) >]dE, (2.4)
−∞
with gh (E) the density of holes in the valence band. Taking into account
that for typical semiconductors at RT, EGap ∼ 1 eV so that EGap >> kB T
E−εF εF −E
− −
and < n(E) >≈ e kB T and 1− < n(E) >≈ e kB T (often referred to as
nondegenerated semiconductors condition), integral evaluations yield:
 E −ε
 − C F
n = NC e kB T
ε −E (2.5)
 p = N e− FkB T V
V
with NC = 2[ 2πmhe2kB T ]3/2 and NV = 2[ 2πmhh2kB T ]3/2 , the effective state

density in the CB and CV, respectively.
An intrinsic semiconductor is characterized by n = p = ni , being ni =
EGap
−
(NC NV )1/2 e 2kB T the intrinsic carrier density. It can be demonstrated
[37] that in this case, εF will lie very close to the middle of the energy gap,
εF ' EV +E
2
C
.
2.4.2 Extrinsic semiconductor

When conduction is dominated by impurities and/or defects, we speak of
an extrinsic semiconductor. To simplify, let’s consider the example of Si
Fig. 2.9: a) Intrinsic Si, b) p-doped Si and c) n-doped Si [40].
in figure 2.9 (for GaN, composed by two atomic species, similar reasoning
can be done). In silicon, every Si atom will share its four valence electrons
with four neighboring Si atoms forming four covalent bonds (figure 2.9 a)).
Replacing one of the matrix Si atoms by Al, for example, will change the
number of electrons in the valence band. Since Al has one less valence
electron than Si, a hole is created at the valence band (figure 2.9 b)). On
the other hand, if a Si atom is replaced by, for example, an atom of P
having one more valence electron than the matrix atoms, P will donate its
extra electron to the conduction band (figure 2.9 c)). The Si semiconductor
where an Al impurity has been introduced is said to be p-type doped, since
positive charges are introduced in the material due to Al doping. Al is
said to be an acceptor impurity. Conversely, Si doped with P is said to be
n-type, as negative charges are introduced in the material. P receives the
name of donor impurity. Once again, in what GaN concerns, some dopants
act as acceptors when replacing Ga or N and some others act as donors.
Others even can act both as acceptors and donors in GaN, depending on
the element they are replacing in the lattice and/or the position they take
(Ga,N-substitutional or interstitial).
In general, electron binding energy is defined as the energy required to
remove an electron from its atom. In the case of impurities, the binding
energy of the electron to the impurity is usually a factor of a thousand
smaller than the ground state binding energy of the free element [39].
For a donor impurity, the binding energy is measured relative to the energy
2.4 Intrinsic and extrinsic semiconductors 31
Fig. 2.10: a) donor level, b) acceptor level, c) deep donor and acceptor levels.
of the CB levels to where the electron will go, leaving the donor impurity
ionized. As such, donor impurities introduce additional electronic states
with energy Ed - figure 2.10a) - in the band gap, which are lower than the
energy of the states at the bottom of the CB, EC . The energy difference is
most of the times small compared to the energy gap EGap .
Concerning acceptor impurities, symmetry arguments allow extending
the previous reasoning of electrons and the CB, to holes and the VB. As
such, the binding energy of the hole to the acceptor dopant is now measured
relative to the VB since the hole will be promoted to a state there. As such,
acceptor impurities introduce additional electronic levels at an energy Ea
above the top of the VB - figure 2.10b).
At T = 0K, the extra electrons in a n-type doped semiconductor are
bound to the impurities, as holes are too in a p-type semiconductor. At
room temperature almost all impurities will be ionized.
Due to the fact that these levels lie close to the boundaries of the band
gap, they are often called shallow levels. Shallow levels have a fundamental
role in the electrical and optical properties of semiconductors. It is far more
probable to have an electron from a shallow donor level being excited into
the CB, or a hole from an acceptor level into the VB, than to promote an
electron directly from the VB into the CB. It is obvious then that for doped
semiconductors, impurities are the major source of free carriers.
Another category of levels can appear in the band gap. In fact, some
types of impurities and crystalline defects can be responsible for the pres-
ence of deeper levels, closer to the middle of the energy band gap - figure
2.10c). These deep levels can also be donors, acceptors, simultaneously

donors and acceptors or multiple donor or acceptor. In general, deep levels
act as very efficient carrier (electron or hole) traps.
Carrier density in an extrinsic semiconductor

Impurities must be taken into account while determining quantities such
as carrier concentrations and the position of the Fermi energy in the band
gap.
For an n-type semiconductor, let’s assume the presence of a shallow impu-
rity with energy ED below the CB and density ND such that ND << NC ,
the effective density of states in the CB. When the Fermi level is far enough
from the conduction band (EC − εF À kB T ), the density of CB electrons
is still given by n in equation 2.5. The amount of ionized donor impurities
is given by
+ ND
ND = ND [1 − Pe (ED )] = 1 εF −ED
, (2.6)
1 + 2 e kB T
where Pe (ED ) is the donor level occupation probability. The total amount
of free electrons will then be given by the sum of contributions from the
intrinsic process (thermal excitation from VB to CB) and impurity ioniza-
tion. Since the semiconductor is neutrally charged, the total amount of
negative created charges must equal the total positive charge. This results
+ +
in n = ND + p. Replacing here the results for n and p from 2.5 and ND ,
we obtain
E −ε
− C F ND ε −E
− Fk T V
NC e kB T = ε −E
+ NV e B . (2.7)
1 + 12 e FkB T D
Considering now that the dopant concentration is such that ND À ni
and that the Fermi energy is well below the donor level energy (ED − εF À
+
kB T ), we obtain ND = ND . This result indicates that under the required
conditions, all donor impurities
q will be ionized. Remembering also that
2 1 2
np = ni , n = 2 [ND + ND + 4n2i ]. In this regime (ND À ni ) we obtain
n = ND , and the concentration of electrons in the CB will be much higher
than the concentration of holes in the VB. In this case, the semiconductor
is said to be extrinsic - its properties are dominated by the impurities,
2.5 Doping 33
as opposite to what happens in a intrinsic semiconductor. Electrons are

said to be the majority carriers whereas holes are referred to as minority
carriers.
Carrier concentrations are, as we have seen, dependent on the tempera-
ture. The regime described above stays valid through a wide range of tem-
peratures, however increasing T high enough will result in a strong increase
of the intrinsic electron-hole pairs generation up to a point where ni > ND .
Beyond this point, even doped semiconductors will behave as intrinsic. On
the other hand, decreasing T to low enough values, the probability of find-
ing donor levels in their neutral state (occupied with an electron) increases,
with the consequence that n will decrease. Electrons at the CB will de-
excite back to the donor levels, where they will be “frozen”. This is often
known as the “donor freeze-out” regime.
This discussion can easily be extended to p-type semiconductors using
simple charge symmetry arguments.
2.5 Doping
As seen in the previous section, properties of semiconductors can be al-
tered through the introduction of impurities into the semiconductor lattice.
Doping can be achieved by introducing the dopants during semiconductor
growth, thermal diffusion into the semiconductor or with ion implantation.
According with the desired property change, either electrical, optical or
magnetic, different dopants can be employed.
2.5.1 Electrical doping

Semiconductor doping has most of its application on the modification of
materials electrical properties. Obtaining n- and p-type materials is cru-
cial for the design of micro-electronic components. As described in 2.4.2,
dopants will introduce extra electron states in de semiconductor band gap.
Here, shallow donors play an important role, since they control the carrier
density in the material. The energy position in the band gap will depend on
the dopant chemistry and where it is incorporated into the host crystalline
lattice. Again, GaN and related semiconductors introduce extra complexity

as compared to mono-atomic semiconductors as Si and Ge. In fact, one has
to consider the effect of dopants when replacing Ga or N in the lattice.
Obtaining n-type GaN has never constituted a problem, since typical as-
grown GaN has already an elevated free electron concentration. This has
its origin on defects created during growth. However the way these defects
are introduced doesn’t allow to control the carrier density.
Si is the most used dopant to obtain n-type GaN [41] in a controlled way,
creating a shallow level at about 30 meV [42] below the CB, when it re-
places Ga. Oxygen will also create a donor state at 30 meV but only about
10% of the O ions will become electrically active. S and Te induce donor
levels at 48±10 and 50±20 meV below the CB, respectively [41]. p-type
GaN is more difficult to obtain. This happens mainly due to the high free
electron concentration in the undoped GaN and due to the inexistence of
suitable shallow acceptors. Mg is the most commonly used dopant to obtain
p-type GaN but still its far from being an ideal acceptor since it induces
an acceptor level at about 170 meV [41] (compared to the 30meV of Si
as donor). With these values, ionization efficiencies of only a few percent
are obtained at room temperature. This implies that, in order to obtain
p-doping, elevated concentrations of Mg are required. It has been observed
that [41] co-doping of Mg with P enhances the substitution of Ga by Mg.
Another possible p-type dopant in GaN is Ca, creating an acceptor level at
about 165 meV below CB. Finally, Be is also predicted to have an acceptor
behavior, inducing a shallower (∼ 60 meV [43]) level than Mg. However,
Be tends to react with N and form Be3 N2 leading to a low solubility of Be
in GaN.
As previously mentioned, deep levels in the band gap play an important
role on the electrical properties of the material since they can trap carriers in
a very efficient manner. Transition metals were reported [44] to create deep
levels in GaN. However Cu, Cr, V, Mn, Fe and Ni are known contaminants
in MOCVD and HVPE grown GaN. As contaminants, these elements will
introduce deep levels in a non-controlled way, which in general is unwanted.
Other authors [45] have reported that Ti, Ni and Au, besides intro-
2.5 Doping 35
ducing deep levels in the band gap of GaN, will also act as donors. Rare
earth ions have also been reported by Filhol et al. [46] to introduce several
levels in the band gap of GaN. Among these, some deep levels that will be
involved in the luminescence mechanisms, as will be discussed later.
2.5.2 Magnetic doping

Another application of dopants is the modification of the magnetic prop-
erties of materials. Electron spin manipulation has opened the possibility
for spintronic devices, such as spin-controlled switches and memories [48].
Integration of this new technology in the existing semiconductor applica-
tions is of capital importance for such devices. For this purpose, several
groups are actively investigating the magnetic properties of such systems,
in particular, ferromagnetism in dilute magnetic semiconductors (DMS).
Ferromagnetic behavior has been observed for some III-V semiconductors
doped with about 1-5 at. % Mn, such as GaMnAs, InMnAs and ZnMnSe.
However, the Curie temperature for these materials is still too low (TC ∼
110 K) to take advantage of their magnetic properties at room tempera-
ture. Theodoropoulou et al. [49] have studied the magnetic properties of
p-doped GaN implanted with 3-5 at. % of Mn. They observed ferromag-
netic behavior in this system with TC of ∼ 250 K. However, they report
that the ferromagnetic properties are due to the formation of Mn platelets
with the same structure of GaN but different lattice constant. Dhar et
al. [50] reported room temperature ferromagnetism from several transition
metal (TM) doped GaN but also observed that this behavior results from
the formation of precipitates rather than from a homogeneous alloy.
Hashimoto et al. [51] investigated the magnetic properties of MBE Eu-
doped GaN and observed evidence of a ferromagnetic-like phase, through
the measurement of hysteresis and saturation at 300 K. However they also
observed the gradual saturation of the magnetic moment with increasing
magnetic field at low temperatures, this being an indication of the co-
existence of a paramagnetic and ferromagnetic-like phases. Another RE
which showed more interesting properties is Gd. Dhar et al. [52] have also
investigated the magnetic properties of GaN:Gd layers. They report an
extraordinarily large magnetic moment (4000 µB per Gd atom) and fer-

romagnetism at temperatures above room temperature, with a Curie tem-
perature around 360 K, even for Gd concentrations as low as 1016 cm−3 . A
DMS with such an elevated TC is obviously a very attractive candidate as
a source of spin-polarized carriers to be employed in future semiconductor-
based spintronics.
Nevertheless, the mechanisms responsible for the magnetic behavior in-
duced by dopants such in the nitrides is still far from understood.
2.5.3 Optical doping
GaN and related materials became interesting mainly due to their optical
properties. With its direct band gap of width 3.4 eV, GaN is an interesting
material for optoelectronics, namely for ultra-violet, violet, blue, green and
yellow light emitting devices [47]. Pankove and Hutchby have performed an
exhaustive study of the luminescence properties of 35 dopants implanted
into GaN [53]. These authors have observed that Mg, P, Zn, Cd, Ca, As,
Hg and Ag produce a characteristic spectral photoluminescence signature.
They also reported a broad peak at about 2.15 eV (yellow region of the
visible spectrum).
The above examples, inter-bands transition luminescence and luminescence
from impurity-induced carrier recombination are not the only reason why
GaN became interesting for optoelectronics. As pointed out in the intro-
ductory discussion, the nitrides are also suitable hosts for a category of
known luminescent agents, the rare earth elements.
Rare earth elements as optical dopants in GaN
As described in section 1.4.1, the rare earth partly filled 4f electron orbitals
are so deeply buried within the electronic shell that they are shielded by
the outer 5s, 5p and 6s electron orbitals. Intra 4f shell electronic tran-
sitions result in very sharp optical emission whose wavelength is almost
independent of the host material. Different RE ions will yield luminescence
2.5 Doping 37
emission with different wavelength. For example, Eu emits around 630 nm

(red), Tm around 480 nm (blue) and Er around 540 (green) and 1540 nm
(infra-red). It has been demonstrated [32] that combining several RE ions
as optical dopants, color combination can be used to obtain other colors.
It should be emphasized that RE luminescence is of different nature than

the one obtained from inter band transitions and electron-hole pair recom-
bination. In the first case, luminescence results from electronic transitions
inside the RE 4f electron shell, whereas in the latter case the luminescence
wavelength is dependent on the band-gap energy or the energy level in the
band-gap that a dopant induces.
As mentioned in section 1.4.2, GaN is a suitable host for RE dopants
due to its ability to incorporate a significant concentration of those optical
dopants without precipitation and without PL or EL intensity quenching
[30]. However, the mechanism of energy transfer from the GaN host mate-
rial into the RE 4f electronic orbitals is still not fully understood.
Measurement of the optical spectrum of RE in III-V semiconductors in-
dicates that these ions will be in the 3+ oxidation state. Density functional
theory (DFT) studies performed within the RENiBEl network [54] have
been employed to conclude that the RE ions have a strong affinity to the
substitutional position of the group III element in the lattice. In this po-
sition, the RE intra-shell 4f -4f transitions will be allowed and thereby RE
characteristic light emission can be observed. These same studies indicate
that, despite the fact that RE substitutional impurities do not introduce
any deep donor or acceptor levels in GaN (as they behave as isoelectronic
impurities), they may introduce carrier traps. These results are in agree-
ment with the work of Lozykowski [55]. In his work on the kinetics of
RE-ions luminescence in III-V semiconductors, he proposes a model for the
energy transfer from host to the 4f electrons.
Lozykowski points out several arguments, both experimental and theo-
retical, indicating that trivalent RE ions constitute isoelectronic substitu-
tional impurities leading to the creation of bound states in the band gap
of III-V’s. Among those arguments is the difference in covalent radius of
the III group element and the RE3+ ions. That difference would account
for a strain field in the close vicinity of the impurity that would generate a
perturbing potential. This potential can be attractive either for electrons
or for holes and it can even bind to an exciton as a single entity.
In his model, Lozykowski proposes three possible mechanisms of en-
ergy transfer. In the first mechanism the energy of excitons bound to the
isoelectronic center is transferred to the RE 4f core electrons.
In a second mechanism, the RE-induced trap is occupied by an electron
(hole) and it will attract a free hole (electron) from the valence (conduction)
band. The recombination energy of the bound electron (hole) with the free
hole (electron) is transferred to the 4f shell through a nonradiative Auger
mechanism.
The third mechanism consists of the transfer through an inelastic scat-
tering process in which the energy of a free exciton near the trap is given to
the localized core excited states. When the initial and final states are not
resonant, the energy mismatch is accommodated by, for example phonon
emission or absorption.
Furthermore, according to this author, the RE-associated trap does not
necessarily imply that the RE ion occupies a perfect substitutional group
III element lattice position. In fact, depending on its chemical activity,
the RE ion can form a more complex center, involving other impurities or
native defects. This opinion was shared by other research groups, includ-
ing RENiBEl. In another DFT study, Filhol et al. [46] have investigated
the structure and electrical activity of RE (Eu, Er and Tm) and RE-defect
complexes in GaN. They concluded that the configuration where the RE
ion substitutes the Ga atom (REGa ) does not generate any deep band gap
states. This result appears to be consistent with the fact that only a small
amount of all the RE ions are optically active, despite Extended X-ray Ab-
sorption Fine Structure (EXAFS) measurements ([56]) showing that REGa
with C3v point symmetry is the most common geometry where RE in GaN
are found.
Concerning RE-defect complexes, the same RENiBEl studies ([46]) point
REGa associated to a nitrogen vacancy (REGa -NV ) as the most favorable
2.5 Doping 39
Fig. 2.11: Schematic of energy levels at Γ of RE-defect complexes in GaN [46].
to form and the most stable pair (up to 1000 o C). This defect complex is
expected to create a half-filled level at about 0.2 eV below the EC for the
three RE elements they investigated. Other RE-defect configurations were
experimented. Figure 2.11 graphically summarizes their results.
Whatever the host-RE energy transfer mechanism might be, it must

provide the 4f -core electrons with enough excitation energy to allow the
intra-4f transitions responsible for the characteristic optical emission. The
most energetic luminescence observed from an intra-4f transition is the
spectral line observed at around 381.6 nm from the 5 D3 →7 F6 transition
from Tb3+ in GaN. To this value corresponds an energy of 3.249 eV. As
such, the lower limit for a trap in the band gap, involved in the population
of the Tb3+ 5 D3 level, is EC -0.2 eV . Considering that the same energy
transfer mechanism involving similar defects for all RE-ions is valid, this
sort of argument immediately excludes any RE-defect complex, creating
deeper levels, to be involved in centers responsible for high energy optical
transitions.
As discussed above, dopants can be employed to engineer a wide range

of materials properties. However, those properties are not only conditioned
by the presence of a foreign species in the host lattice, but by any element
responsible for the break of crystalline periodicity. More generally, crys-
talline defects, independently of their origin, have an important role on the
material behavior. The preceding discussion on RE-ions as optical dopants
in GaN has evidenced the important role of intrinsic semiconductor defects
such as vacancies and interstitials. Due to their relevance, a brief overview
on defects in semiconductors will be presented in the following chapter.
Chapter 3
Defects in semiconductors
3.1 Structural defects classification

The perfect crystal is an ideal structure where the constituent host atoms,
molecules or ions are periodically arranged in space, forming a pattern
extending itself in the three-dimensional space. However, in a real crys-
tal, the structure is always disturbed by some irregularities. Crystalline
imperfections, or defects, will always be present at normal pressure and
temperatures. Defects are usually classified according to their dimensional
extension ([57]):
• Zero-dimensional or point defects:
– Vacancies;
– Interstitials;
– Impurity or dopant atom:
- Substitutional,
- Interstitional.
• One-dimensional or line defects:
– Strings of point defects;

41
42 Defects in semiconductors
– Edge dislocations;
– Screw dislocations;
• Two-dimensional or surface defects:
– Stacking faults;
– Grain boundary;
– Twin boundary;
– Interface boundary at precipitates.
• Three-dimensional or volume defects:
– Voids;
– Bubbles;
– Precipitates.
The way these defects are introduced in the semiconductors can have
several origins. Some are introduced during growth, as for example de-
scribed in section 1.2, while others are introduced during other subsequent
processing steps, such as doping by means of ion implantation as will be
discussed later on chapter 5.
3.2 Point defects

Thermodynamics plays a determining role on the number of defects in crys-
tals. One can speak of a balance between the crystal energy, that tends to
be minimized, and its entropy, that tends to be maximized. The crystal
energy is minimal for a perfect crystalline lattice, whereas entropy increases
with the formation of defects.
At temperatures above 0 K, a crystal cannot exist in a state of per-
fection. Lattice atoms are in continuous vibration about their equilibrium
position. The vibration amplitude increases with increasing temperature
and can be represented as a statistical distribution of thermal energy over
the lattice atoms. As such, there will always be a non-zero probability that
3.2 Point defects 43
Fig. 3.1: Point defects in mono-atomic and diatomic crystalline lattices [58].
sufficient energy is locally concentrated on a group of atoms and that one

of them acquires sufficient energy to spontaneously abandon its equilibrium
position. A lattice imperfection is formed.
Point defects constitute the simplest form of defects. Figure 3.1 illus-
trates several types of point defects existing in monoatomic and diatomic
crystals. An atom missing from its lattice site, is referred to as a vacancy,
whereas an atom occupying a position other than a regular lattice site con-
stitutes an interstitial defect. When an impurity or dopant is introduced in
the lattice, according to the position it will occupy, it can be named sub-
stitutional (when replacing a host atom on its lattice site) or interstitional
(when it doesn’t occupy a regular lattice site).
The various types of intrinsic defects in a crystal are thermally activated,

each one having its own formation energy [37]. As such, it is to be expected
that a certain kind of point defect with the lowest formation energy will be
more abundant in the lattice. However there is an important restriction:
charge neutrality - the crystal must remain neutrally charged. Thereby,
this restriction assures that the concentration of the most abundant defect
type is lowered while the concentration of the most abundant type of the
opposite charge is increased. In a diatomic ionic crystal, such as GaN,
charge neutrality can be achieved by either balancing the number of positive
and negative ion vacancies - Schottky defects, or maintaining the number of
vacancies and interstitials of the same ion at equal levels - Frenkel defects.
The formation energy of an interstitial defect is higher than that of a
vacancy. For this reason, in a pure (undoped) crystal, the concentration of

interstitials will, in general, be several orders of magnitude lower than the
vacancy concentration. Also, due to the fact that an interstitial occupies a
non-regular site, the lattice surrounding the defect will become strained.
The several types of point defects can interact with each other. The type
of interaction depends on the distance between the defects. As such, short
range interactions account for the formation of vacancy-interstitials pairs
(also known as Frenkel pairs) and divacancies, for example. Frenkel pairs
are of particular relevance for this work since their production is favored
during ion implantation. As will be discussed in chapter 5, the radiation
damage caused by ion implantation consists (among other sorts of defects)
of an equal number of vacancies and interstitials, being frequently inter-
stitials associated to neighboring vacancies. The lattice strain near these
pairs is such that if the separation between them is short, they will sponta-
neously recombine in order to reduce the strain. However, when this is not
the case, a defect inducing lattice expansion - such as an interstitial, tends
to pair (without recombination) with a neighboring defect that induces lat-
tice compression - a vacancy. As an example we have stable Frenkel pairs.
The intensity of this elastic type of interaction varies with r−3 ,r being the
distance between the two defects.
Another sort of longer range interaction is related to the charge the
involved defects have. Electrostatic interaction can result in the pairing of
two defects with charges of the opposite sign. The interaction energy in
this case varies with r−1 .
In stoichiometric compound crystals of the form Ax B1−x , such as GaN
where the Ga and N atoms form two interpenetrating sublattices, the com-
plexity of defects is increased. At a certain temperature, T > 0 K, a certain
concentration of vacancies and/or interstitials will be present in each sub-
lattice. Besides, antisite defects (A in the lattice site of B and vice versa)
may also be present.
The nature of a point defect determines the mechanism through which

it can move through the crystal lattice [59]. As such, a defect in a substitu-
3.3 Line and surface defects 45
tional lattice site will move by jumping to the next equivalent substitutional
site when this becomes empty through the generation of a vacancy. On the
other hand, a defect in an interstitial position will move by jumping to a
neighboring equivalent position. An interstitial can also exchange positions
with an atom on a regular lattice site which will be displaced into another
interstitial site.
Vacancy and interstitial dynamics are governed by their diffusivity which
reveals an Arrhenius-form dependence on the temperature and activation
energy ([57]):
− kEaT
D = D0 e B , (3.1)
being Ea the activation energy for the diffusion process and D0 an expo-
nential pre-factor related to the migration entropy.
Being mobile, point defects may vanish by annihilating with point de-
fects of opposite nature or by aggregation with defects of the same kind.
Point defects can also diffuse towards the crystal surface or towards ex-
tended crystalline defects, which will act as sinks for point defects. Aggre-
gation is at the origin of defect clusters. By forming such structures, defects
are allowed to lower their free energy. Due to their nature, clusters have a
high impact on the lattice strain, leading to local lattice expansion. In the
case of GaN, these structures are thermally quite stable, being observed
even at temperatures as high as 1300o C [60].
3.3 Line and surface defects
The amount of energy required for the formation of an extended defect is

much higher than that of point defects. For this reason it is unlikely that
this kind of defects spontaneously forms at temperatures above 0 K.
Extended defects are frequently formed during the crystal growth phase,
for example as described on section 1.2.1; during ion implantation, as a con-
sequence of the clustering of point defects; by the influence of applied forces
to the crystal, or by strong temperature gradients.
Fig. 3.2: Slip motion in a crystal lattice under stress [57].
Fig. 3.3: a) edge and b) screw dislocations [57].
In general, the deformation of a crystal can be classified as elastic - when

it is reversible (when stress is removed, the crystal returns to its initial
shape), or plastic - when the deformation is permanent and irreversible.
There are two frequent modes of plastic deformations in crystals. The
first mode, slip, is associated with a particular kind of line defects, namely
dislocations. The two simplest kinds of dislocations are known as edge and
screw dislocations. Figure 3.2 illustrates how the slip mechanism occurs
in a crystal under applied stress (figs. 3.2 b), c) and d)) [57]. The upper
part of the crystal slips over the lower part. This process can result in the
reminiscence of edge dislocations and/or screw dislocations (figure 3.3) that
occur during the slip motion.
The other frequent mode of plastic deformation is named twinning. Like
3.4 Volume defects 47
Fig. 3.4: During deformation atoms can be pushed out of place. If this happens
to produce a symmetrical arrangement, a deformation twin is formed.
slip, twinning is also mediated by dislocations. At its origin is the fact that
the applied stress causes coherent formation of dislocations along succes-
sive crystal planes. As each dislocation propagates through the crystal it
displaces a lattice plane by a non-Bravais lattice vector. The net effect of
the passage of a set of dislocations is a region in which the crystalline order-
ing is the mirror image (along the plane of the movement) of the original
crystal. This process is schematically represented on figure 3.4 [61].
For MOCVD grown GaN, one of the reasons for the elevated dislocation
density ( ∼ 1010 /cm2 as compared to < 102 /cm2 for Si and < 104 /cm2
for GaAs) found in the grown films is related to the several temperature
steps during growth (see section 1.2.1). Those steps associated to the ther-
mal mismatch between the sapphire substrate and the GaN film are often
responsible for the formation of cracks on the film. Another reason is the
coalescence boundaries between grains on the GaN/AlN buffer layer.
3.4 Volume defects

Finally, voids, gas bubbles and precipitates constitute a third category of
defects often found in semiconductors. As it will be discussed in more detail
in chapter 5, the immense amount of energy locally deposited during ion
bombardment leads to severe lattice disorder. During this process, besides
generation of point defects as described in section 3.2, more complex struc-

tures can be formed. For example, in their review on ion implantation in
GaN, Kucheyev et. al [41] give evidence of the formation of N2 bubbles
in GaN films bombarded with 2 MeV Au ions at a fluence of about 1016
ions/cm2 . Precipitate formation is another example. Employing MBE to
grow doped RE-doped nitrides can result in the formation of precipitates
when dopant concentrations are higher than the material solubility limit
[29]. This constitutes one of the principal disadvantages of RE-doping of
nitrides employing molecular beam epitaxy.
So far, the most relevant properties of GaN and related semiconductors

have been discussed. Also, rare-earth elements have been pointed-out as
important dopants in those materials for optoelectronic applications. It is
however essential to obtain insight in how such dopants interact with the
host material resulting in emission of luminescence.
In chapter 2 the origin of energy bands in semiconductors was briefly
presented, as well as the effects of doping to the material band-gap. In
this scope, shallow and deep band-gap levels have been discussed. Not only
dopants themselves can be regarded as imperfections in the host crystalline
lattice, but also are frequently associated with other structural defects re-
sponsible for band-gap levels. Such defects have their origin, for example,
in size differences between host and dopant ions. Those differences can
cause strain fields in the lattice and consequently induce energy levels in
the band-gap [55].
In the current chapter, a general summary of the most common sorts of
structural defects in crystalline materials was presented. Often, the doping
process itself is the main cause of structural defects in doped semiconduc-
tors. In particular, as mentioned in the introductory chapter, RE doping
of GaN by means of ion implantation introduces significant amount of lat-
tice imperfections. Such implantation-induced structural defects have an
impact on the optical output since they can act as non-radiative recombina-
tion centers, resulting in a reduction of light emission efficiency. However,
the role of defects in the luminescence process is far from understood - as
3.4 Volume defects 49
discussed in section 2.5.3, it is thought that some defects might play an

important role in the RE:GaN luminescence excitation mechanism.
Chapter 4
Deep Level Transient

Spectroscopy
As mentioned in the previous chapters, defects and foreign atoms in semi-

conductors can introduce electronic energy states in the forbidden energy
band-gap. These levels can influence the electrical and/or optical prop-
erties of the semiconductor. In this scope there are two types of levels:
shallow and deep levels. Shallow levels are associated with donor and ac-
ceptor dopants and have relatively small ionization energies. Typical values
of these levels in the band-gap of GaN are 30-50 meV for donor impurities
and between 150-600 meV for acceptor impurities. Deep levels, as their
name suggests, are located deeper in the band-gap. These deep levels can
be charge carrier traps or generation-recombination centers, depending on
their carrier capture/emission rates. Knowledge about band-gap levels is
fundamental to understand the underlying physical processes involved in
electrical conduction and optical emission in these doped semiconductors.
For this purpose, it is fundamental to measure the properties responsible
for the electrical and optical behavior of the material.
Simple current-voltage/capacitance-voltage (IV-CV) and Hall effect mea-
surements can be used to obtain free carrier concentrations and mobility,
resistivity, etc. Luminescence-based techniques can be used to study shal-
lower levels. However, obtaining information on deeper non-radiative cen-
51
52 Deep Level Transient Spectroscopy
ters, such as their activation energy and capture cross section, requires
employing other more elaborated characterization techniques. Deep level
transient spectroscopy (DLTS) is one of such techniques. This spectroscopic
technique, developed in 1974 by D. V. Lang [62], is currently still one of the
most sensitive, rapid and straightforward methods of characterizing deep
levels in semiconductors. DLTS allows distinguishing between majority and
minority carrier traps, offering a wider range of observable trap depths.
Briefly, DLTS uses the capacitance of a p-n junction or a Schottky
barrier as a probe to monitor the changes in the charge state of centers in
the depletion layer. The presence of a center is evidenced by a positive or
negative peak on a baseline plotted as a function of temperature. From the
peak height it is possible to deduce the concentration of the carrier trap,
from its sign (positive or negative peak) it can be inferred whether the level
is due to a majority or minority carrier trap, and from the peak position,
the thermal emission properties of the trap can be extracted.
In this chapter, the main aspects of DLTS characterization will be dis-
cussed.
4.1 Schottky barrier and depletion layer

When two materials are brought in close contact, a contact potential dif-
ference (equal to the difference between their Fermi levels) is established
and forces the whole system to acquire the same Fermi level when thermal
equilibrium is reached.
When the junction is composed by a metal and an n-type semiconduc-
tor, as shown in figure 4.1 a), electrons from the n-type semiconductor can
lower their energy (and reduce the difference in Fermi energies between the
two materials) by traversing the junction to the metal side. While aban-
doning the semiconductor, these electrons leave positive charges behind due
to the ionized donor atoms. This positive charge generates a negative elec-
tric field that acts in the sense of impeding further flow of electrons into
the metal. Electrons will flow in the metal direction until equilibrium is
reached between the diffusion of electrons from the semiconductor into the
4.1 Schottky barrier and depletion layer 53
Fig. 4.1: Schematic energy band diagram of a metal n-type semiconductor junc-
tion. a) before contact, b) after equilibrium is reached, c) spatial charge distribu-
tion along the junction, and d) electric field in the depletion layer [63]. eφM refers
to the metal work-function, eχ is the semiconductor electron affinity, eφS is the
semiconductor work-function, eφB is the potential barrier height, ρ is the charge
density, and W is the depletion layer width, as explained in the text.
metal and the drift of electrons caused by the electric field created by the
ionized impurity atoms. This equilibrium is characterized by a constant
Fermi energy throughout the structure and the forming of a potential bar-
rier at the junction region (figure 4.1 b)). The height φB of this barrier
is given by the potential difference between the metal work-function φM
and the electron affinity of the semiconductor χ: φB = φM − χ [63]. As
such, the barrier height is independent of the semiconductor doping density
and only depends on the metal work function and on the semiconductor
electron affinity.
To study deep levels it is convenient to use asymmetrically doped (p+ n
-highly p-doped with n-doped, or n+ p - highly n-doped with p-doped ma-
terials) or metal-semiconductor junctions due to the fact that the spatial

charge distribution in the high-doped or metal parts of the junction has a
negligible spatial extent (figure 4.1 c)) [64]. In the case of more symmetrical
junctions, carrier traps on both sides of the junction will yield comparable
signals, whereas in the highly asymmetric case the depletion layer is mainly
confined in the low-doped material. As a consequence sensitivity to traps
on the low-doped part of the junction is increased [62].
Electrical characterization performed during this study has been car-
ried out on metal-semiconductor junctions (also known as Schottky barrier
diodes) on n-type GaN. Assuming the absence of surface states (that influ-
ence the barrier height) at the semiconductor side of the junction, the space
charge density in this region is solely determined by the density of donor
impurities and it is matched by an equal negative charge on the metal side
of the junction (with negligible spatial extent).
Due to the presence of the strong electric field (figure 4.1 d)), any free
charge carrier entering this space charge region is swept out. A region
depleted from free charge carriers is then formed at the semiconductor side
of the junction. This so called depletion layer extends itself throughout the
semiconductor up to the point where the electric field vanishes. Under these
conditions, the semiconductor can be divided in two regions: the depletion
layer directly below the metal, and the bulk of the semiconductor. The
charge density in the depletion layer is given by:
½
eND −→ x ≤ W
ρ(x) = (4.1)
0 −→ x ≥ W,
where W is the depletion layer width and ND the concentration of

ionized donor impurities therein. Considering that the semiconductor is
uniformly doped, the one-dimensional Poisson equation is:
d2 φ ρ(x)
2
=− , (4.2)
dx ²S
where φ is the electrostatic potential and ²S the semiconductor dielectric

constant. Double integration of the previous equation (eq. 4.2) yields an
4.1 Schottky barrier and depletion layer 55
Fig. 4.2: Depletion layer width upon application of an external potential difference
Vf . a) Vf = 0 V (no bias), b) Vf > 0 V (forward bias), and c) Vf < 0 V (reverse
bias).
expression from which the width of the depletion layer can be deduced:
s µ ¶
2²S kB T
W = VS − Vf − . (4.3)
eND e
Here e is the electron charge, VS accounts for the built-in potential (after
the metal-semiconductor junction reached equilibrium), Vf is the externally
applied potential and the term kBe T accounts for the contribution of the
majority-carrier distribution tail [63].
As seen from equation 4.3, the width W of the depletion layer can be
altered by adjusting the magnitude of the external voltage Vf . Figure 4.2
illustrates the changes in W with the external applied voltage. The applica-
tion of a positive voltage Vf to the metal with respect to the semiconductor
will bias the junction forwardly. As a consequence, the magnitude of the
electrostatic potential across the junction is decreased by Vf and the de-
pletion layer width follows a similar trend (fig. 4.2 b)).
On the other hand, the application of a positive voltage on the semi-
conductor side with respect to the metal side will set the diode into reverse
bias. The electrostatic potential across the junction is increased by Vf and
the width of the depletion layer is broadened (fig. 4.2 c)).
According to Gauss’s law ( dE(x) ρ
dx = ²S ) it is possible to obtain the mag-
nitude of the electric field as a function of the position across the junction,
Fig. 4.3: Basic processes involved by carrier trapping at a deep level of energy
Et below the conduction band: a) electron capture, b) electron emission, c) hole
capture and d) hole emission.
as illustrated in figure 4.1 d):

½ −eND
E(x) = ²S (W− x) −→ x ≤ W
(4.4)
0 −→ x ≥ W,
The largest value of E is obtained at the metal-semiconductor interface:

E(x=0) = −eN²SD W = −Q ²S , where QD is the space charge (per area unit)
D
in the depletion layer. The existence of this layer and the fact that its
spatial extension can be controlled by an external applied voltage, makes
it possible to characterize the material by measuring the capacitance at
its terminals. From this point of view, the junction formed by the metal
and n-type semiconductor behaves as a parallel plate capacitor does. The
capacitance per unit area at its terminals can be determined by employing
the following equation:
¯ ¯ s
¯ dQD ¯ e²S ND ²S
C = ¯¯ ¯=
¯ kB T
= . (4.5)
dVf 2(VS − Vf − e )
W
4.2 DLTS
As mentioned in the introductory part of this chapter, it is important to
obtain information not only about the shallow donor and acceptor levels
but also about the deeper levels introduced in the band-gap by structural
defects and/or dopant atoms.
4.2 DLTS 57
Deep levels may exchange carriers with the conduction and valence
bands through the emission and recombination of electrons and holes. Fig-
ure 4.3 [65] illustrates the possible recombination processes of electrons and
holes in a carrier trap located Et below the conduction band.
Emission and recombination rates depend on the free energy of ioniza-
tion, electron and hole capture cross-section of the defect-induced level and
on the temperature. Those rates provide essential information about the
electrical characteristics of a particular defect. A defect is said to be an
electron (hole) trap in bulk material when its electron (hole) capture rate
is much larger than its hole (electron) capture rate. A defect is called a
recombination center when its electron capture rate is comparable to the
hole capture rate. However, a recombination center can act as an electron
trap in the depletion layer when electrons are injected to this region. Due
to this ambiguity, instead of characterizing a defect in terms of its capture
rates, which strongly depend on the free carrier concentration in the host
material, it is more convenient to study its emission characteristics.
Furthermore, as opposite to what happens in the bulk material (which is
electrically neutral) where capture and emission of carriers can take place,
no capture processes are allowed within the depletion layer, since all the
mobile charge carriers entering this zone are swept out by the strong electric
field. One can state that due to its nature, the depletion layer decouples
the carrier capture and emission processes, only allowing traps to emit the
carriers they are holding.
As such, in the depletion layer of an n-type semiconductor, electron
traps are the ones presenting electron emission rates much higher than hole
emission rates. On the other hand, generation-recombination centers will
present comparable emission rates for electron and hole emission.
One can define the thermal emission rate of an electron trap in an
n-type semiconductor by [66]:
σn v n Nc k−ETt
en = e B , (4.6)
g
where σn is the electron capture cross section, v n is the electron thermal
velocity, g is the level degeneracy and Et is the trap energy with respect
to the bottom of the conduction band. Nc is the effective state density

at the conduction band edge
q as given in equation 2.5. Approximating the
thermal velocity by v n = 3kmBeT ([70]), and applying the expression for Nc
in equation 4.6, the thermal emission rate becomes
−Et
en = KT 2 σn e kB T , (4.7)
where K for GaN is 4.483 × 1020 cm−2 s−1 K −2 . A similar expression can
be obtained for the emission rate of a hole trap.
The thermal emission rate expression enclosures two parameters which
are fundamental to characterize an electric defect. The energy position
Et within the band gap where the defect creates a level, and its carrier
capture cross section σn define the defect DLTS signature. Measurement of
capacitance changes in the depletion layer is sensitive to any change in the
charge state of defects therein. This means that not only shallow dopants,
but also defects that induce levels closer to the middle of the band gap can
be detected.
4.2.1 Capacitance transient

The extraction of the DLTS signature of defect levels from a DLTS ex-
periment is based on the measurement of the transient capacitance change
observed at the terminals of a p-n or Schottky junction after driving it
momentaneously into a non-equilibrium condition and let it return to equi-
librium. The magnitude of the capacitance transient corresponding to ther-
mal emission of carriers from a deep level depends on the concentration of
the defect causing the level, its emission rate and on the temperature.
Figure 4.4 illustrates the capacitance transient evolution in a Schottky
junction. Initially the junction is under reverse bias (1) to form a depletion
layer as discussed in section 4.1. In this state, referred to as equilibrium
state, the traps are empty because no mobile carriers are available for cap-
ture. When the reverse bias is reduced (2), the width of the depletion
layer (W ) decreases and carriers will now be available for capture. As a
consequence of the depletion layer decrease, the capacitance will increase.
Re-establishing the reverse bias condition (3) will increase the depletion
4.2 DLTS 59
Fig. 4.4: Capacitance transient due to the presence of an electron trap in the
n-type material. The insets labeled 1 through 4 represent the charge state of the
trap and the width of the depletion layer before and during the transient [66].
layer width. However now, some carriers are still trapped leading to a de-
crease of the capacitance junction below the equilibrium value. The filled
defect states will return to their initial empty state if sufficient thermal
energy is present to stimulate the emission of carriers to the conduction
band. At this point the capacitance tends to increase, returning to its
original equilibrium value (4). The trap emptying process gives rise to a
capacitance transient with a characteristic time constant equal to the trap
thermal emission rate en . One can write that the capacitance transient has
the form:
C(t) = C(∞) − ∆Ce−en t , (4.8)
where C(t) is the capacitance transient at time t, C(∞) is the quiescent

reverse bias capacitance at time t = ∞ and ∆C is the difference between
C(∞) and the capacitance measured at t = 0, when the bias conditions are
first changed.
Fig. 4.5: Schematic illustration of the rate window concept. The lower part of the
figure represents the Arrhenius plot for two traps with different energies, while the
upper part shows the response of the DLTS measurement equipment [62].
4.2.2 Emission rate window
The fundamental concept of the DLTS technique is the emission rate win-
dow, illustrated on figure 4.5. Applying a train of repetitive bias pulses to
the junction as specified in figure 4.4, the output signal consists of a series
of capacitance transients with a constant repetition rate reflecting the traps
emptying process. Let’s consider that the measurement apparatus does not
produce a response to this sequence of transients unless the time constant
of the transient is within some interval of emission rate values. This interval
of values receives the name of emission rate window (lower part of figure
4.5). If the emission rate of a trap is varied by varying the temperature
(the transient time constant varies exponentially with 1/T ), the apparatus
will respond with a peak at the temperature where the trap emission rate
falls within the defined window (upper part of figure 4.5). This rate win-
dow may be set using several procedures, being originally implemented by
4.2 DLTS 61
Fig. 4.6: Implementation of a rate window with a double boxcar integrator [62].
a double boxcar integrator.
Double boxcar integrator principle

With this procedure, the transient amplitude is sampled at two gate times
t1 and t2 . The normalized DLTS signal is then given by the difference
between the transient amplitude at those two instants [62]:
C(t1) − C(t2)
S(T ) = , (4.9)
∆C(0)
where ∆C(0) is the capacitance change due to the applied pulse at t = 0.

Figure 4.6 illustrates the use of the double boxcar integrator to define a
rate window. The output signal is zero for either very slow or very fast
transients, corresponding to low or high temperatures, respectively. On
the other hand, when the transient time constant (τ ) is of the order of the
separation |t1 − t2 |, a difference signal is generated and the boxcar output
passes through a maximum as a function of the temperature giving rise to
a DLTS peak in the spectrum. The transient time constant at which the
DLTS signal from the double boxcar has a maximum value can be related
to the rate window by:
t1 − t2
τmax = . (4.10)
ln(t1 /t2 )
The signal-to-noise ratio obtained through this method is proportional to
the square root of the gate width [68]. It is possible to deduce an analytical
expression for the line shape of DLTS peaks obtained using the double
boxcar integrator method, however this expression depends on too many
parameters, namely six, so that the resulting expression is of little practical
use [66].
Miller et. al [66] have investigated ways to optimize the signal-to-noise
ratio of DLTS measurements. They have concluded that the signal-to-noise
ratio is improved by using large gate widths. In order to obtain the highest
sensitivity possible, they employed time domain filter theory to demonstrate
that the use of an exponential weighting function with a single wide gate
setting results in the optimal signal-to-noise ratio. This method would
imply that the DLTS signal at temperature T has the form:
Z T0
S= C(t)W (t)dt, (4.11)
0
where T0 is the measurement period, C(t) is the capacitance transient and

W (t) is the weighting function. These authors have implemented such
system employing a time-domain correlator. However, this system has the
disadvantage of not automatically restoring the baseline, adding further
complexity to the measurement results.
Lock-in amplifier method

An alternative method to set up the rate window consists on using a lock-
in amplifier (LIA). Essentially, a LIA is a filter with an arbitrarily narrow
bandwidth which can be tuned to the frequency of the signal being studied.
In addition to filtering, the LIA provides gain. This device owes its popu-
larity as a DLTS tool to the fact that it is relatively inexpensive, available
in most research laboratories and the analysis of the output spectrum is
quite straightforward [70].
4.2 DLTS 63
Fig. 4.7: Block diagram of a lock-in amplifier [71].
A block diagram of the LIA is shown in figure 4.7. The AC amplifier

is a voltage amplifier combined with variable filters; the VCO is a voltage
controlled oscillator which can be synchronized with an external reference,
both in phase and frequency; the PSD, or phase sensitive detector, is a mul-
tiplier circuit; the low pass filter is a RC filter with tunable time constant;
and the DC amplifier is a low-frequency amplifier.
The LIA also applies a weighting function to the transient (usually a
sinusoidal signal with the same frequency of the applied junction bias).
Figure 4.8 illustrates the pulse sequence, transient response and weighting
function of the LIA. In order to prevent LIA overloading during the filling
pulse and the large pulse recovery transient, the transient signal is often
gated-off. The signal is held at a constant value by using a sample-and-hold
device for the duration of the tp pulse, and the capacitance meter response
time td. The LIA registers the first Fourier component and the phase of the
resulting waveform (bold line in C(t) signal of figure 4.8). This component
is dependent on both tp and td. The response to the input signal is
Z +T0 /2
S= f1 (t)W (t)dt, (4.12)
−T0 /2
where f1 is the first Fourier component of the waveform and W(t) is the
Fig. 4.8: DLTS signal sequence with LIA. V(t) is the junction bias, C(t) is the
modified capacitance curve and W(t) is the LIA weighting function [71].
weighting function, as shown in figure 4.8. Since the LIA uses more of the
signal (than double boxcar method), it is less sensitive to noise and thereby
the signal-to-noise ratio is improved.
In this method, the DLTS rate window is set by choosing the frequency
of the LIA reference signal which is synchronized with the applied junction
bias.
Similarly to the double boxcar method, the value of the transient time
constant at which the DLTS has a maximum value can be obtained by
calculating dS
dτ = 0. For a constant frequency νLIA = 1/T0 , it can be
demonstrated ([70]) that
τmax = 0.424/νLIA . (4.13)

4.2 DLTS 65
Fig. 4.9: Comparing DLTS peak shape as given by equation 4.14 (full line) with
the shape of a gaussian function (dashed line).
The line shape of peaks in a DLTS spectrum obtained with the LIA
method has the form [68]:
1
2πα2 (1 − e− α )
A(α) = , (4.14)
4π 2 α2 + 1
where α = Tτ0 = τ νLIA , being τ the transient time constant and T0 the
reciprocal of νLIA , the LIA operating frequency. Plotting A(α) as a function
of temperature, it can be seen that this function resembles in shape, a
slightly asymmetric gaussian function. As such, a DLTS peak can, as a
crude first approximation, be fitted with a gaussian-shaped peak (figure
4.9). However, the “fitting” procedure with a gaussian function produces no
physical results other than the temperature position of the peak maximum.
It can be seen on figure 4.10 that by changing the rate window to higher
frequencies, the DLTS peak position shifts towards higher temperatures.
This is an indication that at higher temperatures higher emission rates
en , associated to shorter decay rates τ (and thereby higher frequencies -
eq. 4.13) are observed. In fact this constitutes the method by which the
DLTS signature of a defect is obtained. Measuring the temperature at
which a trap is emptying with an emission rate en , within a preset rate
Fig. 4.10: Lock-in amplifier DLTS spectra as a function of temperature and LIA
center frequency.
window, allows obtaining one point in the Arrhenius plot of ln( Ten2 ) v.s.
1/T. For example, in figure 4.10 we have three peak temperature positions
at three different LIA frequencies. From this plot, the trap energy Et is
obtained from the slope using equation 4.7, and the capture cross section
σn is obtained from the intercept with the y-axis.
Apart from its activation energy Et and its carrier capture cross section
σn , knowing the concentration Nt in which a defect is present is often
important. Lang [62] proposed a simple method to estimate the majority
carrier trap concentration Nt by measuring the capacitance change ∆C due
to the complete filling of the traps in the depletion layer. In this method, it
is assumed that the doping is spatially uniform and that ∆C ¿ C, being C
the capacitance at the depletion layer terminals. The defect concentration,
in n-type material, is simply given by (detailed expression derivation can
4.2 DLTS 67
Fig. 4.11: Energy band diagram for a Schottky barrier diode with deep donors
under a quiescent reverse bias. Inside the λ region deep donors are filled with
electrons.
be found in reference [64]):
∆C
Nt ∼
= 2(ND − NA ) (4.15)
C
where (ND −NA ) is the net donor concentration that is often approximated
to the donor concentration ND . This method serves only as an estimate
since it is known to produce values which are about 50% lower than the ones
obtained by more accurate methods [66]. An example of a more accurate
approach consists on profiling the depletion layer by progressively increasing
the forward bias pulse intensity with small increments δV . Zohta and
Watanabe [69] proposed a correction to equation 4.15 where they take into
account a region in the depletion layer where some of the deep donors are
below the Fermi energy (region λ in figure 4.11) and therefore filled with
electrons. The existence of this region within the depletion layer (where
only shallow donors contribute to the capacitance change ∆C) is ignored
in equation 4.15 this being the reason for the underestimation of Nt . Their
formula to obtain Nt is
µ ¶ "µ ¶2 µ ¶2 #−1
∆C W −λ Wp − λp
Nt = 2 ND − , (4.16)
C W W
Fig. 4.12: Block diagram of the equipment required in a DLTS experiment.
with λ and λp the edge of the region where the deep level crosses the bulk
Fermi level before and immediately after applying the forward bias pulse,
respectively and W and Wp are the depletion layer widths before and just
after pulsing, respectively. The value of λ is given by
µ ¶1/2
2² EF − Et
λ= . (4.17)
q ND
4.3 DLTS instrumentation

As indicated in the previous section, in order to perform a DLTS exper-
iment, specialized equipment is required to analyze the capacitance tran-
sients.
After Schottky and Ohmic contacts deposition (described in section 7.1)
the sample under investigation is placed in the measurement setup. Figure
4.12 schematically illustrates the principal elements required for a DLTS
experiment. The pulse generator defines the pulsing conditions applied to
the diode, as represented in figure 4.4. These conditions include the reverse
4.4 DLTS signature temperature dependence 69
(VR ) and the forward (VP ) bias voltages and the pulse duration (tp ) and
delay (td ) times. A Hewlett Packard model 10A 150Hz pulse generator
was used in this work. A Boonton 7200 capacitance meter was used to
monitor the diode capacitance. Coupled with it, a capacitance subtraction
box allowed maintaining the signal in unsaturation levels and increase the
sensitivity scale of the capacitance meter. The intermediate signal was
passed through a double channel oscilloscope to visualize the capacitance
transient shape. This allows taking action in order to optimize the pulsing
conditions before the actual DLTS spectrum is obtained. The capacitance
meter output is fed in to a Stanford Research System Model SR830 lock-in
amplifier. The other input to the LIA is the reference frequency (coupled
with pulse generator) to define the rate window. This value is set by the
user.
With the sample inside a cryostat, its temperature can be varied in
order to perform a temperature scan. At this point, the LIA output signal,
proportional to ∆C
C as described in the previous section, is passed on to
a computer card and registered as a y-value on a x-y plot where x is the
sample temperature T (figure 4.13).
4.4 DLTS signature temperature dependence

The DLTS signature obtained as described in section 4.2 is often called the
apparent DLTS signature, consisting on an apparent carrier capture cross
section and activation energy. It is relatively fast, simple and straightfor-
ward but it ignores the fact that the capture cross section of a trap might
depend on the temperature. This dependence can be expressed as
− kE∞T
σn = σ∞ e B , (4.18)
where σ∞ is the capture cross section extrapolated to T =∞ and E∞ is the

capture activation energy, an energy barrier that a carrier has to overcome
to be trapped on the defect site. The fact that σn might depend on the
temperature also influences the value of the defect activation energy Et .
To evaluate the temperature dependence of σn an Arrhenius plot of ln(σn )
Fig. 4.13: Example of a DLTS spectrum on an unimplanted GaN sample evidenc-

ing two major electron traps.
versus 1/T has to be constructed. Its slope gives the value of E∞ and σ∞
is obtained from the interception with the y-axis. If there is indeed a tem-
perature dependence of σn , the defect activation energy must be corrected.
Its real value will then be given by
E0 = Et − E∞ . (4.19)
For the present discussion, and following the example of most reports
in literature, the contribution of the temperature dependence was ignored.
As such, the values of the apparent DLTS signature of a trap level are
determined and used to estimate the band-gap position of the defect. The
typical error values associated with this approach falls within 10-30% in
excess of the real value E0 .
4.5 DLTS limitations 71
4.5 DLTS limitations
Deep level transient spectroscopy is a powerful and well-established tech-

nique for characterizing defects in semiconductors. However, as with all
experimental techniques, it is relevant to know its limitations and domain
of application. Employing DLTS to analyze Schottky barrier diodes only
allows detecting majority carrier traps since forward bias conditions do not
inject minority carriers into the junction [66].
The doping level of the sample also imposes some limitations. The
sensitivity of the DLTS technique is strongly influenced by the shallow
level doping on the sample. The minimum detectable defect concentration
is typically of the order of 10−4 of the shallow level concentration. As
such, in a material where the shallow level concentration is 1014 cm−3 , the
detectability limit of a particular defect will be of the order of 1010 cm−3 . In
a material doped to a higher concentration, 1020 cm−3 for example, defects
with a concentration lower than 1016 cm−3 won’t be detected.
Doping by means of ion implantation, as it was done in this study,
might also introduce further problems. As will be discussed in more detail
in chapter 5, the structural damage produced during the process of im-
plantation can cause electrical compensation of the n-type semiconductor
leading to an increase of the Schottky diode series resistance. This can have
several consequences on the DLTS experiment results. Electrical compen-
sation leads to a decrease of the free carrier concentration available to fill
the traps during DLTS pulsing. As a consequence, the response on the
capacitance change is compromised. Miller et al. mention in their review
article [66] that as a good rule of thumb, capacitance spectroscopy can be
successfully employed only if the diode capacitance changes significantly
with the applied reverse bias voltage.
On the other hand, the value of the sample resistance in series with the
diode capacitance can dramatically affect the outcome of a DLTS experi-
ment. It can strongly reduce and even reverse the sign of a DLTS peak,
possibly leading to erroneous conclusions over the nature of the defects un-
der investigation.
As pointed out by Broniatowski et al. [72], the series resistance of a sam-

ple influences the quality factor Q of the series circuit composed by that
resistance and the capacitor
Q = Rs Cs ω, (4.20)
ω being the applied pulse frequency. A factor of Q = 1 cancels out the

DLTS signal and this last has its signal reversed for Q > 1. Signal reversal
can lead to confusion between majority and minority carrier traps.
Throughout the previous chapters the properties of the implantation

host material as well as the dopants have been summarized. The interac-
tion between dopant and host has also been discussed from the view-point
of band structure and band-gap energy levels caused by the presence of
dopants and/or crystalline defects. The current chapter described a power-
ful technique to investigate such band-gap levels and to gain more insight
over the effect of dopants and defects on the properties of the host semi-
conducting material. However it is also important to describe the process
through which the dopants are introduced in the host material, in the cur-
rent work - ion implantation. As previously mentioned, ion beams played
a central role in the work described on this thesis. Not only ion beams
were used in doping the GaN thin-films but they were also employed on the
structural characterization of the RE-doped material. Both aspects of the
use of ion beams will be described in the following chapters.
Chapter 5
Ion beams for materials

modification and
characterization
Ion beams are a valuable tool in the field of semiconductor technology

research. They can be applied to modify a wide variety of semiconductor
physical properties in order to tailor the materials electrical and optical
behavior, for example. These beams are also frequently employed in the
characterization of semiconductors to obtain information on dopant levels,
defect concentration and crystalline structural quality, among others.
It is the purpose of this chapter to discuss the basic physical concepts
of the ion beams-solid matter interaction. For a more extensive discussion
on this subject, the reader is referred to, for example, references [73, 74].
5.1 Fundamentals of ion beam-solid interactions

When an energetic incoming ion impinges on a solid, it will interact with
the electrons and nuclei composing the material. The intensity and type
of interaction depends on several parameters, such as the ion energy, and
the masses of both incident ion and target atom. The ion will progressively
lose its energy through a series of small angle deflections with electrons or
73
74 Ion beams for materials modification and characterization
nuclei that will gradually deviate the ion from its initial trajectory. On
the other hand, single-event interactions can account for sudden loss of
significant amounts of energy of the incident ion and strongly deflect its
trajectory. Such drastic interactions include target atom displacements,
sputtering, large angle scattering, etc. The types of interactions between
incoming ions and target materials are usually classified into four groups,
as follows (ref. [75]):
• The energy loss can occur via inelastic collisions with electrons of the
medium leading to their excitation and even ionization of the target
atoms. During this sort of interaction the ion loses a small amount
of its energy and its path is only slightly affected.
• Elastic collisions with target electrons are only to be considered when

the energy of the incoming ion is small ( < 1 keV).
• The incoming ion can also undergo an elastic collision with target
nuclei or atoms. When the impact parameter (closest distance of
interaction) is small enough, and depending on the parameters of the
two-body kinematics (involved masses and energies), a considerable
amount of energy can be transferred from the incoming ion to the
target nucleus. This transfer can be accompanied by a major change
of the ion path direction.
• Finally, as with electronic collisions, nuclear collisions can also be

inelastic. However, nuclear inelastic collisions require incoming ions
to have very high energies. Nuclear excitations and reactions are two
possible consequences of inelastic nuclear collisions.
The slowing down of ions in matter can be described numerically in

terms of a quantity dE
dx , called stopping power. This quantity represents
the amount of energy ions lose in their trajectory through matter per unit
distance (eV/Å).
As mentioned above, the two dominant processes responsible for the en-
ergy loss of the incoming ion beam are the inelastic collisions with electrons
5.1 Fundamentals of ion beam-solid interactions 75
and elastic nuclear collisions. As such, the total stopping power is a sum
of contributions that can be expressed by:
µ ¶ µ ¶ µ ¶
dE dE dE
= + . (5.1)
dx total dx electronic dx nuclear
A probability, or cross-section is associated to each component of the to-

tal stopping power. As such, the stopping cross-section ² (for the electronic
and nuclear contributions) can be described as:
µ ¶
1 dE
²= , (5.2)
N dx e,n
where N is the material density.

The electronic contribution to the stopping power can be further un-
folded in two regimes, depending on the energy of the incoming ion. In
the first regime, often referred to as the slow collision regime, the incoming
ions have a low velocity. In 1963 Lindhard, Scharff and Schiøtt developed
the theoretical background on this regime ([76]), also known as LLS-theory.
According to this theory, the electronic stopping power in the slow collision
regime increases linearly with the ion incoming velocity.
In the fast collision regime, there is a sudden energy transfer from the
incoming ions to a target electron. Due to the shorter interaction time, the
stopping cross-section will be smaller. The complete theoretical treatment
of the electronic stopping power in this regime was performed by Bethe
and Bloch in 1930 ([77]). Their work leads to an energy dependence of the
stopping cross-section of the form ² ∼ 1/E.
As for the nuclear contribution to the stopping power, the elastic colli-
sion between the ion and the target nucleus can be described in terms of a
two-body interaction with impact parameter b. As a result of the collision,
the ion transfers an amount of energy T to the target nucleus, its path is
deflected by an angle θ1 and the target nucleus recoils along an angle θ2 ,
as illustrated on figure 5.1.
As seen from equation 5.2, the nuclear stopping power can be given by
the product of the target atomic density and the nuclear stopping cross-
section. This cross-section depends on the probability for energy transfer
Fig. 5.1: Scattering of two particles showing the deflection angle θ1 of the incident
particle and the recoil direction θ2 of the target particle.
T (E, b) from the ion to the target nucleus:

Z ∞
Sn = T (E, b)dσ, (5.3)
0
E being the ion energy, b the impact parameter and dσ = 2πbdb the cross
section for the transfer of an amount of energy between E and E + dE.
The energy transfer depends on the impact parameter with which the
projectile approaches the target nucleus. This parameter has its minimum
value at bmin = 0, when the two nuclei collide directly. The maximum value
of b, bmax , can be chosen so that it equals the sum of both atomic radii (no
superposition of the respective electronic clouds). To bmin and bmax will
correspond a Tmax and Tmin for the energy transfer, respectively. As such,
the nuclear contribution to the stopping power can be written as:
µ ¶ Z Tmax
dE
= −N T dσ(E, T ). (5.4)
dx nuclear Tmin
Both T and dσ depend on the interatomic potential V (r) between the

two particles. When the incident particle is a heavy ion with low energy,
one often has to consider the influence the screening effect of electrons on
the interaction between the two nuclei (incoming ion and target atom).
The interaction potential can be then described as a “screened” Coulomb
potential:
Z1 Z2 e2 r
V (r) = χ( ), (5.5)
r a
Fig. 5.2: Typical ratio between electronic and nuclear stopping power contribu-
tions.
with Z1 and Z2 the atomic numbers or the ion and target atom, respectively,
r the interaction distance and χ( ar ) a screening function where a is the
Thomas-Fermi screening length. Several approaches were attempted to
obtain an adequate screening function, as described in reference [74]. The
interatomic potential can be approximated to a simple Coulomb potential
in the case of high energy low mass ions, where the screening function is
often found to be negligible.
Figure 5.2 illustrates the relative contribution of electronic and nuclear
stopping powers as a function of the incoming ion energy. The nuclear con-
tribution is dominant at lower ion energies, the maximum typically occur-
ring at energies of the order of 1 keV/amu. The maximum of the electronic
stopping power occurs at higher values, at about 100 keV/amu [78].
As seen in the previous discussion, the atomic number of the incoming
ion plays an important role on the stopping power, in particular, dictating
what sort of energy loss process dominates at a certain energy range. For
example, it is observed that the nuclear stopping contribution for very light
ions slowing down in heavy materials, is much weaker than the electronic at
almost all energies. Figure 5.3 shows the result of the SRIM Monte Carlo
computer simulation program ([79]) for two extreme examples of how the
two contributions for the stopping power (electronic and nuclear) change
with the ion mass.
The top graph illustrates the stopping power of 153 Eu, a heavy ion, in
GaN. The curves indicate that, in this mass region and in the energy range
of 10 - 300 keV, the predominant mechanism contributing to the energy
loss of the incoming ions are elastic collisions with target nuclei. It should
be emphasized that this range of energies coincides with the typical values
from ion implantation.
The lower graph depicts the stopping power of 4 He ions in GaN. Al-
ready at around 1 keV the electronic contribution to the total stopping
power begins to dominate, following a steep increase of its intensity while
the nuclear contribution is already decreasing. In the range of the typi-
cal energies that ions are accelerated for Rutherford backscattering (RBS)1
measurements (1 - 3MeV), the contribution of nuclear stopping power is
negligible.
In the context of this thesis, the previous examples illustrate the two
relevant regimes for the application of ion beams. The first regime is char-
acterized by the use of heavy-mass ions with relative low energies (∼ 10 to
300 keV) - ion implantation. In the second regime, the incident light-mass
ions (typically 4 He+ or H + ) reach the target with energies of about 1-3
MeV, as used for structural characterization by means of RBS/Channeling.
Due to its importance for this work, the essential concepts concerning ion
implantation will be discussed in the following section. Concerning RBS/C,
a description of the basic principles and physical concepts can be found in
Appendix A. However, the technical details of the use of RBS/C for the
characterization of implanted material are discussed later in section 5.4.
1
See appendix on RBS/C
Fig. 5.3: Stopping powers of Eu and He in GaN, calculated with SRIM.

5.2 Ion implantation
Ion implantation is a well-establishd technique in industry, employed dur-

ing several processing steps. Among its most common applications are
electrical isolation and electrical and optical selective-area doping of semi-
conductors. The reason for its popularity lies within the simplicity and
efficiency of this technique.
The process begins by placing a compound containing the element to im-
plant in an ion source. Here the material is heated and ionized - frequently
by collisions between the compound molecules and electrons emitted from
a hot metallic filament. The created plasma in then extracted out of the
source and accelerated through an electrostatic field. The ionized atoms
acquire energies typically in the range of 1 keV/amu. After acceleration
the ions are mass-separated through an analyzing magnet. This separation
step allows obtaining an isotopically pure beam. Before bringing it to the
implantation chamber, the beam is shaped and focused with the help of op-
tical elements such as magnetic lenses and quadrupoles. Faraday cups are
generally placed along the beam line allowing to measure the beam current
intensity.
Ion implantation offers several advantages as compared to other doping
techniques, such as thermal diffusion and doping during growth. Due to
the fact that mass selectivity is employed, impurities are removed from the
beam. Unlike in-situ doping during material growth, the solubility limit of
the dopant in the host material can be exceeded by ion implantation, as
this is a non-equilibrium ballistic process. This technique further allows to
have control over the concentration of the introduced dopant by integrating
the current transported by the beam. Finally, since the beam can be well
focused with the help of the optical elements present along the beam line,
using simple electrostatic deflection it is possible to sweep and move the
point-convergent beam over the target surface. On one hand, sweeping
assures homogeneity on the implanted dopant concentration, while on the
other hand, it can be used in lateral patterning and selective area doping.
Besides these advantages, ion implantation offers speed, reproducibility and
5.2 Ion implantation 81
153
Fig. 5.4: Damage cascade originated from one Eu ion in GaN.
good process control.

However, to successfully employ ion implantation as a semiconductor
doping technique, it is necessary to have a fair degree of understanding over
the production of damage in the semiconductor as a result of irradiation.
When the incoming energetic ion reaches the target it interacts with
the host atoms as described in section 5.1. During its trajectory through
the material, a single incoming ion may experience several elastic nuclear
collisions with host atoms. At each collision the ion will transfer part of
its energy to a target atom. If enough energy is transferred the atom can
be displaced from its lattice position. This recoiling energetic atom, also
known as primary knock-on atom (PKA), will lose its energy through col-
lisions with neighboring atoms, which on their turn might displace others
in their vicinity. This multiple collision and displacement process is often
referred to as a collision cascade. This process is illustrated on figure 5.4
where the result of a SRIM simulation is shown for one 153 Eu ion accel-
erated at 80 keV hitting a GaN target. The trajectory of the incoming
ion in the material as well as several collision damage cascades are clearly
visible in the figure. These simulation results indicate that about 1300 host
atoms (Ga+N) are displaced per incoming 80 keV Eu ion. The results also
indicate that about 1/3 more of Ga-atoms are displaced, as compared to
the amount of N-displacements. This fact is attributed to the higher av-

erage threshold displacement energy of N, as compared to Ga, as will be
discussed later in this section.
As a result of host atoms displacement, structural defects are introduced
into the crystalline lattice. Depending on the incident ion mass, energy and
fluence, such defects consist not only of displaced host atoms (vacancies and
interstitials) but also more complex defects, as discussed in chapter 3.1.
Not only does the transferred energy lead to collision cascades forming
structural defects, but it is also responsible for a sudden increase of the local
lattice temperature. As a consequence of this local temperature increase
some of the formed defects may acquire enough kinetic energy to migrate
and relax back to a site equivalent to their original lattice position. This
is the case for simple point defects, such as interstitials and vacancies.
The recombination (and thus elimination) of defects during implantation,
as they are being created, is a process known as dynamic annealing. For
GaN such mechanism is very efficient even at very low temperatures (77
K) [41]. Dynamic annealing is thought to be the responsible mechanism
through which the (experimentally measured) lattice damage level is kept
much lower than that predicted by simulation codes, which only take into
account collisional processes and ignore diffusion and annihilation of defects.
This process strongly depends on the host material properties and on the
implantation conditions (ion mass, energy, fluence, substrate temperature).
Report [41] and references therein give significant evidence of the presence
of a very efficient dynamic annealing mechanism is GaN, as observed at
several implantation conditions. When two or more incoming ions have
sufficiently close trajectories, their respective collision cascades may overlap
(figure 5.5). As a consequence of the density increase of these cascades,
the concentration of point defects formed in the region increases as well
as the number and size of defect complexes and clusters. Depending on
the host material and implantation conditions, as the density of collision
cascades becomes sufficiently high, the lattice temperature can locally rise
to extremely elevated temperatures in a time frame of nanoseconds after the
generation of the PKA. This rapid lattice temperature increase is known
153
Fig. 5.5: Damage cascade originated from three Eu ion in GaN.
as the thermal spike. A thermal spike can be seen as a ultra-fast local

melting of the implanted region resulting in the formation of small highly
disarranged volumes in the local crystal lattice. As more and more of
such amorphous volumes are formed, overlapping occurs and eventually
the crystalline structure in the region of implantation collapses, resulting
in the formation of an amorphous region. For a more extensive description
on the physics of implantation damage and collision cascades, the interested
reader is referred to [80].
As mentioned above, the concentration of structural defects caused by
implantation is a function of several parameters, including the implanta-
tion conditions, and the properties of the target material. In particular,
the strength of the bonds between atoms composing the crystal plays an
important role on the formation of damage. The bond strength has a direct
impact on the threshold displacement energy of host atoms - the minimum
value of energy that an incoming ion has to transfer to a lattice atom in
order to displace it from its site.
GaN is known to be more radiation resistant than several other common

semiconductors, such as Si, Ge or GaAs. As compared to Si, ion fluences
one order of magnitude higher, are required to amorphize GaN [81]. Nord
et al. [82], have employed Molecular Dynamics (MD) studies to investigate
the mechanisms of damage accumulation in GaN during ion implantation.
Their results indicate that the main reason for the elevated radiation dam-
age resistance of GaN, as compared to other semiconductors, lies within
the considerably high average threshold displacement energy values. These
authors report values of 45 ± 1 eV and 109 ± 2 eV for the average threshold
displacement energies for Ga and N atoms, respectively. They also report
that the threshold displacement energy is direction-dependent. The mini-
mum value for Ga atoms is obtained in the direction of the second-nearest
Ga neighbor on the negative side of the c-axis. For N, the minimum value
was found to be associated to a direction of about 10o off the c axis, away
from the Ga bond in the (0001) direction. According to these authors, the
high threshold displacement energy values are responsible for a low produc-
tion of damage in individual collision cascades. They observed that most
of the damage is strongly scattered and mainly composed by point defects
(vacancies, interstitials and antisites) and small clusters of less than six
defects.
Other computational methods, such as Monte Carlo simulations, can
be employed to estimate the profile of the defects created during implanta-
tion. Figure 5.6 shows the profile of the Ga vacancies (N vacancies follow a
similar trend) produced in GaN by implantation with 80 keV 153 Eu ions,
as calculated with SRIM. It can be seen that the atomic displacements
follow an approximate Gaussian distribution profile. It should, however,
be mentioned that the theoretical calculations at the origin of these esti-
mations do not take defect recombination into account, regarding merely
the ballistic character of the implantation process. On the same figure,
the concentration profile of the implanted Eu ions reveals also a gaussian
profile, centered somewhat deeper into the bulk material, as compared to
the vacancies distribution profile.
The range R(E) of an incident ion in a target can be directly obtained
Fig. 5.6: Profile distribution of Ga vacancies and 153 Eu ions in GaN, as calculated
with SRIM.
from the stopping power:

Z E
dE
R(E) = , (5.6)
0 (−dE/dx)total(e,n)
with E the initial ion energy. However, during its inwards path the ion will
experience several randomly distributed collisions. Each of those collisions
are likely to modify the direction of the ion motion. As a consequence
the ion trajectory will most probably be different from the initial straight-
line path, as illustrated on figure 5.5. As such, it is more meaningful to
refer to the projected range Rp - projection of the ion trajectory over its
initial direction as represented on figure 5.7. In the same manner, in a
three-dimensional volume it is not difficult to visualize that in the lateral
direction, perpendicular to the in-depth direction, a lateral range (Rl ) can
be defined.
Fig. 5.7: Illustration of the projected range of an ion.
Fig. 5.8: Depth and transverse distribution of Eu ions in GaN.
As seen on figure 5.8, each ion has a different trajectory inside the host
material. The reason for this resides on the statistically fluctuating nature
of the interaction between ions and host. In fact, as SRIM results indicate
on figure 5.6, the depth profile of the implanted ions is best described by a
gaussian distribution:
(x−Rp )2
Φ − 2
n(x) = √ e 2∆Rp
, (5.7)
2π∆Rp
where Φ is the ion fluence (ion/cm2 ), Rp is the projected range as defined

above and ∆Rp is the range straggling, or the depth variation at which
the ion concentration decreases to 1/e of the maximum concentration. A
similar gaussian distribution is obtained for the transverse profile of the
implanted ions.
5.3 Parameters influencing implantation damage 87
5.3 Parameters influencing implantation damage
As seen in section 5.1, the stopping power is a function of the target and
ion atomic numbers and the incoming ion energy. It is then expected that
radiation damage builds up differently for lighter and heavier as well as for
slower and faster ions.
Kucheyev et al. [41] have investigated the irradiation damage behavior
of two ion mass regimes. They compared the effects of implanting 12 C and
197 Au in GaN. From their RBS/C and Transmission Electron Microscopy
(TEM) results they concluded that there are similarities and differences in
the results from the two ions. In both mass regimes, the effect of dynamic
annealing is noticeable. Also, in both situations, two defect regions are
observed, one at the surface and another deeper in the bulk material. How-
ever, the authors observed differences on the efficiency of defect annihilation
for both regimes. Comparing disorder levels as obtained from RBS/C with
the results of SRIM simulations, they concluded that the defect generation
rate is larger in the case of heavy ion irradiation. A larger defect generation
rate is thought to enhance the rate of interaction between mobile defects.
As this rate increases, the probability of complex defect formation increases
as well, outbalancing defect annihilation promoted by dynamic annealing.
Concerning the effect the incoming ion energy, a more energetic ion will
have a deeper range in the target. However, not only the projected range
Rp will be higher, but also the dispersion ∆Rp will increase. This effect
is illustrated on figure 5.9. As such, the defect distribution will also be
affected, being more spread over a greater depth. The same is possible
to conclude from the results presented by Kucheyev et al. in another [83]
report. Besides the spread, it is also expected that the more energetic ions
generate a higher amount of defects as depicted on figure 5.10. Figure 5.11
illustrates the evolution of the number of Ga vacancies produced in GaN
during the implantation Eu ions at energies ranging from 10 to 300 keV as
obtained from SRIM simulations.
The degree of implantation damage a crystal undergoes is not only
dependent on the mass and energy of the implanted ion but also on other
Fig. 5.9: Depth distribution of Eu ions implanted in GaN at energies ranging from
10 to 300 keV as obtained from SRIM.
implantation parameters. One of such parameters that has been thoroughly

investigated (see [81, 83, 84, 85], for example) is the implantation fluence.
As mentioned in section 5.2, the density of collision cascades has a direct
influence on the number and sort of defects formed. However, thermally
driven recombination mechanisms have to be taken into account as well.
Wendler et al. [85] have investigated the damage build-up in GaN irra-
diated by several ions at increasing fluences at 15 K. They observed from
RBS/C measurements that damage formation follows a three-stage mech-
anism. At low ion fluences (< 8 × 1014 Ar/cm2 ), damage formation is
dominated by the nuclear energy deposition. At this stage, the presence of
the dynamic annealing mechanism is strongly noticed, even at temperatures
as low as 15 K. Due to this fact, the level of defect recombination, while
they are being created, is high. As such, the concentration of defects in-
creases only slowly with increasing ion fluence. The authors have concluded
that there is a certain critical value for the defect concentration, beyond
which the dynamic annealing process becomes less efficient due to the im-
Fig. 5.10: Comparison between the damage produced in the collision cascades
originated by one Eu ion implanted at 50 and 300 keV.
Fig. 5.11: SRIM depth distribution of the Ga vacancies produced during irradia-
tion with Eu ions at energies ranging from 10 to 300 keV.
perfect structure of the local lattice. The PKA becomes again efficient in
the production of damage causing a second stage of damage formation. At
this stage the damage concentration increases steeply with the ion fluence
until it begins to show saturation features (at about 7× 1015 Ar/cm2 ). It is
proposed that the saturation of the damage concentration is related to the
nucleation of amorphous pockets that increase in size during subsequent
implantation. The overlapping of these amorphous pockets eventually lead
to the formation of an amorphous layer.
Another experimental parameter that can be controlled during the im-
plantation process is the beam flux. This parameter is a measure of how
many ions, per unit of time, reach the target. As reported by Kucheyev et
al. [41], an increase in the beam flux will decrease the average time interval
between overlapping collision cascades. This leads to an increase in the
generation rate of point defects which enhances interaction between mobile
defects and thereby, enhances the formation of defect complexes. However,
as reported in [83], the effect of beam flux on implantation damage in GaN
appears not to be strong.
Despite the fact that GaN presents a high radiation damage resistance,
the efficient removal of retained implantation damage has proven to be a
challenge. Attempts to employ post-implantation thermal treatments up to
600 o C, to recover from the accumulated damage have proven to be useless,
whereas annealing between 600 o C and 1100 o C result in only a reduction of
the implantation damage [60]. This can be understood taking into account
the thermal energy requirements for point defects to become mobile and
recombine, and for breaking defect clusters formed during implantation
(figure 5.12). In fact, it has been observed that compound semiconductors
typically require a damage recovery temperature exceeding two thirds of
their melting point. Being the melting temperature of GaN about 2500
o C, one can expect efficient annealing temperatures for GaN to be above
1600 o C. However, material decomposition begins already at about 1000

o C, with the loss of N from the surface.
Several techniques [41], such as the use of a nitride proximity cap or

a constant flow of nitrogen gas during the annealing procedure, can be
Fig. 5.12: Diffusion, recovery, and activation processes of ion-implanted impurities

in GaN as function of annealing temperature (ref. [60]).
helpful in minimizing the decomposition, but these still do not allow an-
neals at temperatures higher than 1100 o C without destroying the surface
stoichiometry.
Extreme annealing conditions with temperatures of 1500 o C under an
overpressure of about 15 kbar of nitrogen have delivered the best results. In
fact, through this method, the complete removal of implantation-induced
damage without macroscopic surface decomposition was achieved. How-
ever, this method requires special technical equipment that is not available
in every research laboratory.
Another alternative to achieve high temperature annealing without sur-
face decomposition is to use a protective capping layer. This method had
been developed within the RENiBEl network. For this purpose, a layer of ∼
100 Å of AlN has been grown by MOCVD on GaN films and the behavior of
the samples has been investigated upon annealing at temperatures ranging
from 1100 to 1300 o C [86]. After 300 keV Eu ion implantation through the
protective layer, the samples have been thermally treated at the indicated
temperature range. It has been concluded that the protective AlN layer
effectively fulfills two tasks. During implantation the layer protects the
GaN surface and even inhibits the formation of the previously mentioned
surface defect region. It is thought that during the thermal treatment, this
layer prevents the outdiffusion of N from the GaN surface. Nevertheless,
complete damage recovery was not achieved, even at 1300 o C.
It can be concluded that, indeed regardless of the fact that radiation
resistance is higher in GaN, as compared to other semiconductors, restoring
the original crystalline quality is a problem! However, some experimental
results ([41, 84, 85, 86, 87, 88]) obtained from RBS/C structural analysis,
revealed that when the substrate temperature is increased during implanta-
tion, the concentration of implantation damage can be significantly reduced.
Such results indicate that elevating the substrate temperature during im-
plantation enhances the dynamic annealing mechanism, helping to limit the
density of defects in the implanted material.
Finally, the angle between the direction of incidence of the ion beam
and a major crystalline direction, is another experimental parameter that
can be controlled during implantation.
In their study on the importance of channeled implantation to the syn-
thesis of erbium silicide layers, Wu et al. [89] report that the implantation
of Er ions along a direction making an angle of about 0o ± 1.5o with the
< 111 > axis of Si, allows drastically reducing the lattice disorder caused by
implantation, as compared to the values from implantation along an angle
of 7o . This fact is confirmed by Hogg et al. [90], who further concluded that
implantation along the main crystalline direction - channeled implantation
- also allows a deeper penetration of the ions in the crystal and to reduce
the sputtering yield.
Pipeleers et al. have investigated the influence of the implantation angle
on the generation of defects for erbium-implanted GaN [87, 91]. Similarly
to what happens for Er implantation along the < 111 > axis of Si, these
authors have observed that the implantation of Er along the < 0001 > axis
of GaN results in a relatively small defect density due to the reduced num-
ber of nuclear collisions between the incoming ions and the lattice atoms.
They also observed that progressively increasing the implantation angle up
to 10o away from that axis, leads to a gradual increase of the defect density.
Fig. 5.13: Environment encountered by an incident ion along two different direc-
tions with respect to the GaN crystal. Top: random orientation; bottom: incoming
beam oriented with the c-axis.
The drastic reduction of the defect density caused by ion implantation

can be understood by considering the environment the ion will encounter
when it penetrates into the crystal along one of the main crystalline di-
rection (figure 5.13). By simple geometric arguments considering figure
5.13, one can conclude that the apparent atomic density the incoming ion
encounters when it reaches the crystal, changes dramatically when the ap-
proach is done along a random direction or along a major crystalline axis
or plane. In fact, the axial orientation offers the incoming ion regions of
Fig. 5.14: Representation of the ion trajectory along a crystalline channel [92]
open spaces where the ion won’t encounter lattice atoms. These regions are
known as channels (figure 5.14).
As mentioned in section 5.1, an incident ion undergoes a series of colli-
sions with target atoms, which can be described by considering a screened
Coulomb interaction potential. However, when the incident beam is aligned
with a crystal axis (or plane), the atoms constituting the crystal are ar-
ranged along rows (or planes) that border the channels. The Danish physi-
cist Jens Lindhard has formulated a theory on the channeling of ions in
crystalline solids [93]. In order to theoretically describe the channeling
phenomenon, instead of considering the potential at each individual inter-
action with the lattice atoms, Lindhard proposed that these rows of atoms
offer a continuous potential for the interaction with the ion. According to
Fig. 5.15: Trajectories of ions along a channel [94].
this model, if the ion enters the crystal along an axial direction, it will be
gently steered along the channel by small angle deflections, each time it
approaches one of the atomic rows. As a result, the channeled ion follows
an oscillatory forward trajectory, as illustrated on figure 5.15. However, in
order to maintain the channeling motion, the ion must not approach the
rows of atoms too closely. As such, there is a critical angle above which ions
entering the crystal will no longer be channeled. The value of the critical
angle can be determined from Lindhard’s formalism (briefly described on
appendix A). This value depends on the atomic number of both ion and
target atoms, interatomic distances and the ion energy.
Lindhard’s formalism was more specifically developed for the case of
low-mass ions impinging the target at high energies. In this context Lind-
hard treats the high-mass low-energy regime (usually employed in ion im-
plantation) as a particular, more complicated case. Nevertheless, as Hogg
et al. demonstrated in [90], the formalism remains valid in the regime
of interest for ion implantation. Employing this formalism, one obtains a
value of 7.3o for the critical angle of 80 keV 153 Eu in GaN. This value is
in good agreement with the experimentally obtained value of 6.5o reported
by Pipeleers et al. ([91]) for 80 keV 166 Er in GaN.
The explanation for the defect density reduction during channeled im-
plantation, as compared to implantation along a random direction, resides
in the fact that the well-channeled ions are solely gently steered along the
crystal. In this case, the incoming ions do not experience the potential
of individual lattice atoms (as is the case in random implantation), but

the effect of the continuum potential of the rows of host atoms compos-
ing the channel “walls”. Due to the gentle steering towards the center of
the channel, for channeled implantation the contribution of nuclear stop-
ping is much weaker than when compared to random implantation. As
a consequence channeled ions reach far deeper inside the crystal without
experiencing head-on collisions with target atoms. This has a great impact
on the crystalline host defect distribution.
To evaluate defect concentrations on implanted material, and more gen-
erally to perform the structural characterization of that material, one can
employ another sort of ion beam: light mass MeV accelerated ions, as em-
ployed by RBS/C.
5.4 Rutherford backscattering and channeling

spectrometry
Rutherford backscattering and channeling spectrometry is a powerful ana-
lytical technique, employed in the characterization of materials. This tech-
nique makes use of a well collimated beam of light ions (4 He+ ions for this
work) accelerated in the range of 1-4 MeV, to interact with the atoms con-
stituting the target material. When these ions reach the target, they mainly
suffer inelastic collisions with the target electrons, as described in section
5.1. However, at a certain instant along their inwards trajectory they can
experience a head-on nuclear collision with the nucleus of target atom. A
small percentage (∼ 0.01%) of those ions, will have their trajectories, after
the collision, deflected by an angle larger than 90o - they are said to be
backscattered. Placing a particle detector in the backscattering direction
allows counting the number, and measuring the energy of the backscattered
ions. The result of plotting on a x-y graph the amount of particles (y) de-
tected with a certain energy (x), is a backscattering spectrum from which
information on the structural composition of the target can be obtained as
a function of depth. Figure 5.16 exemplifies such a spectrum. RBS is a
very powerful solid state analytical technique. By using appropriate tools
5.4 RBS\C 97
Fig. 5.16: RBS spectrum of the compositional analysis of an AlInN thin film
grown on a GaN film
(computer codes based on the theory) to perform fittings of RBS spectra

one can deduce very relevant information about the sample in study. In
particular, it is possible to deduce the sample elemental composition (which
elements?), the distribution of elements through the material (where?) and
the quantities of those elements in the sample (how much?). Those pa-
rameters are deducible from three physical concepts, fundamental for this
analytical technique: the kinematic factor; the stopping cross section; and
the scattering cross section. A more detailed description on these quantities
and concepts can be found in appendix A.
In the same way that heavy ions can be channeled through the crystal
during implantation, when the collimated beam is aligned with one major
crystalline direction, the He-ions from that beam are channeled throughout
the crystal. As a consequence, the number of backscattered particles is
drastically reduced.
From the number of backscattered ions along a channeled direction,
Fig. 5.17: RBS spectra obtained with the beam aligned with a random direction
(•) and aligned with the < 0001 > axis of GaN, for unimplanted (∗) and Eu
implanted samples (◦). Above 1.4 MeV, the signal corresponding to the Eu ions
implanted along 10o away from the < 0001 > axis (4).
information about the target crystalline quality can be obtained. In fact,

if the incident ion is well aligned with a channel from a perfect lattice, the
probability of a close encounter event, resulting on the backscattering of
that ion is very small. However if the lattice is damaged, the channeled
particles interact strongly with host atoms on non-regular lattice positions
that obstruct the channel. As a consequence, the yield of backscattered
particles increases.
By comparing the spectra from the randomly aligned with the channel-
aligned beam situations, it is possible to extract information about the
crystalline quality of the host material. This is illustrated on figure 5.17,
where the spectra, measured with the beam aligned with the < 0001 >-axis
of GaN (also known as the c-axis) of an unimplanted and a 153 Eu-implanted
sample are compared with the randomly-oriented spectrum.
Attending to the aligned spectrum of the implanted sample (◦), the
increased 4 He+ backscattering yield at the region close to the surface (be-
5.4 RBS\C 99
Fig. 5.18: Increase of dechanneled ion fraction with depth.
tween 1.3 and 1.4 MeV), is an indication of the amount of Ga atoms dis-
placed during implantation. Furthermore, in the same spectrum, the yield
below 1.3 MeV (undamaged crystal) is considerably higher than the equiv-
alent region of the unimplanted sample spectrum (∗). This yield increase at
the undamaged lattice is a consequence of the 4 He+ ions dechanneling at
the surface damaged region on the implanted sample. The incoming He-ions
are first dechanneled by the displaced host atoms and are then backscat-
tered during other collision events with host atoms from the undamaged
region. The dechanneled fraction of ions has to be taken into account for
the quantitative evaluation of the lattice disorder. Usually, a linear increase
of the dechanneling fraction is assumed ([102]), but a more correct treat-
ment of this analysis was proposed by Schmid in 1973, as described in [103].
The result of this treatment is compared with the simpler linear increase
of the dechanneling fraction, on figure 5.18. Pipeleers has used the latter
approach to develop an iterative method to calculate the fraction of dis-
placed Ga atoms in implantation-damaged GaN samples ([104]). Using the
Ziegler, Biersack and Littmark stopping powers ([105]) for 4 He+ in GaN, a
Fig. 5.19: Random and channeled aligned spectra with energy to depth scale
conversion.
conversion between backscattered ion energy and depth scale is obtained.

Figure 5.19 illustrates the conversion to the depth scale of both random
and aligned spectra obtained from the Eu-implanted GaN sample. This
conversion is useful to obtain the lattice disorder depth profile (subtracted
from the dechanneled fraction), as described in [102] and [103]. For GaN,
due to the fact that the cross section for scattering from N atoms is very
small (as compared to Ga), only the displaced Ga atoms will be considered
in accessing the implantation induced damage. Figure 5.20 illustrates the
concentration of displaced Ga atoms with increasing depth.
The quality of the crystal can also be evaluated by performing an angu-
lar scan of the incident beam direction with a major crystalline direction.
To obtain such a scan, it is necessary to define an energy window in the
region below the surface, on the aligned spectrum, as shown in figure 5.21.
Then, by plotting the counts of particles detected with energy within the
window, as a function of the beam direction from a particular crystalline
direction, an angular yield profile as shown in figure 5.22 is obtained. The
5.4 RBS\C 101
Fig. 5.20: Concentration of displaced Ga atoms with depth. A disorder level of

100% implies an amorphized crystalline lattice.
Fig. 5.21: Energy window selection on the aligned RBS spectrum, for a channeling
angular scan.
Fig. 5.22: Angular yield profile of an unimplanted GaN sample.
relation between the angular scan and a random-aligned spectra combina-

tion is indicated on the three-dimensional representation on figure 5.23.
An angular scan can be described, to a first approximation by the two
values indicated on figure 5.22, namely the half-angle - Ψ1/2 , taken at
1/2(1 + χmin ), and the normalized minimum yield - χmin . These quan-
tities are an indication of the crystalline quality of the analyzed material.
In a simple manner, Ψ1/2 describes the maximum angular tilt from the
channeling direction that a beam of incident ions is allowed to have, in
order to still be gently steered throughout the channels - it is often refereed
to as the critical angle. For GaN and for a 1.57 MeV 4 He+ ion beam, a
value of Ψ1/2 around 0.7 − 0.8o , is obtained from excellent quality crystals.
This value is in good agreement with the value deduced from Lindhards’
channeling theory: 0.9o for 4 He+ in GaN, at room temperature - calculated
considering one-dimensional root mean-square vibration amplitudes for Ga
and N of 0.074 Å and 0.081 Å, respectively [107]. With these values, the
Debye temperatures for Ga and N are ΘGa N
D = 344 K and ΘD = 747 K,
respectively. More detailed information on these calculations can be found
5.4 RBS\C 103
Fig. 5.23: Three-dimensional representation of the angular yield profile [106].
in appendix A.
The minimum yield, χmin , is an indication of the number of ions that
are backscattered when the beam is well aligned with the channel axis.
A good crystal is normally characterized by a low χmin . In the case of
GaN, a crystal presenting a value of about 2% along the c-axis, is generally
considered of excellent quality.
RBS in the channeling mode can also be employed to determine the
lattice location of an impurity. For this purpose, angular scans as described
above (now also defining an energy window for ions backscattered at the
impurity) are employed. However, as can be seen in figure 5.24, it can
happen that, for a particular crystalline direction, the host atoms hide
an impurity. As such, angular scans in more than one direction - named
triangulation - are required to locate the impurity lattice position.
Figure 5.25 shows scans along four different directions in Eu-implanted
GaN. It can be seen that the Eu-related signal follows the same trend as
the one of Ga. This is an indication that the Eu-ion is located at a Ga-
Fig. 5.24: Conceptual angular yield profiles for a two dimensional crystal [102].
substitutional lattice site. The deviations between the two signals in all the
four scans are due to the low count statistics from the Eu signal and due to
the difference in atomic number between the host Ga (Z=31) and the Eu
impurity (Z=63).
As mentioned by Wahl et al. in [108], due to uncertainties on the accu-
racy of the azimuthal angle of the scans (influenced by remaining implan-
tation lattice damage, for example) it is difficult to derive precise values for
the root mean squared (rms) displacement of RE ions from the perfect sub-
stitutional Ga site. However, these authors have used Monte Carlo methods
([109]) to simulate and fit the angular scans for the Ga and seven RE ions
(Ce, Pr, Eu, Dy, Er, Tm and Lu) along the < 0001 > and < 101̄1 > direc-
tions. The comparison between their experimental and simulated results
can be seen on figure 5.26. These authors observed that all the implanted
RE, except Eu, present an rms displacement of about 0.07Å from the sub-
stitutional Ga position. For Eu, the only successful fit, for the < 101̄1 >
direction, was obtained considering a displacement of about 0.2Å along the
< 0001 > direction. The displacement value seems to be in good agreement
with the value De Vries et al. ([110]) obtained through the Emission Chan-
5.4 RBS\C 105
(a) c-axis (b) < 101̄1 >
(c) < 1̄102 > (d) < 2̄113 >
Fig. 5.25: Angular scan along the < 0001 >, < 101̄1 >, < 1̄102 > and < 2̄113 >
directions in GaN, measured on the signals from Ga and Eu.
neling technique (rms ∼ 0.13 − 0.16 Å). A comprehensive description of the

Emission Channeling technique can be found in reference [111]. The fact
that these results indicate that RE ions occupy a Ga-substitutional lattice
site is in good agreement with the theoretical predictions obtained from
Density Functional Theory, as described in section 2.5.3. Furthermore, the
slight displacement of RE-ions from the perfect Ga-substitutional site (as
suggested by these angular scans) agrees well with the RENiBEl theoreti-
cal studies ([46]) suggesting that the REGa − NV is the most favorable and
stable configuration that can be optically active.
Fig. 5.26: Angular scan along the < 0001 > and < 101̄1 > directions, measured
on the signals from Ga and Ce, Pr, Eu, Dy, Er, Tm and Lu. [108]
5.4 RBS\C 107
As described in this chapter, ion beams are a powerful tool in the do-
main of semiconductor processing and characterization. The two-fold ap-
plication of this tool has been crucial for the investigation work herein
reported. The essential aspects related to the doping of semiconductors by
ion implantation have been discussed, with particular incidence given to
the implantation of 153 Eu in GaN, structural defect formation, ion ranges
and parameters that condition the process. Following this, the second ap-
plication of ion beams has been discussed, namely, ion beams for structural
characterization. In particular, the robustness of Rutherford backscattering
and channeling spectrometry has been demonstrated. This elegant analyt-
ical technique allows not only to detect which impurities are present in
a host, but also their concentration and depth distribution profile. Fur-
thermore, the channeling variant of this technique allows to investigate the
host crystalline quality before and after doping and even obtain information
about the lattice site occupied by the dopant. An example of both of these
applications is the implantation of an 153 Eu beam into GaN followed by the
structural analysis of the implanted material. RBS/C further allowed to
conclude that the implanted Eu ions preferentially occupy a substitutional
Ga-site in the GaN lattice.
Chapter 6
Structural characterization
of Eu-implanted GaN
So far, the motivation, theoretical framework and employed analytical tech-

niques have been described. In this chapter, the experimental results of this
work will be presented and discussed, with special focus on the results of
structural characterization of Eu-implanted GaN. Mainly two techniques
were employed in this characterization, namely RBS/C and High Reso-
lution X-ray diffraction (HRXRD). Optical characterization by means of
photo and cathodoluminescence analysis were also performed on certain
key samples in order to complement the information obtained by RBS/C
and HRXRD.
6.1 Experimental details
Nitride samples
The nitride films employed as host material for this work, unless specifically
otherwise mentioned, were grown by the Groupe d’Etudes des Semiconduc-
teurs (GES) of the University of Montpellier II, a partner institution of
the RENiBEl network. The growth method to obtain such films has been
described in section 1.2.
109
110 Structural characterization of Eu-implanted GaN
Fig. 6.1: Eu-implanted areas on two GaN samples implanted with 1 × 1014 (left)
and 5 × 1014 (right) Eu/cm2 at 80 keV.
Ion implantation
Similarly, unless otherwise mentioned, the isotope employed in this study
was 153 Eu. Other, to lesser extent, implanted isotopes were 158 Gd, 166 Er
and 132 Xe. The typical implantation beam current density was between
0.1 and 2µA. The samples are placed on a goniometer in a chamber with
a vacuum level of about 10−9 Torr. The implantations were performed
by sweeping the beam, through an aperture of 0.7 × 0.7 cm2 placed in
front of the sample holder, in order to achieve homogeneous implantation
areas. The implanted area is visible for fluences above 5 × 1013 Eu/cm2
at 80 keV. The change of color in the implanted area occurs due to the
fact that implantation induced defects absorb incident light that normally
would simply be reflected or transmitted. This color change is visible in
figure 6.1. Simply through inspection with the naked eye it is possible
to conclude that, as expected, the lattice damage is higher on the sample
implanted with a higher fluence.
RBS/C
After implantation, the samples are mounted on a high precision (0.01o )
three-axis goniometer inside a vacuum chamber, for RBS and RBS/C anal-
ysis. This chamber is connected to the beam line coming from a Pelletron
6.1 Experimental details 111
Fig. 6.2: Scheme of beam-sample-detectors geometry.
accelerator, operating according to the principle of a tandem Van de Graaff

accelerator. An incident, 1.57 MeV 4 He+ , beam with a diameter of approx-
imately 1 mm, is backscattered by the sample and detected by two silicon
barrier detectors. The detectors are coplanar with the perpendicular to the
sample surface and incident beam direction. One of them, known as the an-
nular detector, is placed at an angle of 168o to the direction of the incident
beam, optimizing the mass resolution. The other, the glancing detector is
mounted on a circular movable frame that allows placing the detector on
a variety of angular direction. Normally this detector is placed at an angle
of 105o with the direction of the beam (figure 6.2), in order to increase the
resolution in depth. Also, at this angle, it is still possible to separate the
signal from Ga and Eu in the RBS spectrum. The typical energy resolution
of both detectors is 14 keV.
The obtained backscattering spectra were analyzed employing the RUMP
computer code [112]. The defect concentration profile was determined by
employing a C++ computer program based on the algorithm developed by
Bert Pipeleers, as indicated in section 5.4. This program has recently been
modified to allow its use for similar studies in other nitride systems and
germanium [113].
High-resolution X-ray diffraction
High-resolution X-ray diffraction (see appendix B) allows obtaining comple-

mentary information on the quality of the crystalline structure. Diffraction
measurements on the planes perpendicular to the GaN c-axis, such as the
{0002} family of planes, allow measuring the out-of-plane lattice strain.
Diffraction from inclined planes, such as the (101̄5) GaN planes, allows
obtaining information concerning the in-plane strain. The HRXRD mea-
surements were performed on a D8 Discover from Bruker. In this system
X-rays are generated from a Cu source operating at 40 mA and 40 kV. The
X-rays are then monochromated by a set of four Ge(002) crystals in order
to obtain only the Kα1 component of this radiation. The beam is then
collimated by a set of slits with an aperture of about 1 mm and after being
diffracted at the sample, the beam passes through another set of slits (1 and
0.6 mm) before it is detected at a scintillator. The sample is mounted on a
three axis goniometer commanded by a computer. The computer controls
both sample position and data acquisition.
Optical characterization
As mentioned above, optical characterization by means of photo and cathodo-

luminescence measurements was also performed. Briefly, photolumines-
cence consists of the absorption of light by a material followed by the emis-
sion of light (usually of longer wavelength than the absorbed) by that ma-
terial. In a semiconducting material, the energy of the absorbed light can
promote an electron from the valence band into the conduction band, leav-
ing a hole in the valence band. When the electron from the CB recombines
with the hole in the VB, the de-excitation energy can follow radiative or
non-radiative paths. In a radiative path, the released energy is emitted as
a photon. In non-radiative paths, the released energy can occur in several
ways: absorption by the material producing other electron-hole pairs, and
dissipation in the crystalline lattice in the form of phonons, for example.
6.2 Structural damage due to ion implantation 113
In photoluminescence (PL) spectroscopy, the energy of the emitted light

is related to the energy difference between the excited and fundamental
states of the promoted electron, while its intensity is related to the relative
contributions of the radiative process. PL results were obtained by charac-
terizing the samples with a Helium-Cadmium laser with a wavelength of 325
nm in a temperature range from 15 to 300 K, controlled by a closed-cycle
He cryostat.
Cathodoluminescence (CL) spectroscopy is an optical characterization
technique similar to PL, however the excitation process employs energetic
electrons (keV) instead of photons (eV). By tuning the acceleration voltage
of the CL electron beam it is also possible to obtain depth-resolved measure-
ments. CL measurements were performed with an Cameca SX100 electron
probe microanalyser (EPMA), employing electron beams with typically 10
kV and 30 nA and detecting luminescence on a CCD camera.
PL and CL measurements were performed by RENiBEl members Iman
Roqan and Dr. Emilio Nogales from the Department of Physics of the Uni-
versity of Strathclyde, Glasgow, United Kingdom.
In this chapter, the effect of several implantation parameters on the

integrity of the crystalline structure, as pointed out in section 5.3, will
be discussed considering the results of structural characterization. This
discussion will be performed in the framework of the physical processes
involved in the luminescence mechanism of RE-doped nitrides.
6.2 Structural damage due to ion implantation

In order to evaluate the level of structural damage produced on a sample by
ion implantation, one has to define a standard of quality for the crystalline
structure. Such a standard can be obtained from an as-grown, unprocessed
sample presenting a structural quality considered exemplar, with character-
istics as described in section 5.4. Figure 6.3 shows the random and c-axis
oriented RBS/C spectra of an unimplanted sample. The remarkable differ-
ence between the backscattered yield from the two alignment directions is
Fig. 6.3: Random and c-axis aligned RBS spectra obtained from an unimplanted
GaN sample, showing a χmin value of about 1.6%.
an indication of this sample’s excellent crystalline quality. As indicated in

section 5.4, this can be quantified by the minimum yield - χmin .
The structural defects generated in the crystal structure upon ion im-
plantation drastically alter the shape of the aligned RBS spectrum, as men-
tioned on section 5.4. This can be seen by comparing figures 6.3 and 6.4.
Converting the energy scale from figure 6.4 into a depth scale and sub-
tracting the dechanneled ion fraction, as described in section 5.4, the aligned
spectrum can be plotted as shown on the top spectrum of figure 6.5. It can
immediately be seen that the displaced Ga atoms are spread in depth over
two overlapping defect regions. The figure illustrates that it is possible to
fit this part of the spectrum with a sum of two gaussian functions. The
first gaussian is approximately centered around 55 Å and has a full width at
half-maximum (fwhm) of about 80 Å. This region will be referred to as the
surface defect region. The second gaussian has its central value at about
170 Å and 150 Å of fwhm. These two last values are in good agreement
Fig. 6.4: Random and aligned spectra of a 4 × 1014 Eu/cm2 implanted GaN
sample.
with the projected range and straggling (fwhm/2.355) for 80 keV Eu ions
in GaN as calculated from SRIM, namely 200 Å and 72 Å, respectively. At
this depth range the implanted Eu ions come to a stop and lose most of
their energy on nuclear collisions with target atoms, causing an elevated
number of host-atoms displacements. Due to this fact, this second region
will be referred to as the near end-of-range (EOR) defect region. As can
be seen in figure 6.5, the EOR defect region is in good agreement with the
vacancy (both Ga and N) distribution profile as calculated by SRIM [114].
It should be mentioned that the analyzed sample has been implanted
with the incoming Eu ion beam directed 10o away from the c-axis direction.
It was done so, with the purpose of minimizing the channeling effect of the
Eu ions in GaN. In fact, as it will be later discussed, channeling can smear
out the Eu ion distribution very deep inside the GaN host.
As mentioned in the introductory section, HRXRD was also performed

Fig. 6.5: Top: c-axis aligned backscattering spectrum of a 4 × 1014 Eu/cm2

implanted GaN sample. It is possible to distinguish two overlapping regions of
damage, one near the surface and another deeper in the sample. Bottom: Dis-
tribution of the displaced Ga atoms superposed with the vacancy distribution as
obtained from SRIM, and the experimental implanted Eu ion distribution.
Fig. 6.6: HRXRD spectra obtained from the (0002), (0004) and (0006) symmetric
reflections in GaN.
in order to complement the structural characterization obtained by RBS/C.

Figure 6.6 shows the (0002), (0004) and (0006) reflection peaks of an unim-
planted GaN sample, obtained from a θ−2θ scan (see appendix B). Despite
the fact that the higher the index plane is, the better angular resolution the
angular scan offers, figure 6.6 shows that the diffracted intensity is strongly
reduced (notice the logarithmic scale) for the higher index planes. For this
reason, during this study, mainly the GaN (0002) reflection has been used
to analyze the effect of implantation damage on the lattice structure along
the c-axis direction. To analyze the same effect on the in-plane direction
(a-axis), the GaN (101̄5) plane reflections were chosen.
Figure 6.7 compares the θ − 2θ scans on the (0002) reflection of a unim-

planted and 4×1014 Eu/cm2 implanted GaN samples. As the figure shows,
along with the main GaN (0002) reflection peak, a shoulder with a long tail
falling to the lower angle side appears on the spectrum measured on the im-
planted sample. The significance of this shoulder can be understood taking
Fig. 6.7: HRXRD θ − 2θ spectra obtained from the (0002) reflection of an unim-
planted and 4 × 1014 Eu/cm2 implanted GaN samples.
into account the law of Bragg:
nλ = 2d sin θ, (6.1)
where λ is the X-ray wavelength, d the distance between the diffracting

planes and n an integer equal to the reflection order. From this equation
it is possible to conclude that a smaller θ angle corresponds to diffractions
from planes with a larger interplanar distance. The larger interplanar dis-
tance reveals lattice expansion caused by the implantation process. In the
case of RE-implanted GaN, such lattice expansion does not originate by the
fact that the RE ion mainly substitutes the Ga atom in the lattice after im-
plantation, since the ionic radius of Ga3+ and RE 3+ are comparable (0.62
and 0.9-1.0Å) ([55]). The expansion of the lattice is most probably caused
by the generation and accumulation of interstitial defects during implanta-
tion. Such an effect has been observed by Bai and Nicolet ([115]) for the
case of self-implanted Si. These authors concluded that self-interstitials are
the main origin for the lattice strain in Si-implanted Si.
It is then expected that the lattice strain profile follows the same dis-
tributional behavior as the implantation induced defects. Attending to the
gaussian distribution defect profile, as obtained from SRIM, one can expect
the lattice parameter to have its maximal value where the concentration of
defects is higher. Also, a gaussian distribution of lattice parameters in the
implanted region can be assumed. Consequently, to such distribution of
lattice parameter values, a similar profile of values for the Bragg angle will
be associated, with the minimum value of θ corresponding to a maximum
value of the lattice parameter. Both distributions are represented in figure
6.8. The diffraction intensity strongly depends on the lattice quality. A
strongly disordered lattice will produce a less intense diffraction peak than
the one due to an expanded but still ordered crystalline lattice. However,
the intensity of diffraction from the expanded lattice, will be considerably
lower than that of the undamaged bulk material. As such, the intense peak
centered around 34.6o on figure 6.7 corresponds to diffractions at the bulk
GaN, whereas the shoulder and the tail to the lower angle values correspond
to diffractions from the implanted GaN region.
Combining the observed results from RBS/C and HRXRD measure-
ments, it can be concluded that implantation damage is distributed through-
out two defect regions, one at the surface and another close to the ion end
of range. This damage generates strain along the direction perpendicular
to the surface.
It is important to evaluate how the several parameters as discussed in

section 5.3 affect the buildup of the structural damage upon implantation.
For this purpose, a systematic study will be presented on the influence of
the dopant fluence, the angle between the beam and c-axis directions, the
substrate temperature during implantation, the composition of the nitride
film, the dopant mass and the energy of the incoming ion beam. Also,
the effect of implanting through a protective AlN layer grown on top of
the GaN, as discussed in 5.3, will be analyzed. Finally, a method will be
discussed to extend the analytical possibilities of RBS/C to conclude about
the nature of implantation defects.
Fig. 6.8: Lattice parameter and Bragg angle value distribution of implanted GaN.
6.3 Fluence dependence 121
6.3 Fluence dependence

One of the parameters that can be controlled during semiconductor doping
by ion implantation, is the dopant concentration. As previously discussed,
the dopant fluence has a strong weight in the generation of structural dam-
age on the host lattice. It is thus important to assess how this damage
builds up with increasing dopant fluence. For this purpose, a set of GaN
samples was implanted with 153 Eu ions at room temperature, along a di-
rection making an angle of 10o with the GaN h0001i-axis (to minimize
channeling) with ion fluences ranging from 1 × 1014 to 3 × 1015 Eu/cm2 .
After the implantations, each sample has been characterized by RBS/C.
Figure 6.9 presents the normalized h0001i-aligned RBS/C spectra from the
set of implanted samples as compared to the randomly aligned backscatter-
ing yield. The amount of displaced Ga atoms, that translates into the struc-
Fig. 6.9: Damage build-up in GaN at room temperature by implantation of Eu

with fluences in the range of 1 × 1014 to 3 × 1015 , along 10o with respect to the
GaN c-axis.
tural damage upon implantation, increases non-linearly with the dopant

fluence.
For low implantation fluences (≤ 3 × 1014 ) the damage concentration is
still relatively small and limited to the surface, with no indication of end
of range (EOR) damage peak, as described in the previous section. At
these low fluences the density of collision cascades is still small and thereby
strong in-cascade defect recombination occurs without significant influence
of neighboring cascades. The remaining damage is mainly composed of
point defects such as Ga and N interstitials and vacancies, and small defect
clusters that failed to recombine while the energy within the cascades was
being dissipated. These point defects are mobile at room temperature and,
as will be discussed in section 6.6, they are thought to migrate and accumu-
late at the host surface, which acts as an effective sink. This is illustrated
in figure 6.9 for fluences below 3 × 1014 Eu/cm2 where the vast majority of
the damage is at the surface, and no bulk damage is measurable.
Increasing the fluence leads to a more frequent overlapping of collision
cascades from ions entering the target along trajectories that are close to
each other. Consequently, the concentration and size of defects has in-
creased giving rise to the bulk defect peak shown in figure 6.9 for fluences
above 3 × 1014 Eu/cm2 . Two damage regions are now distinguishable on
the RBS/C spectrum: the surface damage peak is increased in magnitude,
and the EOR damage peak is now present.
Further fluence increase results in a further increase of the disorder level
in both regions. However, the amplitude of the surface damage peak grows
significantly faster than that of the near-RE-EOR damage peak. In fact,
the surface damage peak reaches the random level already at a fluence of
8 × 1014 Eu/cm2 , if not even earlier - it should be noticed that due to the
energy resolution of the detector (about 14 keV/channel) it might not be
possible to obtain information about a thin amorphous layer at the surface,
formed already at lower fluences.
While the surface damage area reaches random levels already at only
intermediate doses (8 × 1014 Eu/cm2 is below the amorphization threshold
level of 5 × 1015 Er/cm2 [116]), the amplitude of the EOR damage region
Fig. 6.10: Bright field TEM cross section image of a GaN sample sample implanted
with a fluence of 4 × 1014 Eu/cm2 10o off the c-axis.
starts to saturate at about 60% of the random level, already at a fluence

of about 6 × 1014 Eu/cm2 . It has been proposed ([84, 117]) that this sat-
uration behavior is due to two factors, namely, the migration of defects to
the surface, and the strong efficiency of the dynamic annealing mechanism
in GaN. As ions come to a stop they deposit most of their energy in this
(EOR) region. As a consequence generated defects are either annihilated
in recombinations due to the dynamic annealing mechanism, or they ac-
quire enough thermal energy to quickly diffuse away towards the surface.
As a consequence, the bulk region saturates whereas the surface damage
peak increases in amplitude until the random level in the RBS spectrum
is achieved - amorphous surface. From this point on crystal amorphization
proceeds inwards in the direction of the bulk material.
The difference in behavior between the two defect regions suggests a
different nature of the defects therein. This is in fact confirmed by the
Transmission Electron Microscopy (TEM) analysis of such a sample. Fig-
ure 6.10 shows a bright field TEM image of a 4 × 1014 Eu/cm2 random
implanted GaN sample. The image reveals a region, between the surface
and 15 nm below, of completely disordered lattice structure. Below the
amorphous surface, a region of high density of stacking faults, planar de-
fects and point defect clusters can be observed. These observations are
compatible with the assumptions that upon irradiation defect complexes
and point defects are formed in the RE-ion EOR region and that the size
and complexity of defects in that region are strongly influenced by the ef-
ficiency of the dynamic annealing mechanism. In the case of GaN, the
efficiency of that mechanism is considerably high (as compared to Si, for
example) and consequently the mobility point defects is high, leading to
in-cascade recombinations and migration towards the surface. As a result,
the disorder level in the EOR region increases at a much slower pace that
that of the surface, where point defects accumulate.
Further insight in the influence of fluence on the damage build up is

brought by HRXRD. Figure 6.11 shows the evolution of the shoulder on
the spectra with increasing ion fluence. This shoulder, as described above
(section 6.2), is accounted for by the expansion of the lattice in the region
of implantation due to structural damage. As seen from the RBS/C results,
for low implantation fluences the lattice damage is small and mostly con-
sists of point defects (vacancies and interstitials) and small clusters. The
presence of such defects will locally induce lattice strain. In this case it
is possible to conclude that lattice expansion occurs, as is seen from the
spectrum for 1 × 1014 Eu/cm2 (¥ ) on figure 6.11 by the lower value of 2θ (∼
33.9o ) as compared to the value for the unimplated GaN (∼ 34.6o ). Despite
the fact that there is expansion in the implanted region (locally generating
a distribution of lattice parameters (fig. 6.8)), the lattice is still diffracting
a considerable amount of the incident X-rays. Increasing ion fluence has
the effect of shifting the end of the decaying tail towards lower values of
2θ, revealing an increase of the lattice expansion. However for 3 × 1014 ,
despite the fact that the minimum value of 2θ is slightly lower (higher lat-
tice expansion) than for 1 × 1014 , the overall crystalline quality appears to
Fig. 6.11: HRXRD θ − 2θ spectra of the (0002) reflection of samples implanted

with fluences ranging from 1 × 1014 to 1 × 1015 Eu/cm2 .
be higher, as can be seen by the higher intensity of the shoulder peak for
that fluence. This might be an indication that for 3 × 1014 Eu/cm2 there is
a smaller dispersion of lattice parameter values, as compared to 1 × 1014 ,
giving then rise to a more intense diffraction shoulder on the spectrum.
As the fluence increases to 3.6 × 1014 Eu/cm2 and higher, an increase
of concentration and size of defects occurs, as seen by the RBS/C results.
This increase of structural defects is responsible for the appearance of the
EOR defect region in the RBS/C spectra but also for the increase of lattice
expansion (2θ ∼ 33.6o and lower) and decrease of diffraction intensity from
the implanted area.
Similar results have been observed by Liu et al. [81] for the case of Ca
and Ar-implanted GaN. These authors propose that the lattice expansion at
the origin of the shoulder peak is limited in magnitude, in order to main-
tain the crystalline structure. For low implantation fluences, the lattice
expands but still maintains its basic integrity as structural defects are only
composed by relatively low concentrations of point defects and small clus-

ters. However, exceeding a threshold magnitude of lattice expansion results
in local collapse of the lattice into amorphous clusters. With increasing ion
fluence, the dimensions of these amorphous clusters are increased, as well
as their density. The amorphous regions grow through damage accumula-
tion into the underlying crystalline regions as fluence increases. Eventually
overlapping of amorphous clusters starts to occur resulting in a broader
continuous amorphous region.
Figure 6.12 shows the cathodoluminescence spectra of two GaN sam-
ples implanted at room temperature (RT) with Eu ions, along 10o off the
c-axis with Eu fluences of 1 × 1014 and 5 × 1014 /cm2 . After implantation
the samples were thermally treated at 950o C for 30 minutes under N2 flow
with a GaN proximity cap to recover from the accumulated implantation
defects. The spectra were acquired at room temperature with incidence
of a 5 kV electron beam with a current of 30 nA and 10 nm defocusing,
for 1 second. In both spectra, the main Eu-related luminescence lines are
visible: 5 D1 →7 F1 (543 nm), 5 D0 →7 F1 (600 nm), 5 D0 →7 F2 (621
nm) and 5 D0 →7 F3 (663 nm). As can be seen, luminescence intensity is
stronger for the 1 × 1014 Eu/cm2 sample. This fact indicates that the much
larger lattice damage fraction (as measured by RBS/C) caused by the im-
plantation of 5 × 1014 Eu/cm2 is quenching the luminescence, even after
applying 950o C thermal treatments. This fact is in good agreement with
the discussed RBS/C results. As seen, fluences above 3 × 1014 Eu/cm2
generate not only larger defect concentrations, but also extensive defect
configurations. Unlike simple point defects, the extensive defects are ther-
mally more stable and thus more difficult to recover by posterior thermal
treatments. Implanting at a lower fluence (5 times less) causes less damage
to the lattice and, even though the amount of introduced Eu -ions is lower,
the luminescence yield is higher due to less defect-related quenching.
80 keV 153 Eu implantation introduces structural defects in the GaN lat-

tice. The level of lattice disorder increases non-linearly with increasing ion
fluence. Low fluences generate small concentrations of point defects (VGa,N ,
Fig. 6.12: Cathodoluminescence spectra of 1×1014 and 5×1014 Eu/cm2 implanted

GaN samples.
IGa,N ) and small defect clusters. At room temperature such defects are mo-
bile and tend to recombine or migrate towards the crystal surface. Remain-
ing defects in the Eu EOR region generate lattice expansion. Increasing the
fluence leads to the formation of more complex defect structures, due to an
increase in the density of collision cascades. These defects further expand
the lattice in the region of implantation. The concentration and dimensions
of such defect complexes is limited by the dynamic annealing mechanism
in GaN. Simultaneously, generated point defects keep on migrating and ac-
cumulating at the surface forming a completely disordered region. Further
increasing the ion fluence leads to further lattice expansion accompanied by
deterioration of the crystalline structure. At the same time the concentra-
tion of point defects at the surface keeps increasing and consequently the
thickness of the amorphous region increases inwards. Eventually the two
defective regions (surface and EOR) overlap and amorphization occurs.
6.4 Implantation direction
As discussed in chapter 5, the incidence angle of the incoming ions with

respect to a major crystalline direction has a strong impact on the implanta-
tion generated defect density. A study on the influence of the implantation
angle on the generation of lattice damage has been published by Pipeleers
et al. [91]. In that study, the authors have compared the defect density
caused by the implantation of 2.5 × 1014 Er/cm2 in GaN samples, along
a series of decreasing angles ranging from 10o to 0o between the direction
of the incoming ion beam and the h0001i-GaN axis. The density of de-
fects is drastically reduced from about 1 × 1017 Ga-displacements/cm2 for
the implantation at 10o to about 2.5 × 1016 Ga-displacements/cm2 for an
implantation along the c-axis. As described in section 5.3, the reason for
the reduction in lattice damage is the fewer head-on collisions the incoming
ions experience with the lattice host atoms, as they penetrate the material
along a direction close to a main crystalline direction. In their study, the
authors experimentally derived a critical angle - maximum angle for which
the incident ions are still gently steered along the crystalline channels, of
about 6.5o . This value is in good agreement with the value obtained from
Lindhard’s theory (∼ 7o ). Due to the proximity in mass and chemical be-
havior, a similar result is to be expected for the case of Eu in GaN. In this
thesis, the simple comparison will be made between the level of damage
obtained by implanting along the c-axis and along a random direction (10o
off the c-axis). For a more sophisticated study of the implantation angle
effect on the lattice damage, the reader is directed to reference [104].
Figure 6.13 shows the evolution of host Ga-displaced atoms with in-
creasing Eu fluence, for implantation along the c-axis of GaN. The level
of lattice damage is considerably lower than the one obtained after im-
planting along a direction making an angle of 10o with the c-axis shown
in figure 6.9. Figure 6.14 illustrates the in-depth-integrated areal defect
density with increasing ion fluence for both implantation geometries. The
plotted solid line curves are mere guides to the eye. As evidenced in the
figure, the concentration of displaced host Ga atoms caused by channeled
6.4 Implantation direction 129
Fig. 6.13: Damage build-up in GaN at room temperature by channeled (c-axis

of GaN) implantation of Eu with fluences in the range of 1 × 1014 to 1.6 × 1015
Eu/cm2 .
implantation, remains below the correspondent level as obtained from 10o

implantation. However, for both implantation geometries, a sigmoidal in-
crease of defect concentration with implanted fluence is observed. Such
behavior has been associated with nucleation-limited amorphization of the
material [119]. Due to the highly efficient dynamic annealing mechanism
of GaN, amorphization is difficult to initiate and only at high ion fluences
does the amorphous phase nucleate on a dense network of extended defects.
With increasing fluence, the density of such defects increases and gradually
leads to the raising of the system free energy until amorphization becomes
energetically favorable.
Comparison of damage level is better assessed by comparing the full
depth profile of the damage created to the lattice by implantation of the
same ion fluence along both directions (0o and 10o with the GaN-h0001i
axis). Such a comparison is shown on figure 6.15 (a). From this figure it
Fig. 6.14: Evolution of defect concentration with increasing implantation fluence

for random and channeled implantation.
is clear that implanting along the c-axis produces less structural damage.
Furthermore, as illustrated on figure 6.15 (b), while implanting along the
GaN c-axis, a larger amount of dopant can be introduced in the host while
keeping lattice damage at the same level as the one obtained for lower
fluences implanted along 10o away from that direction.
Considering the results obtained from HRXRD characterization, further
conclusions can be inferred about the effect of the implantation direction.
Figure 6.16 illustrates the effect of increasing fluence on the HRXRD spec-
trum of c-axis implanted samples. This figure is to be compared with figure
6.11. One observes the difference in shape and intensity of the satellite
shoulder caused by implantation. In fact, in the case of channeled implan-
tation this shoulder is better pronounced and more intense. Also, referring
to the spectra concerning the higher fluences (≥ 1 × 1015 Eu/cm2 ), the tail
decay reaches the baseline at higher 2θ values (∼ 33.7o ) as compared to the
spectra of random implanted samples (∼ 33.4o ).
Fig. 6.15: (a): Displaced host Ga-atoms by implantation of 6×1014 Eu/cm2 along
the c-axis and 10o away from that direction. (b): Introduced lattice damage by
implantation of 6 × 1014 and 4 × 1014 Eu/cm2 along the c-axis and 10o away from
that direction, respectively.
Fig. 6.16: HRXRD θ − 2θ spectra of the (0002) reflection of samples implanted

along the c-axis with fluences ranging from 2 × 1014 to 1.6 × 1015 Eu/cm2 .
At intermediate fluences (∼ 5×1014 Eu/cm2 ), figure 6.17 a) reveals that

the main difference between the spectra concerns the intensity of the shoul-
der peak. The intensity of that peak is more than one order of magnitude
higher in the case of channeled implantation.
HRXRD information allows obtaining extra insight on the crystalline
quality of the implanted lattice. The RBS/C spectra shown on figure 6.15
indicate that the amount of lattice damage, is approximately the same for
the samples implanted with fluences of 6×1014 along the c-axis and 4×1014
Eu/cm2 10o away from that direction. However, the HRXRD spectra from
figure 6.17 b) reveal a better pronounced satellite peak for the case of the
channeled implantation at higher fluence. This is an indication of a better
crystal structure.
One can then conclude from the intensity of the satellite peak and the
value of the minimum 2θ angle, that not only the lattice suffers less expan-
sion for the case of channeled implantation, but also the crystalline integrity
is better preserved for this implantation geometry.
Fig. 6.17: HRXRD θ − 2θ spectra of the (0002) reflection of samples implanted:

a) with a fluence of 5 × 1014 Eu/cm2 along the c-axis (¤) and 10o away from that
direction (¥); b) with 6 × 1014 (◦) and 3.6 × 1014 (•) Eu/cm2 along the c-axis and
10o away from that direction, respectively.
Figure 6.18 shows the CL and PL spectra of 5 × 1014 Eu/cm2 implanted

GaN samples. The CL spectra were acquired at room temperature with a
30nA, 5 kV electron beam with 10 nm defocusing, for 1 second. PL spectra
were acquired at 25 K during 15 seconds using above band gap excitation
with a wavelength of 325 nm. Both samples were thermally treated at
950o C for 2 minutes with constant N2 flow and employing GaN proxim-
ity caps. The figure illustrates the effect of the implantation direction on
the Eu-related luminescence output. The CL intensity of the channeled
implanted sample is about 10 times stronger than the one obtained from
the random implanted sample. The intensity of Eu-related luminescence,
as measured by PL, is also considerably stronger for the channeled im-
planted sample. This is an indication that structural defects introduced
during implantation along the two directions (channeled and random) have
a different impact on the Eu-related luminescence. Random implantation
introduces considerably more luminescence quenching defects, as compared
to implantation along the c-axis of GaN. The RENiBEl luminescence stud-
ies of 166 Er-implanted GaN performed by A. Braud et al. [149] indicate
a similar behavior with the implantation direction - PL luminescence is
stronger for the case of channeled implantation, as compared to random
implantation. Those results suggest that the observed luminescence has
two origins, namely, Er ions occupying a site with a well defined symme-
try (regular Er ions), and Er-ions associated to local defects or impurities
(Er-defect complexes). The regular Er ions are responsible for the typical
intra 4-f sharp luminescence lines, whereas Er-defect complexes give rise
to the broadening and appearance of extra lines in the emission spectrum.
These conclusions were drawn after verifying that the typical Er sharp lumi-
nescence lines are only observed during resonant excitation of the intra 4-f
electronic shell transitions, whereas considerably broader lines are observed
for non-resonant excitation. It was further concluded that despite the fact
that the amount of optically active Er-defect complexes appears to be very
small when compared to the amount of regular Er ions, the luminescence
from such complexes is not negligible, as their absorption cross-section ap-
pears to be considerably larger than the one of regular Er ions. Braud et
Fig. 6.18: CL and PL spectra of 5×1014 Eu/cm2 GaN samples implanted, at room
temperature, along the c-axis and 10o away from that direction. Post-implantation
thermal treatment was performed at 950o C with a GaN proximity cap and under
N2 flow
al. suggested that regular Er ions are located at the substitutional Ga site
(ErGa ) in the GaN lattice, as the PL intensity of the regular Er ions is
slightly higher for the case of channeled implantation. This result is con-
sistent with RBS measurements ([104]) showing that the Er substitutional
fraction (SGa (Er)) of Ga in GaN is higher for channeled implantation. For
the case of Er-defect complexes, the authors observed that the luminescence
from such optically active complexes is much stronger for the channeled
implanted samples than for the random geometry of implantation. This
fact leads to the conclusion that channeled implantation generates a larger
amount of optically active Er-defect complexes, whereas random implan-
tation leads to Er-defect complexes where luminescence quenching processes
are more effective. These conclusions are in good agreement with the lumi-
nescence results of Eu-implanted GaN shown in figure 6.18. Furthermore,
RBS/C and HRXRD results of figures 6.15 and 6.17 a) and b), respectively,
indicate that not only the amount of structural defects as measured with
RBS/C is lower for channeled implantation (for the same ion fluence), but
also the integrity of the crystalline lattice, at the site of implantation is
superior. These facts possibly explain the higher luminescence output from
the channeled implanted sample: more optically active Eu-defect complexes
and less luminescence quenching defects.
The level of structural lattice damage is strongly dependent on the im-

plantation direction, with respect to the major crystalline axis. A compari-
son was made between the degree of introduced lattice disorder upon 80 keV
153 Eu implantation along the GaN c-axis and 10o away from that direction.
One concludes that both implantation geometries yield a sigmoidal increase

of the concentration of lattice defects with increasing dopant fluence. Such
sigmoidal behavior is the “fingerprint” of a highly efficient dynamic an-
nealing mechanism, as previously discussed. Amorphization is difficult to
achieve for GaN requiring relatively high ion fluences. Despite the sim-
ilar behavior, the disorder level caused by implantation along the c-axis
is kept considerably below the level from random implantation, through
the entire investigated implantation fluence range. As a consequence, for a
6.5 Temperature dependence 137
certain level of lattice disorder, a higher dopant fluence can be introduced

by the channeled geometry of implantation. Moreover, HRXRD results
seem to suggest that, for the same level of lattice disorder, as measured
with RBS/C, the crystalline quality (along the direction of implantation)
is better preserved by implanting along the channeled direction.
Concerning the luminescence output of samples implanted along both
implantation geometries, as measured by CL and PL, a considerably higher
intensity is observed on the channeled implanted samples. Structural de-
fects introduced during implantation along both geometries differently af-
fect the Eu-related luminescence. Attending to the difference in integrated
luminescence intensity (about 10 and 4 times higher, for CL and PL, respec-
tively), and to the fact that the RBS/C lattice disorder level is only a factor
3/2 higher in the case of random implantation, one can conclude that ran-
dom implantation introduces a considerably higher amount of luminescence
quenching defects, as compared to channeled implantation. Furthermore,
it seems that not all introduced defects are detrimental for the RE-related
luminescence. In fact, attending to several theoretical and experimental
results obtained within the RENiBEl network [46, 147, 148], one is led to
conclude that certain structural defects (REGa -complexes) might play an
important role in the excitation of the RE 4f electronic transitions.
6.5 Temperature dependence
As discussed on the previous chapter, temperature plays a key role in the

suppression of structural damage during ion implantation. In particular,
the dynamic annealing phenomenon is strongly dependent on the tempera-
ture. Increasing the substrate temperature during the implantation process
results in increasing the mobility of point defects and hence, increasing their
recombination probability. However, the existing literature reports are not
consensual about the effect of temperature on the damage buildup. Wenzel
et al. [121], reported the increase rather than the decrease of the amount of
damage with increasing substrate temperature ranging from room temper-
ature (RT) to 550o C. Usov et al. [122] studied the damage build-up over a
wider range of temperatures, from RT to 1000o C. They reported that the

behavior of the two defect regions, as seen by RBS, is different at different
temperatures. The magnitude of the surface peak decreases with increasing
temperature, reaching the levels of the unimplanted sample. Concerning
the bulk, or end-of-range region, the authors report the decrease of the
backscattering yield from this region from RT up to 500o C. In the region
between 500 and 700o C, an inversion of the previous trend is observed, with
the increase, rather than the decrease, of the backscattering intensity. For
higher temperatures, the backscattering yield from this region decreases
again. The reports above are in contradiction with the report of W. Jiang
et al. [123], where the authors report an decrease of relative disorder in
both Ga and N sublattices, with increasing temperature in the range from
150 to 800 K. Also, Parikh et al. [124], report the decrease of lattice damage
with increasing implantation temperature.
The focus of this section resides on a study of the effect of substrate tem-
perature on the build-up of lattice damage for a series of 5 × 1014 Eu/cm2 -
implanted GaN samples at temperatures ranging from RT to 800o C. Im-
plantations were performed both along the c-axis and 10o away.
Random implantation - at 10o to surface normal

The set of spectra shown on figure 6.19 illustrates the evolution of lattice
damage with increasing temperature in the range of RT to 800o C for a
batch of GaN samples implanted with 5 × 1014 Eu/cm2 along a direction
making an angle of 10o with the crystal’s c-axis. Remarkably, at a substrate
temperature of only 180o C the amount of structural damage, as measured
by RBS/C, is reduced by approximately a factor of 2. Further temperature
increase appears to lead to the lowering of the backscattering yield from
these samples, however the behavior of the two damage regions appears to
differ.
For the sake of clarity, figure 6.20 shows the RBS/C spectra for three
temperature sub-ranges. The set on top reveals the trend of decreasing
damage with the increase of the substrate temperature. This trend con-
tinues up to 400o C (middle set on figure 6.20), where the lattice damage
Fig. 6.19: Lattice disorder as measured by RBS/C on a series of samples implanted

with 5×1014 Eu/cm2 10o off the c-axis at temperatures ranging from RT to 800o C
reflected on the RBS/C minimum yield has its lowest value. For this tem-
perature, the surface damage peak reaches the same level of magnitude as
for an unimplanted sample, while the EOR damage peak has its lowest
intensity value.
At 500o C there is a slight increase of the RBS/C minimum yield. In fact,
this increasing trend appears to continue for higher temperatures, as can
be seen from the spectra for 700 and 800o C (bottom set of spectra in figure
6.20). Also, it should be noticed that the magnitude of the EOR damage
peak increases more significantly than that of the surface peak (which does
not drastically increase). The increasing trend of the irradiation-related
damage with implantation temperature is unexpected since for other semi-
conductors such as Si, Ge and GaAs, the effect of increasing the substrate
temperature is always in the direction of reducing implantation damage.
This is an indication that there must be fundamental differences between
Fig. 6.20: RBS/C spectra of the batch of GaN samples implanted with 5 × 1014
Eu/cm2 along 10o off the c-axis and at temperatures ranging from RT to 800o C
the defect accumulation mechanism in GaN compared to other semicon-

ductors. A possible explanation for this result might lie in the formation
of certain temperature-specific defects responsible for the significant lattice
disorder as observed by RBS/C. Examples of such defects in GaN might be
surface decomposition due to N loss, and N2 bubble formation. HRXRD
measurements on these samples, as seen on figure 6.21, show the same trend
as RBS/C. Although there is no drastic change on the lower value of 2θ
at which the decaying tail meets the baseline at the spectra from the tem-
perature range, there is a change in the amplitude of diffraction from the
damaged area. The amplitude of the shoulder in the temperature range
between RT and 250o C decreases only slightly with temperature (top set
of spectra in figure 6.21). In this range, the shoulder is better pronounced
at 250o C. In the range of 250 and 500o C (middle set in figure 6.21) the
amplitude and shape of the spectra in the damaged region show more sig-
nificant changes. The amplitude of the diffracted intensity from that region
drops considerably, being the lowest for 500o C. This reveals a decrease in
the lattice strain due to the presence of less defects, as shown by RBS/C.
Above 500o C (bottom set of spectra in figure 6.21) there is a slight increase
of the diffraction intensity in the lower 2θ part of the spectra, indicating
a slight increase in the lattice strain. This is in good agreement with the
observed results from RBS/C (bottom set in figure 6.20). These results
seem to confirm a slight worsening in structural crystalline quality of the
implanted films, as the temperature is increased from 500 to 800o C.
Channeled implantation - along the c-axis

Figure 6.22 depicts the evolution of lattice damage as measured by RBS/C
of a batch of GaN samples implanted with 5 × 1014 Eu/cm2 along the GaN
c-axis, at substrate temperatures ranging from RT to 800o C. Not only the
level of damage is considerably lower than for the case of random implan-
tation (figure 6.19), but also already at 90o C there is a drastic reduction
of the structural damage. Even more striking is the fact that at 90o C and
higher implantation temperatures, the EOR (more in depth) damage re-
Fig. 6.21: HRXRD spectra of the GaN(0004) reflection of the batch of samples
implanted with 5 × 1014 Eu/cm2 along 10o off the c-axis and at temperatures
ranging from RT to 800o C
Fig. 6.22: Lattice disorder as measured by RBS/C on a series of samples implanted

with 5 × 1014 Eu/cm2 along the c-axis and at temperatures ranging from RT to
800o C
gion is strongly reduced or even eliminated, a fact that is not observed for
the case of random implantations even at much higher temperatures (up to
800o C).
In figure 6.23 the RBS/C spectra shown together in figure 6.22, are
now separated by temperature intervals with the purpose of facilitating the
comparison. As illustrated in 6.23 a), the gross in change of the defect level
is observed in the temperature range between RT and 120o C. At 70o C a
small decrease in the damage level, as compared to the RT level is observed,
however the spectrum main features are still present, namely the two defect
regions. However, raising the substrate temperature by only 20o C results in
an abrupt intensity reduction of the EOR damage peak, accompanied by an
overall reduction of the defect concentration. Implanting with a substrate
temperature of 120o C further reduces the damage. Figures 6.23 b) and
c) show that in the temperature ranges of 120 to 400o C, no considerable
Fig. 6.23: RBS/C lattice disorder of a batch of samples implanted with 5 × 1014
Eu/cm2 along the c-axis and at temperatures ranging from RT to 800o C
reduction is observed in the level of implantation induced damage. Finally,

figure 6.23 d) shows a further decrease of the surface defect level from 400
to 500o C. As illustrated, the RBS/C spectrum almost reaches the level of
an unimplanted sample, however a small amount of defects is still present,
even at 800o C. Also interesting to notice is the fact that, similarly to the
case of random implantation, the EOR defect level slightly increases for
temperatures above 500o C.
RBS/C data are complemented with the help of HRXRD. Concerning
the minimum value of 2θ and the intensity and shape of the shoulder peak
in the XRD spectrum (implantation damage region) one observes in figure
6.24 a) a considerable reduction in lattice strain already by increasing the
substrate temperature from RT to only 70o C. At 120o C the intensity of
the shoulder peak has a maximum value and its shape is best defined indi-
cating a higher crystalline quality in the implanted region. As can be seen

in figure 6.24 b), even though the 2θ minimum value doesn’t considerably
change (∼ 72o ), the intensity and shape of the shoulder peak do change. At
220o C the shoulder peak is not so well defined and its intensity is lower, as
compared to the spectrum of the sample implanted at 120o C. Figure 6.24
c) not only further accentuates the previous trend of the peak intensity
but also illustrates the increase of the minimum value of 2θ, indicating a
reduction of the lattice strain in the damaged region. In this range, the
minimum of lattice strain is observed for an implantation temperature of
400o C. Finally, figure 6.24 d) shows that up to 500o C a further decrease
of the satellite peak amplitude and a slight increase of the minimum 2θ
value (∼ 72.2o ) is observed. The latter is an indication that there is a
Fig. 6.24: HRXRD spectra of the GaN(0004) reflection of the batch of samples
implanted with 5 × 1014 Eu/cm2 along the c-axis and at temperatures ranging
from RT to 800o C
slight decrease in lattice expansion in this temperature range. However, in

the range of implantation temperatures between 500 and 800o C there is a
slight decrease of the 2θ value (∼ 72.2o → ∼ 71.8o ). This fact reveals an
increase in lattice expansion. The crystalline quality has slightly deterio-
rated. This is in good agreement with the RBS/C results (slight increase
of backscattering yield from the EOR damage region for the 800o C spec-
trum in figure 6.23 d)). Once again, this observation is consistent with the
formation of temperature-driven defects, such as N2 gas bubbles inside the
material. Confirmation of this hypothesis needs to be supported by other
structural analytical techniques, such as high resolution TEM.
Comparing the results from channeled and random implantations at el-

evated substrate temperatures, it is clear that for implantations along the
GaN c-axis, the density of implantation generated defect is much smaller
than for random implantation. Furthermore, a striking feature has been
observed in the case of channeled implantation: at implantation temper-
atures above 70o C the EOR damage region is suddenly suppressed. Such
suppression is a very interesting observation. As previously pointed out
in section 6.3, the two defect regions, as observed by RBS/C, demonstrate
a different behavior with increasing ion fluence. This difference has been
attributed to the nature of defects formed in both regions and the efficiency
of the dynamic annealing mechanism in GaN. Whereas at the EOR region,
more complex defects are formed, the surface is thought to act as a sink for
mobile simple defects. Also, the size and complexity of defects in the EOR
region is strongly conditioned by the thermal properties. If the tempera-
ture during implantation is sufficiently increased (above 70o C as results in
figure 6.22 suggest), a considerable enhancement of the dynamic annealing
mechanism is observed. This enhancement has a clear impact on the defect
formation in the EOR region. Not only does it prevent or strongly sup-
presse the formation of stable defect complexes in this region, but it also
increases the mobility of simple point defects. This mobility increase leads
to a faster recombination/annihilation of point defects in the region where
they are formed, while promoting a faster migration to the crystal surface of
the remaining point defects. Such defect removal from the EOR region pre-
vents them from clustering into larger sized and complex defects resulting
in a low level of lattice disorder in this region, as observed by RBS/C. The
reason why such suppression is not observed for the random implantation
geometry (figure 6.19) is probably related to the fact that this geometry
generates a considerably higher level of lattice imperfections, increasing not
only the number but also the complexity of defect aggregates. However,
as seen in figure 6.19, the substrate temperature during implantation plays
an important role in the formation of defects in both regions even for this
implantation geometry.
Another interesting observation is the fact that, for both implantation
geometries, a slight decrease of the crystalline quality, as observed by both
RBS/C and HRXRD, seems to occur for substrate temperatures above
500o C. At 800o C a clear increase of the lattice disorder in the EOR region
was observed for both implantation geometries. Interestingly this temper-
ature coincides with the formation temperature of N2 molecules suggesting
that N2 bubble formation in the region of implantation might be the cause
of such behavior of the damage build-up with increasing temperature.
Figure 6.25 compares the evolution of the integrated level of Ga dis-
placements (EOR+surface defects), as obtained from RBS/C for 5 × 1014
Eu/cm2 -implanted GaN, along both implantation geometries, through a
range of substrate temperatures from RT to 800o C. The solid lines are
guides to the eye. As can be concluded from the figure, simply by heating
the substrate during implantation by only about 100o C, the integral of the
defect concentration as compared to RT implantation, is decreased by a
factor of 5 in the case of channeled implantation. Such reduction favors
elevated substrate temperature implantation as an effective method to in-
troduce RE-ions in GaN while keeping implantation damage at low values.
In fact, the more conventional procedures for damage recovery by post-
implantation treatments, such as thermal annealing and laser annealing
have inherent problems that prevent an efficient recovery of implantation
damage. For a compound semiconductor such as GaN, the ideal annealing
temperature is two-thirds of the material melting point [60]. For GaN, with
a melting point of about 2500o C [125], the required annealing temperature
Fig. 6.25: Concentration of displaced host Ga atoms, as obtained from RBS/C

measurements, for 5 × 1014 Eu/cm2 -implanted GaN, along the c-axis (¥) and 10o
off (¤), at substrate temperatures ranging from RT to 800o C
is then above 1600o C. However, even though GaN has an elevated melting
point, its surface starts decomposing already at much lower temperatures.
At about 800o C N2 molecules begin to form, resulting in the loss of ni-
trogen accompanied by the formation of Ga droplets on the surface. As
shown on figure 5.12 of section 5.3, the recovery of structural defects only
starts at about 600o C, but annealing temperatures of about 900o C are re-
quired for significant reduction of implantation damage in GaN [126]. As
such, the employ of standard post-implantation thermal treatments for de-
fect recovery is limited. Variants of these thermal treatments include the
use of proximity caps and N2 flow during the annealing process to prevent
nitrogen loss and surface decomposition.
For this work, two post-implantation thermal treatment methods have
been employed: conventional annealing at 900o C in a furnace during 30
minutes, with a GaN proximity cap and constant flow of N2 ; and rapid
thermal annealing (RTA) with a temperature increase rate of 100o C/s,
plateau at 950o C for 120s and temperature decrease rate of 125o C/s, also
with a GaN proximity cap and constants N2 flow to minimize the loss of
nitrogen from the surface. Both variants yield similar results without signif-
icant differences concerning recovery of damage. Attempts to increase the
annealing temperature to 1050o C during RTA resulted in surface degrada-
tion, visible with the naked eye as the appearance of a grey-toned layer (Ga
droplets) at the surface. Concerning laser annealing, despite the fact that
it implies extremely short processing times (∼ 50 ns), only few studies have
employed laser annealing to recover implantation-damaged GaN [127, 128].
As such, an incomplete knowledge of optimal parameters has prevented the
widespread use of this annealing method.
From this discussion it can be concluded that, the success of post-
implantation thermal treatments is limited by the thermal stability of the
nitride surface. Alternatively, as seen in figure 6.25, simply by keeping the
substrate temperature during implantation at about 100 − 200o C, the level
of structural damage is drastically reduced, as compared to room temper-
ature implantation.
The spectra on top of figure 6.26 allow to compare the level of im-
plantation damage, as measured by RBS/C, for 5 × 1014 Eu/cm2 - ran-
dom implanted GaN, as implanted at room temperature (¥), after post-
implantation thermal treatment with RTA as previously described (¤), and
as implanted with the substrate temperature kept at 180o C (•). It is strik-
ing to observe that by simply heating the substrate temperature to 180o C
during implantation, the level of structural damage is kept well below the
level of a sample implanted at room temperature which was posteriorly an-
nealed at 950o C in a RTA furnace. Even more remarkable is the fact that
for the case of channeled implantation (bottom of figure 6.26), an even lower
substrate temperature (120o C) is sufficient to keep the damage level a factor
of 2 lower than the level of an RTA annealed room temperature implanted
sample. Notice that even after annealing at 950o C, the EOR damage region
is still present in the RBS/C spectrum - a feature that is suppressed in the
spectrum of the 120o C as implanted sample. This fact alone gives evidence
that by simply heating the substrate during implantation, the dynamic an-
Fig. 6.26: Top: RBS/C lattice damage, for 5 × 1014 Eu/cm2 random implanted
GaN, as implanted at RT (¥), after 120s RTA at 950o C (¤), and as implanted
at 180o C (•)(no post-implantation annealing). Bottom: RBS/C lattice damage,
for 5 × 1014 Eu/cm2 channeled implanted GaN, as implanted at RT (¥), after
120s RTA at 950o C (¤), and as implanted at 120o C (•)(no post-implantation
annealing)
nealing mechanism is enhanced, allowing to recover even more implantation

induced defects, as they are being created. By doing so, it is possible to pre-
vent the formation of more complex (and temperature stable) defects that
otherwise would be formed and would “survive” post-implantation thermal
treatments at temperatures as high as 950o C. It should be noticed that
attempting to elevate the post-implantation annealing temperature above
950o C results in surface degradation.
Concerning the optical properties of the elevated temperature implanted
samples, figure 6.27 shows the PL spectra of samples implanted at 70 and
90o C implanted along the channeled and random geometries, respectively.
After implantation and structural characterization, both samples were an-
nealed at 950o C for 2 minutes in a rapid thermal annealing unit.
For the channeled implanted sample at 70o C, small differences were
observed in the intensity of the Eu-related luminescence peaks. Comparing
the intensities of the Eu-related luminescence lines (5 D0 −7 F1 , 5 D0 −7 F2
and 5 D0 −7 F3 ), the luminescence at 25K with above band-gap excitation
(325 nm) is slightly less intense for the 70o C implanted sample. However,
an extra line appears in the spectrum of the 70o C sample at about 617 nm.
In the case of the RT implanted sample, this line is almost absent. As a
result, the integrated PL intensity of the sample implanted at 70o C is about
10% higher, as compared to the RT implanted sample. This line at about
617 nm can possibly be attributed to the formation of an optically active
Eu-defect complex at 70o C, which remained stable even after annealing at
950o C. Such line has been reported by Katchkanov et al. in reference [148],
as being related to the 5 D0 −7 F2 transition. As previously mentioned in
section 6.4, it is thought that Eu:GaN luminescence is due to EuGa -defect
complexes. As such, it is possible that channeled implantation at 70o C
favors the formation of such Eu-defect configuration that enhances emission
at 617 nm, as compared to RT implantation.
With respect to the sample randomly implanted at 90o C, the PL spec-
trum reveals an intensity increase of about 2.5 times (for the 622 nm line)
as compared to the RT implantation. This fact does not strongly correlate
with the results obtained from RBS/C, as observed in figure 6.19, where
Fig. 6.27: PL spectra of 5 × 1014 Eu/cm2 -implanted GaN, along the c-axis at
70o C (top) and 10o off at 90o C (bottom) - post-implantation annealing at 950o C
only a small recovery of the lattice damage is obtained after 90o C implan-
tation. However this mismatch is not surprising as RBS/C does not allow
to obtain information on specific types of defects that might be associated
with the RE-luminescence, nor defects involved in luminescence quenching
- only integrated defects.
Figure 6.28 illustrates the effect of further increasing the substrate tem-
perature during implantation to 160o C, for the case of channeled implan-
tation of 5 × 1014 Eu/cm2 . The CL spectrum was acquired after annealing
the sample at 950o C in the same fashion as previously described. A con-
siderable luminescence intensity increase is observed, as compared to RT
implantation.
From the analysis of the luminescence output from elevated substrate
temperature implantations it can be concluded that the increase of sub-
strate temperature during implantation results in the decrease of concen-
tration of non-radiative or luminescence quenching defects, as compared to
Fig. 6.28: CL spectra of 5 × 1014 Eu/cm2 -implanted GaN, along the c-axis at
160o C - post-implantation annealing at 950o C
RT implantation, for both implantation geometries. However, by compar-

ing the intensities of the PL spectra of samples implanted along the c-axis
and 10o away from that direction, it can be concluded that even at ele-
vated implantation temperatures, channeled implantation yields stronger
Eu-related luminescence.
Although no luminescence was expected from as-implanted samples

(to our knowledge, no luminescence has previously been observed on as-
implanted RE-doped GaN [108]), it was interesting to attempt to measure
the luminescence spectra of samples implanted at elevated substrate tem-
perature, without subsequent thermal treatment. For this purpose, a set of
5 × 1014 Eu/cm2 as-implanted GaN samples, at temperatures ranging from
50 to 800o C and has been characterized by cathodoluminescence measure-
ments. Figure 6.29 shows the CL spectra of as-implanted (not annealed)
5 × 1014 Eu/cm2 GaN implanted at 500, 700 and 800o C along the c-axis of
GaN. It is surprising to observe that for implantation temperatures above
500o C the CL spectra show weak Eu-related luminescence peaks. How-
ever, no Eu-related luminescence was observed for samples implanted at
temperatures below 500o C. A possible explanation for these observations is
related to the population of luminescence quenching structural defects in-
troduced by this implantation geometry. At temperatures below 500o C such
defect population dominates the optical properties of Eu-implanted GaN,
resulting in a total quenching of Eu-related luminescence. Above 500o C, as
dynamic annealing becomes more and more efficient, the population of lu-
minescence quenching defects decreases and thereby the Eu-related optical
output increases.
Even more surprising was the observation of luminescence from the
random as-implanted samples. Figure 6.30 compares the CL emission in-
tensity of the samples implanted at 250, 700 and 800o C along the random
geometry of implantation. The intensity of 622 nm line is about 25 times
stronger for the higher implantation temperature samples, as compared to
the sample implanted at 250o C. However, it is remarkable that for this im-
plantation geometry, Eu-related luminescence is observed for implantation
Fig. 6.29: CL spectra of 5 × 1014 Eu/cm2 -implanted GaN, along the c-axis at 500,
700 and 800o C - No post-implantation annealing!
temperatures below 500o C, in contrast to the case of channeled implanta-

tion. Furthermore, as shown in figure 6.31, by zooming-in on the 622 nm
line CL spectra of samples implanted at temperatures below 250o C, it is
possible to conclude that Eu-related luminescence in random as-implanted
samples is already observed at temperatures as low as 50o C. This observa-
tion is totally unexpected, since no luminescence is observed from RT RE
as-implanted GaN samples ([108]).
Moreover, attending to the RBS/C structural characterization results
summarized in figure 6.25, the amount of lattice defects for the case of ran-
dom implantation along the entire temperature range, is at least a factor
of 2 higher than the value obtained from channeled implantation. As such,
from an intuitive point of view, stronger luminescence quenching would
be expected in the case of random implantation, even at elevated substrate
temperatures during implantation. The spectra in figure 6.32 allow to com-
pare the CL intensity of as-implanted 5 × 1014 Eu/cm2 samples, at 700o C
Fig. 6.30: CL spectra of 5 × 1014 Eu/cm2 -random implanted GaN at 250, 700 and
800o C - No post-implantation annealing!
along the channeled and random geometries of implantation. The CL in-

tensity of the Eu-related 622 nm emission line is about 20 times stronger
for the random as-implanted sample. The same conclusion can be taken
from the spectra of 800o C as- random and channeled implanted samples
(not shown here).
These results, combined with the ones obtained from structural char-
acterization, lead to the conclusion that not all defects are detrimental for
the optical properties of Eu-implanted GaN. In fact this opinion is shared
within the RENiBEl network, as indicated in references [46, 147, 149]. On
one hand the existence of two components in the decay time of Er-related
luminescence was demonstrated ([149]). This revealed two sorts of lumi-
nescent centers, from which, at least one sort involves Er-defect complexes
while the other was associated to the ErGa configuration. On the other
hand, considering the variations in the fine structure of the luminescence
spectrum of Eu-doped GaN ([147, 148]), it has been suggested that a set of
centers composed by REGa associated with slightly different defect configu-
Fig. 6.31: Zooming-in on the 622 nm line CL spectra of samples implanted at 50,
160 and 250o C - No post-implantation annealing!
rations constitutes the major contributor for the luminescence in RE:GaN.

These observations suggest that some defects hinder RE-related lumines-
cence, while others seem to be strongly related to that luminescence. Taking
into account that most of the irradiation damage in GaN is formed by point
defects ([82]) and that certain defects combine with RE-ions and form ther-
mally stable complexes up to 1000o C (for example REGa − VN - reference
[46]), the following reasoning can be made. Structural characterization re-
sults indicate that the level of lattice defects (luminescence quenching +
optically active) is considerably higher for the case of random implanta-
tion. However, for room temperature implantation, no RE-luminescence
emission is observed for both directions (c-axis and 10o away), indicat-
ing that the population of luminescence quenching defects dominates the
optical emission properties for both geometries. After annealing, the re-
covery of lattice defects is considerably stronger for the case of channeled
implantation. However, since certain RE-defect complexes “survive” high
temperature thermal treatments, it is possible that the majority of the re-
Fig. 6.32: CL spectra of 5 × 1014 Eu/cm2 random and channeled implanted GaN
700o C - No post-implantation annealing!
combined defects are the ones responsible for luminescence quenching. As

such, even though channeled implantation at room temperature introduces
less defects (quenching + active), after annealing the population of lumi-
nescence quenching defects is considerably more reduced than in the case of
random implantation - figure 6.26. As a result, the luminescence intensity
of channeled implanted (and annealed) samples is much stronger than that
of random implanted samples.
Considering now the luminescence results from the elevated tempera-
ture as-implanted samples, the same arguments can be used. Figure 6.25
shows that the integrated defect concentration is significantly higher for the
random geometry, along the entire range of implantation temperatures. As
such, a larger number of defects (quenching + active) is introduced by that
geometry, as compared to channeled implantation. As the substrate tem-
perature during implantation is increased, the mobility of generated defects
increases, leading to more recombinations, but possibly also to an increase
of the number of optically active RE-defect complexes. As such, the popu-
lation of luminescence hindering defects tends to decrease as the population
6.6 AlN protective layer 159
of optically active defects tends to increase. However, since more defects

(of both kinds) are introduced by random implantation, more optically ac-
tive defects will “survive” and thereby, the luminescence intensity will be
stronger for this implantation geometry. However, it should be noticed that
the luminescence intensity of these as-implanted samples is at least a factor
10 less intense than the intensity obtained from RT implanted and annealed
samples. This fact is due to the relatively large number of persisting lu-
minescence quenching defects on the as-implanted samples. Nevertheless,
after annealing the elevated temperature implanted samples, a higher emis-
sion intensity is obtained (figure 6.28), as compared to the RT and annealed
sample. This fact reveals that further recovery of luminescence quenching
defects occurred. It can be then concluded that elevating the substrate tem-
perature during implantation not only allows to reduce the concentration of
luminescence hindering structural defects, but also allows obtaining higher
luminescence intensities upon post-implantation annealing. Even though,
as previously indicated, conventional annealing techniques are limited by
material decomposition issues, alternative methods are being investigated.
One of such methods consists on employing a protective layer that prevents
surface decomposition, as will be discussed in the following section.
6.6 AlN protective layer
In order to prevent decomposition and material loss during high tempera-

ture annealing, a protective thin (∼ 10 nm) AlN cap layer can be deposited
on the GaN surface. Zolper et al. [130] performed RTA annealing studies
of GaN implanted with 5 × 1015 Si/cm2 at 210 keV and at RT. After im-
plantation, a 100-150 nm AlN cap layer was deposited on the GaN surface
by reactive ion sputtering. The samples were then annealed during 30 s
at temperatures between 1100 and 1500o C. Electrical activation results of
encapsulated samples were compared with the ones of bare GaN. Despite
the fact that an initial increase in electron concentration is observed for the
unencapsulated samples, above 1300o C the GaN layer disintegrates. By
contrast, the AlN-capped samples showed (Si+ ) electrical activation levels

peaking at about 90% at 1400o C.
High-temperature annealing studies have also been performed within
RENiBEl ([131]) on Eu-implanted GaN with a 10 nm AlN protective cap on
its surface. In contrast with the work of Zolper, the AlN layer on RENiBEl’s
samples was epitaxially grown on GaN by MOCVD, prior to implantation.
RBS/C analysis of the as-implanted samples has revealed the suppression
of the surface damage peak on the as implanted AlN-capped samples. As
such, not only does the AlN cap protect the GaN surface during annealing,
but it also allows to reduce defect formation during implantation. The
reason for this suppression is still not completely understood. However, it
seems to be related to the role of the GaN surface on the formation and
accumulation of implantation defects. Kucheyev et al. [132] are favorable
to the hypothesis that the surface of GaN acts as a sink for migrating
point defects. Being so, even when the AlN cap is grown on top of the
GaN surface, implantation defects should still be able to accumulate at the
region below the interface between the GaN surface and the AlN cap. This
does not correspond to what is experimentally observed.
Figure 6.33 presents RBS/C spectra of Eu-implanted GaN samples, at
80 and 160 keV unprotected and protected with a AlN cap. The analyzed
samples were not annealed after the implantation process. A striking fea-
ture, common to all the spectra of AlN-capped samples, is the fact that
the surface damage peak is simply suppressed. In fact, the only peak ob-
served in the surface region of these samples is the surface peak, present
in all samples, even when unimplanted - as mentioned in section 6.2. As
discussed in reference [131], the presence of an implantation-related surface
damage peak is quite likely to be related to the preferential sputtering of
nitrogen from the unprotected surface of (uncapped) GaN during implanta-
tion. Furthermore, that RENiBEl report suggests that the surface damage
peak suppression is probably due to a complex interaction of several fac-
tors, including the host crystalline quality prior to implantation. In fact,
ion channeling along the c-axis of the AlN capping, which is aligned with
the c-axis of the underlaying GaN substrate quite possibly contributes to
Fig. 6.33: RBS/C random and c-axis aligned spectra of as-implanted Eu:GaN
uncapped and AlN-capped samples. a) 80keV random implantation; b) 80keV
channeled implantation; c) 160keV random implantation; and a) 160keV chan-
neled implantation
reduce the lattice disorder level. Incident ions are channeled through cap
and host without generating much damage as they penetrate through the
host material. This would also explain the deeper range of ions in GaN,
as observed by the deeper disorder level in the Ga-backscattering signal, as
observed by RBS/C on figure 6.33. However, as seen in figures 6.33 a) and
c), surface peak suppression also occurs when the direction of the incoming
beam is deviated 10o from the c-axis direction, avoiding channeling effects
as previously discussed.
Furthermore, strong attenuation of the surface damage peak was also
achieved in the following experiment. A fluence of 4.5 × 1014 Eu/cm2 was
implanted at room temperature, on a GaN sample on the surface of which

an 80 Å AlN cap was epitaxially grown by MOVPE. To prevent oxidation
of the AlN-cap ([148]), an amorphous 30 Å Si3 N4 passivation layer was
grown on top of the cap. Two implantation geometries were employed,
namely, 10o -off the normal to the surface, and perpendicularly to the surface
(coinciding with the GaN and AlN c-axis). In this case, by crossing the
amorphous SiN film at the surface, the initially c-axis aligned ions will
probably be deflected ([148]). As a consequence, more damage should be
present in the region below the GaN surface. However, as can be seen in
figure 6.34, strong attenuation of the surface damage peak is still present,
both for channeled and random implanted samples.
These results indicate that possibly, a stronger factor is responsible for
the suppression of the surface damage peak on the AlN-capped samples.
In fact, Kucheyev et al. [134, 135] demonstrated that the presence of Al in
Alx Ga1−x N , even at amounts as small as x = 0.05, is responsible for the
absence of preferential surface disordering in heavy ion implanted layers.
Being so, and since implantation occurred through the GaN/AlN interface
(AlN cap deposited before implantation) it cannot be excluded that a mix-
ture between the GaN and AlN at the interface might be responsible for
the suppression of the surface damage peak. In any case, the presence of an
AlN cap on the surface of GaN during implantation, adequately fulfils the
role of substrate protector, allowing to decrease the level of implantation
damage, as demonstrated on figures 6.33 and 6.34.
The RENiBEl study reported in reference [131] proceeded to further
investigate the efficiency of the AlN capping as protector during post-
implantation thermal treatments at higher (> 900o C) temperatures. An-
nealing of AlN-capped Eu-implanted samples occurred in a conventional
tube furnace with a 4 bar nitrogen overpressure, for 20 minutes at temper-
atures in the range between 1000 and 1300o C. Results show a very good
crystalline recovery already at 1000o C, with a still significant level of lat-
tice defects, as compared to the unimplanted sample. Annealings at higher
temperatures did not significantly improve the crystalline quality. How-
ever, after annealing at 1100o C and above, the intensity of the peak in the
Fig. 6.34: RBS/C random and c-axis aligned spectra of random (top) and chan-
neled (bottom) as-implanted Eu:GaN uncapped and AlN-capped (with SiN passi-
vation cap grown on top) samples.
c-axis aligned RBS/C spectrum corresponding to the GaN/AlN interface

region starts to increase. This increase reveals an increasing amount of Ga
atoms that are displaced from substitutional sites, fact that these authors
attributed to an interaction with defects or Al atoms from the cap. After
annealing, the samples were optically characterized with cathodolumines-
cence (CL). Their results indicated that the CL emission intensity from the
Eu intra-4f electronic shell transitions exhibits a very strong dependence
on the annealing temperature. This intensity increased by one order of
magnitude by increasing the annealing temperature from 1100 to 1300o C.
However, there are limitations to the efficiency of AlN caps as protecting
layers during the annealing of implanted GaN. Another RENiBEl study (by
Nogales et al. [136]) reports a microscopic study of the structural proper-
ties of AlN caps grown on GaN. It concludes that extended defects, mainly
cracks formed on the AlN caps due to the large lattice mismatch between
the two materials, lead to the local dissociation of GaN below those cracks,
at elevated annealing temperatures. As such, in order to obtain efficient
protective caps, this problem has first to be tackled.
6.7 Substrate composition
As discussed in section 1.1, the concentration of Al and In in Alx Ga1−x N

and Inx Ga1−x N alloys can be varied in order to engineer the band gap of
the alloy within the range of 0.7-1.9 eV (for InN) and 6.2 eV (for AlN). How-
ever, the composition of the nitride film also strongly affects the buildup of
structural damage upon irradiation.
Kucheyev et al. [135] demonstrated that an increase in the In concentra-
tion in InGaN films, strongly suppresses dynamic annealing processes and
enhances the buildup of stable lattice disorder. On the other hand these au-
thors reported that by increasing the Al content in AlGaN alloys increases
the material resistance to irradiation damage and enhances dynamic an-
nealing. They attribute the increase (decrease) in dynamic annealing with
increasing Al (In) content to the larger (smaller) energy of the Al-N (In-N)
bond, as compared to the energy of the Ga-N bond. However, the difference
6.7 Substrate composition 165
in mass between Al(or In) and Ga might also play a role, since from a bal-
listic view point, a knocked-out lighter host atom will induce less damage,
as compared to a heavier atom.
Recently, Lorenz et al. [139] have reported on the influence of the
Al concentration on the formation of irradiation damage and photolumi-
nescence emission in europium implanted Alx Ga1−x N films. These authors
concluded that the implantation damage decreased considerably for all films
containing Al, with the best results observed for AlN. Once more, this seems
to be the reason why such a strong suppression of damage occurs in the
AlN-capped GaN samples, as discussed in the previous section. Concerning
the substitution of the cation in the alloys by the Eu dopant, the highest
substitutional fraction (Sf (Eu)) was observed in GaN, while the lowest was
in AlN. A gradual decrease in the Sf (Eu) was observed as the Al content
in the alloy increased. However, neither structural damage results nor the
substitutional fraction correlate with the photoluminescence intensity re-
sults. Their results indicated a strong increase of the luminescence from 0
to 30% of Al, and steep drop of intensity for higher Al contents.
Another interesting nitride alloy is Alx In1−x N . The composition of
these layers can be engineered in order to lattice-match them to GaN
[140, 141] and consequently, these layers can be grown strain free on GaN.
As such, Alx In1−x N layers are suitable to be used as cladding layers with-
out strain on LD structures, leading to significant defect reduction. Fur-
thermore, by adjusting the Al and In contents, the alloy can be used as
an active layer for light emitting devices in the spectral region from UV to
red, as previously illustrated in figure 1.4 of section 1.3.3. When the InN
content of this rather unexplored alloy is about 18%, the lattice parame-
ter a matches that of GaN. However, the band-gap is considerably higher
than that of GaN (4.3 eV [142] instead of 3.4 eV) making this material an
attractive host candidate for RE dopants.
To investigate the properties of this alloy as a host for RE light emission
a set of Alx In1−x N thin films were grown on GaN by MOVPE (Metalor-
ganic vapor-phase epitaxy) at the University of Strathclyde. Several growth
parameters such as temperature ([760,840]o C), thickness ([130,260] nm) and
Al and In relative stoichiometries ([0.12,0.24]% In) were adjusted in order to

study their effect on the crystalline quality and luminescence. That range of
In/Al stoichiometries has been chosen in order to remain in the vicinity of
minimal strain between Alx In1−x N alloy and GaN: Al0.82 In0.18 N ([142]).
After initial structural characterization with RBS/C and HRXRD (al-
lowing to determine each sample’s composition), the samples were im-
planted with a nominal fluence of 5 × 1014 Eu/cm2 and annealed in a
furnace at 800o C with a GaN proximity cap, under constant N2 gas flow
for 30 minutes.
Figure 6.35 shows the random and c-axis aligned RBS/C spectra of
two such films evidencing different crystalline qualities. Both samples were
grown at 820o C however, during growth of sample 338 an attempt was made
to obtain a thicker layer by increasing the precursors flow rate by a factor
of 2.5, as compared to sample 337 ([143]). Sample 337 presents a very good
crystalline quality with minimum backscattering yields, measured on the In
signal from the film and Ga signal from the buffer layer, of χmin (In) = 3.6%
and χmin (Ga) = 2.6%. On the other hand, sample 338 reveals much worse
quality with χmin (In) = 56.2% and χmin (Ga) = 37%. Clearly the precursor
flow rate increase during growth has a negative impact on sample quality.
In order to assess the composition of the films, two techniques were
employed, namely the fitting of the RBS spectra with an iterative computer
code (RUMP [112]); and the application of Vegard’s law to the information
obtained by HRXRD. Concerning the films stoichiometry as obtained from
fitting with RUMP, figure 6.36 shows the overlapping of the fit with the
RBS/C spectrum for both samples. For sample 337 the best fit to the
RBS spectrum was obtained by considering the AlInN to be composed of
two layers with slightly different compositions as shown in table 6.1. As for
sample 338, the best fit was achieved by considering a composition gradient
for the concentrations of Al and In. This is consistent with the fact that
precursors flow rates were modified during growth.
Concerning the analysis with HRXRD, figures 6.37 and 6.38 show the
HRXRD spectra diffracted on the (0004) and (1015) planes of GaN and
AlInN for both samples. From the symmetric (0004) reflections one ob-
Fig. 6.35: Random and c-axis aligned RBS/C spectra of two Alx In1−x N layers
epitaxially grown on GaN. The information from both detectors (glancing - upper
figure, and annular - lower figure) is necessary to accurately determine the film
stoichiometry.
Fig. 6.36: RUMP fit of the RBS spectra of samples 337 and 338.
Fig. 6.37: HRXRD spectra measured on the (0004) symmetric and (1015) asym-
metric planes of GaN and AlInN layers of sample 337.
Fig. 6.38: HRXRD spectra measured on the (0004) symmetric and (1015) asym-
metric planes of GaN and AlInN layers of sample 338.
tains the c-lattice parameter of the AlInN film by simply employing the
diffraction law of Bragg (equation 6.1). Obtaining the a-lattice parameter
requires measuring the diffraction from asymmetric or inclined planes (with
c and a components). For a hexagonal lattice one has the following expres-
sion ([145]) for the distance between planes of the (h,k,l ) family, being h,k,
and l the Miller indices:
µ ¶
1 4 h2 + hk + k 2 l2
2 = 2
+ 2, (6.2)
dhkl 3 a c
which can be rewritten as
s
4 2 2
3 (h + k + hk)
a = c × dhkl . (6.3)
c2 − l2 d2hkl
From equation 6.1 one obtains dhkl from the θ value on the spectra
corresponding to the maximum intensity of the peak. As such, the values
of c and a for the AlInN layer are obtained.
The composition of the film can be obtained attending to the theoretical
c and a lattice parameters for AlN and InN as found in table 1.1, and
employing Vegard’s law:
a(Alx In1−x N ) = x × a(AlN ) + (1 − x) × a(InN ), (6.4)
Layer thickness Å InN%

350 13.2
1020 15
GaN buf f er
Table 6.1: Fit result for sample 337.
Layer thickness Å InN%

1680 13.5
250 15.5
650 18.5
GaN buf f er
Table 6.2: Fit result for sample 338.

and
c(Alx In1−x N ) = x × c(AlN ) + (1 − x) × c(InN ). (6.5)
As such, the composition of the films as given by HRXRD is displayed

in tables 6.3 and 6.4.
It should be noticed that obtaining the composition of sample 338 from
the a-parameter was not possible. Not only the peak intensities on the
asymmetric scan are very small but also, unlike the spectrum of the sym-
metric scan, there was only one peak for the AlInN film registered on the
asymmetric scan. As such, the film composition is only given by the in-
formation as obtained from the c-lattice parameter. The compositions of
both films are then: Al0.85 In0.15 N / Al0.87 In0.13 N as obtained by fitting
the RBS spectrum, and Al0.83 In0.17 N by HRXRD for sample 337. Concern-
ing sample 338, the gradient Al0.82 In0.18 N / Al0.85 In0.15 N / Al0.87 In0.13 N
was obtained from fitting the RBS spectrum. Applying of Vegard’s law to
the HRXRD spectra of this sample yielded the compositions Al0.77 In0.23 N ,
Al0.80 In0.20 N and Al0.84 In0.16 N . Remarkable is the fact that both tech-
niques allowed quantifying the gradient of concentrations caused by altering
the growth conditions of sample 338. However, InN and AlN contents on
the layers as determined by both methods do not perfectly coincide. One of
the reasons might be related to the accuracy of the fit to the RBS spectra.
Besides layers compositions and thicknesses, other parameters (interface
InN% ±
16.6 1.7
Table 6.3: Composition of sample 337 as obtained from HRXRD.
InN% ±
15.6 1.9
19.5 2.5
22.6 2.1
Table 6.4: Composition of sample 338 as obtained from HRXRD.

mixing, detector resolution, etc) can be adjusted to obtain “optimal” fits

to the experimental data. Not all of the adjustable parameters will nec-
essarily have a physical meaning concerning the sample composition. On
the other hand, the method here employed to obtain the composition of
the layers from HRXRD does not take into account effects of lattice strain.
In fact there is evidence that AlInN alloys epitaxially grown on GaN are
strained, and therefore do not exactly follow Vegard’s law. Reference [144]
discusses the necessity of introducing correction factors to the a and c lat-
tice parameters, as determined from HRXRD, before applying Vegard’s law
to determine the composition of AlInN layers epitaxially grown on GaN.
With the correction, excellent agreement may be obtained between results
obtained by XRD and those from RBS.
Optical characterization of Eu-implanted AlInN vs. GaN

After assessing the composition and crystalline quality of these samples,
they were implanted at room temperature with a fluence of 5×1014 Eu/cm2
along the c-axis direction. Along with these samples, a control GaN sample
was also implanted at the same conditions. After implantation the samples
were annealed in a furnace at 800o C as previously described. These samples
were then optically characterized by photo and cathodoluminescence at
the Department of Physics of the University of Strathclyde. It should be
mentioned that due to the small dimensions of the samples (∼ 0.5 × 0.5
cm2 ), it became impractical to investigate the impact of Eu implantation
on their crystalline quality with RBS/C (∼1 mm beam spot diameter)
before and after annealing, without compromising the results of optical
characterization. However, visual inspection of the samples indicated that
the typical brown color after implantation, as observed in GaN samples was
less intense for as-implanted 338 AlInN and considerably lighter for the case
of 337, as shown in figure 6.39. This fact indicates possible differences in the
level of lattice disorder in GaN and AlInN after implantation. Assuming
that color centers are representative of the level of lattice disorder, one is led
to conclude that the AlInN lattice is less disordered than the GaN lattice.
Fig. 6.39: Samples AlInN 337, 338 and GaN 107, as-implanted with 5 × 1014
Eu/cm2 along the c-axis.
Upon annealing, both types of nitride samples have the same appearance.
Figure 6.40 compares the optical properties of the 5 D0 −7 F2 emission
line from the three Eu-implanted nitride samples (AlInN 337 and 338 and
GaN 107), as measured by PL with an excitation wavelength of 325 nm,
at 20 (top) and 240 K (bottom). The most striking feature in both sets of
spectra is the fact that AlInN sample 338 produces a very broad emission
band centered at about 623 nm. This band can undoubtedly be associated
with the Eu intra-4f 5 D0 −7 F2 transition. In contrast with this broad band
both AlInN 337 and GaN 107 samples produce very sharp luminescence
lines. In fact the 5 D0 −7 F2 fine structure (triplet at 20 K and duplet
at 240 K), as discussed in section 6.5, can here be seen for both these
samples. Furthermore, the sharp Eu-related luminescence intensity from
sample AlInN 337 is much more intense than that from GaN 107. Also,
Fig. 6.40: PL spectra on samples AlInN 337, 338 and GaN 107, implanted with
5 × 1014 Eu/cm2 and annealed at 800o C.
as can be seen from both sets of spectra, even for sample 337 the sharp
luminescence peaks seem to be superposed on a broader band centered at
about 624 nm. The broadening of the Eu-related luminescence for sample
338 appears to be related to the worse crystalline quality, as measured by
RBS/C.
Concerning CL characterization, figure 6.41 compares the intensities of
the Eu-related luminescence 622 nm line from the three samples, excited
at room temperature with a beam of 5 kV electrons. In terms of intensity,
the same trend as with PL is now also observed: the wider band-gap AlInN
host emits considerably more intense luminescence than GaN. However,
both AlInN samples reveal now a broader band, as compared to GaN.
The RE:AlInN band is also slightly red-shifted. The lower luminescence
intensity of sample 338, as compared to 337, can be attributed to its lower
crystalline quality, as observed by RBS/C on the unimplanted sample.
Depth information can be obtained from CL by changing the incident
beam energy. The more energetic the electron beam is, the deeper it pene-
Fig. 6.41: CL spectra on samples AlInN 337, 338 and GaN 107, implanted with
5 × 1014 Eu/cm2 and annealed at 800o C.
trates inside the sample. For this purpose,the CL intensity of sample AlInN
337 was collected (at 20 K) as a function of the electron beam energy, rang-
ing from 1 to 6 keV. Figure 6.42 shows the CL spectra obtained at the sev-
eral electron beam acceleration voltages ([141]). For electron beam energies
below 3 keV the CL spectra are composed of a single broad peak with a
fwhm of about 4 nm. Increasing the beam energy results in obtaining fine
structure on the CL spectra, namely a triplet of sharp peaks (characteristic
of the 5 D0 -7 F2 transition of Eu3+ ) on top of the broad band observed for
lower beam energies. A Monte-Carlo simulation was performed to calculate
the range of energy deposition of 4.5 keV electrons in AlInN films. This
simulation showed that 90% of the electron energy is deposited within a
depth of 1500 Å. Bearing in mind that the thickness of the 337 AlInN sam-
ple (as measured by RBS) is 1370 Å, the CL spectra of figure 6.42 suggest
that the sharp peaks obtained for energies above 3 keV originate from Eu
ions that reached the underlying GaN layer. This fact indicates that the
channeling effect during Eu implantation brought the Eu-ions to a depth,
Fig. 6.42: CL spectra on samples AlInN 337 as a function of the excitation energy
for the 5 D0 -7 F2 transition of Eu3+ .
about 5 times larger than the projected range obtained by SRIM (∼ 300 Å).
Such mismatch is not surprising considering that SRIM does not take into
account the crystalline structure of the host material, and thereby neglects
channeling effects. The presence of traces of Eu ions (about 3 orders of mag-
nitude less than at the surface) at this depth in the GaN layer was confirmed
by time-of-flight secondary ion mass spectrometry (TOF-SIMS) measure-
ments (not shown here - [141]). These measurements also suggest that the
implanted Eu-ions displaced some In and Al ions through the AlInN/GaN
interface, generating a region of mixed In, Al and Ga composition. It can
be concluded from the observations above that the Eu3+ ions implanted
in the AlInN film generate the broad band observed in the CL spectra,
and that the small fraction (∼ 1%) of Eu ions that reach the underlying
GaN layer generate the sharp luminescence lines. This considerably intense
sharp luminescence from the very low concentration of Eu-ions in the GaN
film suggests that those ions have an extremely high excitation efficiency.
It should however be mentioned that, once again here, the level of lattice
damage plays a very important role: as only a very small fraction of the im-
planted Eu ions reached the GaN layer, the level of luminescence quenching
lattice defects in that region is very reduced and consequently quenching
of luminescence from the optically active centers is equally reduced.
Figure 6.43 illustrates the influence of increasing the annealing temper-
ature from 800 to 900o C on the luminescence of sample Eu:AlInN 338. As
shown in the spectra, increasing the annealing temperature by 100o C has
the effect of increasing the Eu-related CL intensity by a factor of 2. This
indicates that considerably more luminescence quenching defects were suc-
cessfully annihilated at 900o C as compared to 800o C. Notice that 900o C is
already above the growth temperature of these samples - 820o C. It is possi-
ble that by further increasing the annealing temperature the luminescence
intensity will also significantly increase, as observed for RE:GaN ([131]).
Another interesting result is the observation of RE-luminescence from
as-implanted (at room temperature) AlInN. This is in contrast with what
is observed in the case of room temperature as-implanted RE:GaN: no RE-
luminescence. Moreover, as seen in section 6.5, weak luminescence (about a
Fig. 6.43: CL spectra of sample Eu:AlInN 338 after annealing at 800 and 900o C.
factor 200 times less intense than after annealing at 900o C) is observed for
as-implanted samples at about 250o C. Figure 6.44 demonstrates that room
temperature implanted AlInN samples already show considerably strong
RE-related luminescence, while comparing with 900o C annealed. This fact
indicates that, a significantly lower amount of luminescence quenching de-
fects is generated in the AlInN lattice during implantation, when compared
to GaN.
It can be concluded from this discussion that the nitride host com-
position has a drastic impact on the RE-luminescence output. On one
hand, as discussed in section 6.6 it is quite possible that the concentra-
tion of Al in the nitride layer strongly conditions lattice damage build-up.
In fact, TOF-SIMS measurements indicate that ion-beam mixing occurs
at the interface between AlInN and GaN. Such observation reinforces the
hypothesis that the mixing of Al and Ga at the interface of AlN/GaN in
Fig. 6.44: CL spectra of samples Er:AlInN 337 and 338 before and after annealing
at 800o C. CL spectrum of Er:GaN is shown for comparison
the AlN-capped samples, is responsible for the suppression of the surface

damage peak in these samples. This same argument can be used to explain
the much stronger RE-luminescence intensity observed from RE:AlInN, as
compared to RE:GaN. The large concentration of Al in this alloy seems to
contribute to keep the concentration of luminescence quenching defects at
a much lower level than that of GaN. As previously mentioned, this can
be attributed to the enhancement of the dynamic annealing during implan-
tation: more energetic Al-N bond as compared to Ga-N, lighter mass of
Al, and possibly also higher mobility of Al interstitials as compared to Ga.
Furthermore, Dynamic annealing enhancement also explains why relatively
strong emission is observed in as-implanted AlInN samples. As less defects
are introduced during implantation, less quenching occurs, even already
in as-implanted samples. On the other hand, another observed effect is
the broadening and red-shift of the RE-luminescence lines of RE:AlInN, as
6.8 Energy dependence 181
compared to RE:GaN. Broadening of luminescence lines might be related

to the site occupied by the RE-ion in the ternary alloy lattice. In the case
of GaN, Braud ([149]) suggests that the broadening of PL lines during non-
resonant excitation is related to the RE-ions in lower symmetry sites, as
compared to REGa . As such, it is possible than in the case of the more
complex AlInN lattice the RE-ions assume less well defined positions and
associate with local defects. As a result, broad RE-luminescence lines are
observed. However, further studies on RE:AlInN are required to clarify the
reason of line broadening and red-shift, as well as the influence of [Al] and
[In] in the damage build-up of this ternary alloy during ion implantation.
6.8 Energy dependence

As discussed in section 5.3, the energy of the incoming ions is an important
parameter to take into account while doping by means of ion implantation.
As shown by the SRIM depth profile simulation in figure 5.9, increasing the
ion energy has the effect of decreasing the ion concentration, by smearing
it out in depth through the target.
Concerning the lattice structural defects caused by implantation, as
shown on figure 5.11, SRIM simulations predict an increase of the damage
level with increasing ion energy: more energetic ions will follow a longer
path inside the host, generating more collision (more displacements and
damage) until they come to rest. This image of damage generation based
on ballistic collisions does not take into account other relevant effects such
as thermal effects, and in particular, dynamic annealing mechanisms. In
this section, the effect of the implantation energy on the lattice damage will
be discussed from an experimental view point. Results will be compared
with SRIM damage distribution calculations and other results from existing
literature.
For this experiment two sets of samples were implanted at room temper-
ature with a fluence of 3 × 1014 Eu/cm2 , along the c-axis direction and 10o
away from that direction, at energies in the range 60 to 140 keV. Implant-
ing above 80 keV introduced additional complications as doubly-ionized Eu

(Eu2+ ) ions had to be selected. As a result the beam intensity is consider-
ably reduced, so the fluence to implant had to be reduced as well in order
to keep the implantation times at reasonable levels. Figure 6.45 shows the
c-axis aligned RBS spectra of 60, 70, 80 and 100 keV 3 × 1014 Eu/cm2
random implanted samples. No drastic changes are observed in the spectra
for this series of energies. The level of displaced Ga-atoms as measured by
RBS is comparable for the four implantation energies. The spectra shown
on the bottom of figure 6.45 represent the level of structural damage with
increasing depth, for the four implantation energies. It can be seen from
this figure that as a result of the ion increasing energy, its depth profile is
increased. Consequently, the degree of lattice damage in depth increases
as well, as observed by the inwards shift of the EOR damage peak. This
is in good agreement with the simulation results obtained with SRIM, as
shown in figure 6.46. Experimentally, this effect is observed by, for exam-
ple, comparing the spectrum of the sample implanted at 60 keV with the
one at 100 keV.
As mentioned in section 6.2, the RBS/C EOR damage peak coincides
with the Ga (and N) vacancy depth profile, as obtained by SRIM. This is
illustrated in figure 6.47 with the spectra of 60 and 100 keV Eu-implanted
GaN. The fact that SRIM does not take into account effects such as, defect
recombination, migration to the surface or preferential sputtering, explains
the lack of a surface defect peak on the damage profile obtained by SRIM.
Also, SRIM does not take into account the crystalline structure of mate-
rials nor channeling effects. As such, SRIM is not adequate to simulate
defect depth profiles of implantations along a crystalline direction. For this
purpose, the MARLOWE code [150] would be a more suitable alternative.
Figure 6.48 illustrates the effect of increasing the implantation energy
for the case of channeled implanted samples. As can be seen, increasing the
implantation energy does not significantly alter the intensity of the surface
damage peak. The EOR damage region is not present at this low fluence.
Another element limiting the extraction of clear conclusions from these
results is the fact that the range of energies employed in this experiment
Fig. 6.45: Top: Lattice damage as measured by RBS/C, for 3 × 1014 Eu/cm2 RT
random implanted GaN, at 60, 70, 80 and 100 keV. Bottom: Depth concentration
of the implantation generated lattice damage
Fig. 6.46: Ga-vacancies depth profile for Eu-implanted GaN in the range of 40-140
keV, as obtained from SRIM
is limited by the physical parameters of the implanter. Even though the

nominal energy range for single charged particles is 20 keV to 100 keV, in
practice while attempting to obtain a beam of double charged particles, the
maximum (workable) energy obtained was 140 keV.
Kucheyev et. al [83] have also studied the effect of the implantation
energy on the defect formation of Au implanted GaN, in the range of 100
to 2000 keV. These authors report that by increasing the energy of im-
plantation, the two damage regions (surface and EOR) are progressively
separated, with the spectra essentially keeping the same main features (one
damage area at the surface and another buried in the bulk material). The
effect of increasing the energy is then the smearing-out of the damage associ-
ated to the EOR of the implanted species. Several factors might contribute
to this effect. On one hand, straggling is associated to the energy loss of
particles in a medium. As such, not only fluctuations in the ion range are
Fig. 6.47: Superposition of the RBS/C EOR damage peak (Eu-implanted GaN)
with the SRIM Ga-vacancy depth profile, for 60 and 100 keV Eu implanted samples
Fig. 6.48: Top: Lattice damage as measured by RBS/C, for 3 × 1014 Eu/cm2
RT channeled implanted GaN, at 60, 70, 100, 120 and 140 keV. Bottom: Depth
concentration of the implantation generated lattice damage
Energy [keV] max (SRIM )

Nvac dpa
40 2.98 1.01
50 3.15 1.06
60 3.25 1.10
70 3.44 1.16
80 3.56 1.20
100 3.64 1.23
120 3.83 1.29
140 3.99 1.34
300 4.26 1.43
Table 6.5: Number of displacements per atom (dpa) caused by implanting 3×1014
Eu/cm2 in GaN at energies ranging from 40 to 300 keV
observed (as illustrated in figure 5.9) but also, from a collisional viewpoint,
damage generation is governed by the same principle. On the other hand,
the balancing effect between amount of displacements per atom (dpa) for
a certain energy value and the density of deposited energy might also play
an important role. For the range of energies and the low implanted fluence
employed in this experiment, the dpa value only increases by 10 - 20%, as
can be seen from table 6.5. Here, dpa is simply given by [137]:
max [vac/Å/ion]
Nvac
dpa = F luence[ion/cm2 ] × , (6.6)
nat [at/cm3 ]
where Nvacmax is the maximum of the vacancy distribution as obtained from
SRIM, and nat is the atomic density of GaN.

The fact that the dpa value does not considerably increase for the range
of energies of this experiment and for the implanted fluence, is responsible
for the fact that no drastic changes are observed in the RBS/C spectra of the
implanted samples. Figure 6.49 illustrates the evolution of the integrated
Ga-displacements with increasing incoming ion energy. Surprisingly, both
curves in the graphic show a decrease in the defect concentration with in-
creasing ion energy, for both implantation geometries. Considering simply
the ballistic aspects of ion implantation, an increase in the defect concen-
tration would be expected, as more energy is deposited into the lattice, by
Fig. 6.49: Evolution of the integrated defect concentration (Ga displacements)

with increasing ion energy, for random and channeled implantation (3 × 1014
Eu/cm2 )
more energetic ions. On the other hand, a more energetic beam will have
a larger range straggling, and consequently the deposited energy density
will be lower. For less energetic ions, even though the transferred energy
per ion is lower, the density is in fact higher and thereby more dislocations
will occur. However, as previously discussed implantation damage build-
up cannot correctly be described only in terms of ballistic processes. In
particular, for the case of GaN, dynamic annealing must be taken into ac-
count. In fact, attending to the relatively low fluence of implantation used
in this experiment (3 × 1014 Eu/cm2 ), and to the discussion in section 6.3,
dynamic annealing is expected to very effectively limit the concentration
of implantation defects. Furthermore, ion energy is expected to strongly
influence the efficiency of dynamic annealing ([82]): recoils with more en-
ergy will induce more local recombination of defects produced by earlier
recoils. As such, both effects - deposited energy density, dynamic anneal-
6.9 Ion mass dependence 189
ing enhancement with increasing ion energy - might explain the unexpected
results from figure 6.49.
6.9 Ion mass dependence

As pointed out in section 5.3, the incoming ion mass has a strong impact on
the build-up of crystalline structural damage upon ion irradiation. How-
ever, there are similarities and differences on the disorder build-up caused
by heavy and light ion implantation in GaN. For both mass regimes, sig-
moidal distributions of damage with increasing ion fluence were observed
([83]). Also, two lattice disorder regions are observed on the RBS/C spec-
tra of samples implanted with both regimes of ion mass : the surface and
the EOR damage regions.
The main difference between the two regimes appears to be related to
the bulk (EOR) damage build-up. As Kucheyev et. al observed [83], for
the case of heavy ion implantation, the bulk damage level saturates well
below the random level, with amorphization proceeding layer-by-layer from
the surface. In the case of light ion implantation, the random level in the c-
axis oriented spectrum is achieved for the bulk damage region even without
superposition of the surface damage peak.
For the present work, mostly 153 Eu has been implanted into the nitride
films, however 158 Gd and 132 Xe were also employed, especially for electrical
characterization studies, as discussed in chapter 7. Despite the fact that
no extreme mass differences were employed, it was interesting to assess the
level of damage caused by ions within these two mass regions (130 and
150-160 a.m.u.). As such, two sets of GaN samples were implanted at RT
with 80 keV 132 Xe and 158 Gd ions with a fluence of 5 × 1014 /cm2 . Implan-
tations occurred along both channeled and random geometries. Structural
characterization after implantation was performed by RBS/C. Posteriorly
the samples were annealed at 950o C with GaN proximity caps and constant
N2 flow, by RTA for 2 minutes, following the same procedure as described
in section 6.5. Once more, RBS/C was employed to assess the recovery
of structural damage achieved by the thermal treatment. Figure 6.50 il-
Fig. 6.50: Top: RBS/C lattice damage profile for 5 × 1014 132 Xe, 153 Eu, 158 Gd
and 166 Er/cm2 RT random implanted GaN. Bottom: Respective damage profile
for the channeled implantation geometry.
lustrates the progression of the lattice disorder upon implantation of four

ion species in the mass regions 132 and 153 to 166 a.m.u. The effect of
the ion mass is better seen by comparing the spectra of Xe-implanted with
Eu-implanted GaN. As can be seen by the top illustration, both masses
generate two damage regions (surface and ion-EOR), however the relative
level of lattice disorder is considerably smaller for the Xe-implanted sam-
ple (∼ 1/3). Yet, comparing the dpa values as calculated by equation 6.6
for 132 Xe and 158 Eu, the values are not drastically different: 1.88 dpa for
132 Xe and 2.08 dpa for 158 Eu. Furthermore, differences in deposited energy
density do not explain the large difference in defect concentration: there

is only a small difference in projected range, as calculated from SRIM, for
both ion masses - 215 Å for Xe and 200 Å for Eu. Such effect is possibly
explained by differences in dynamic annealing during implantation of each
of the species. Since both ions have the same energy, and about the same
projected range, the density of deposited energy is approximately the same.
However, less implantation defects are introduced by Xe implantation and
thereby a higher-recovery rate of defects, while being created, is observed
for Xe:GaN. On one hand, from a collisional point of view, less defects
are introduced during Xe implantation, as compared to RE implantation;
on the other hand, the deposited energy during implantation, which also
leads to local temperature increase, will more efficiently contribute to defect
recombination since less defects are introduced.
This trend is also observed while comparing the structural damage intro-
153 158 166
duced by the three RE-ions: [Gadispl. ] Eu < [Gadispl. ] Gd < [Gadispl. ] Er .
Similar observations are made for the channeling implantation geom-
etry: steep increase of the level of disorder while comparing Xe with Eu,
followed by a slight increase of that level with the implantation of Gd.
However, the EOR damage peak is absent for channeled implanted Xe,
indicating that considerably less damage is formed in the bulk region of
Xe:GaN.
As previously mentioned, the samples were posteriorly annealed at
950o C and RBS/C measurements were performed on these samples to eval-
uate the efficiency of the thermal treatment in the recovery of implantation-
induced disorder.
Figure 6.51 shows the RBS/C spectra of the as-implanted and after an-
nealing samples for both implantation geometries of Gd in GaN. As seen
from this figure, even after annealing at 950o C a considerable amount of
lattice disorder is still present. The best recovery is achieved for the chan-
neled implantation geometry, in agreement with the results of section 6.5.
It should also be noticed that for both implantation geometries and sim-
ilarly to Eu:GaN, the strongest recovery occurs at the surface region. As
discussed in section 6.3, this is an indication of the different nature of de-
fects at the surface and in the bulk regions. The point defects accumulated
at the surface recombine easier upon high temperature thermal treatment
than the extensive and more stable defects formed in the bulk region.
Concerning the spectra from the Xe-implanted samples, figure 6.52 com-
pares the effect of post-implantation annealing for both implantation ge-
ometries. Recovery of disorder is strong for the channeled implanted sam-
Fig. 6.51: RBS/C spectra of as-implanted and after annealing for the Gd im-
planted samples, along both implantation directions
Fig. 6.52: RBS/C spectra of as-implanted and after annealing for the Xe implanted
samples, along both implantation directions
ple, where the EOR damage peak was absent. However, in the case of
random implantation, the reduction of amplitude of the surface damage
peak is accompanied by an increase of the amplitude of the EOR defect re-
gion upon annealing at 950o C. It is possible that this behavior is associated
with the formation of Xe gas bubbles in the bulk region. The reduction of
surface disorder could be explained by diffusion of Xe towards the surface,
as well as towards the region where most implanted Xe ions come to as stop
- the EOR region. In this region, the accumulation of Xe will lead to the
formation of noble gas pockets that would contribute to further increase the
level of lattice disorder. However, it is not possible to assess the existence
of such noble gas pockets using RBS/C characterization. For that purpose
microscope analysis techniques such as TEM, would be more useful.
It can be concluded from these results that the implanted ion mass plays
an important role on the process of damage build-up. However, as partly
concluded already from previous sections, damage build-up is not merely
governed by collisional physics. The ion mass also affects the dynamic
annealing mechanism: it seems to be enhanced for lighter incoming ions,
as Xe versus RE results indicated. Nevertheless, in order to properly assess
the effect of the implanted ion mass on the damage formation mechanism
in implanted GaN, a wider range of masses should be implanted, as Xe only
differs from Eu by 20 a.m.u..
6.10 Beyond the limitations of RBS/C
As seen throughout this chapter, RBS/C presents itself as a powerful an-

alytical technique for the structural characterization of defects in semicon-
ductors. However, it often must be complemented with other techniques,
such as X-ray diffraction and electron microscopy in order to obtain further
insight on the sort of defects formed during implantation, for example. Nev-
ertheless, it is possible to expand the conventional application of RBS/C, in
order to obtain further structural information about the analyzed samples.
As previously mentioned, dechanneling of the axis-aligned incoming ion
beam occurs even in a “perfect” crystal. Several small angle multiple-
scattering collisions with the electrons of the medium are responsible for the
progressive defocusing of the ion beam as it penetrates deeper in the crys-
tal. This multiple-scattering will increase the probability of close-encounter
collisions with lattice atoms displaced from their static positions because
of thermal vibrations on the lattice. These close encounters might set the
ions in a trajectory with an angle larger than the critical channeling an-
gle, as discussed in section 5.3. As a result the ions will be dechanneled.
In a defective crystal, dechanneling is much stronger. Displaced atoms lo-
cated at the center of a channel provide efficient scattering centers for the
aligned incoming beam. Also, extended defects such as dislocations and
stacking faults, can cause the distortion of the channels and increase the
dechanneling effect.
In general, one can define the probability of dechannelling per unit of
depth in the crystal as ([138]):
6.10 Beyond the limitations of RBS/C 195
dPD
= σD × nD (z), (6.7)
dz
where σD is the dechanneling factor and nD (z) the density of defects.
Different sorts of defects will affect differently the dechanneling phenomenon
on defective crystals. As such, each type of defect will have a certain σD
associated to itself. It can be demonstrated ([138]) that:
for point defects

πZ12 Z22 e4 1
σD ∼ 2 2 ∼ , (6.8)
E Ψ1/2 E
with Z1 , Z2 , e the parameters as discussed in section 5.1, E the beam
energy and Ψ1/2 the critical angle (see appendix A);
for dislocation lines
b √
σD = ∼ E, (6.9)
πΨ1/2
where b is the modulus of the Burgers vector associated with the dislocation;
for stacking faults
σD = χmin , (6.10)
as the stacking fault will introduce the same scattering effect as the surface
of the crystal (χmin ) - see figure 6.53;
for amorphous clusters

πZ12 Z22 e4 1
σD = Cc 2 2 ∼ , (6.11)
E Ψ1/2 E
where Cc is the average number of atoms per cluster. Concerning their

effect on the dechanneling of aligned ion beams, amorphous clusters can be
treated as isolated point defects as long as the value of Cc over the depth
traversed by the beam is < 1017 /cm2 . For higher areal concentrations,
multiple scattering effects must be considered.
Figure 6.54 summarises the energy dependence of several types of de-
fects, as discussed above. RBS/C can be employed to obtain such qualita-
tive information. In fact, as previously mentioned (section 5.4), the value
Fig. 6.53: Scattering at the interior surface caused by the stacking stacking fault
boundary [138]
of χmin is an indication of the probability of a close encouter between the

incoming ion and a lattice atom (or defect) and thus it offers an experimen-
tal procedure to assess the dechanneling factor. Intrinsically χmin shows
some dependence on the beam energy E, especially at low energies. How-
ever, it can be demonstrated ([138]) that at sufficiently high energies, the
value of χmin becomes energy-independent. For the values of energy em-
ployed in this experiment (Eα ≥ 0.7M eV ), the energy-independent regime
of χmin is reached.Consequently, any eventual changes of χmin with en-
ergy will only reflect the energy dependence of the dechanneling factor, as
mentioned above.
For this study, two samples implanted under different conditions were
measured with RBS/C along the c-axis with 4 He+ beam energies in the
range between 0.7 and 2.5 MeV. Sample A was implanted with a fluence
of 1 × 1015 Eu/cm2 at RT and with the Eu beam direction tilted 10o away
from the perpendicular to the sample’s surface. Sample B was implanted
with a beam fluence of about 5 × 1014 Eu/cm2 along the c-axis direction at
70o C.
Figure 6.55 shows the evolution of the minimum yield χmin with in-
6.10 Beyond the limitations of RBS/C 197
Fig. 6.54: Energy dependence of the dechanneling factor for several sorts of defects
[138]
creasing 4 He+ -beam energy as obtained from the c-axis aligned RBS/C
spectra for both sets of implantation conditions. For both data-sets, fitting
functions of the form a × E b were applied, with the correspondent a and b
parameters given as inset in the figure. The data-set corresponding to sam-
ple A shows an exponential decay of the χmin with increasing beam energy,
with coefficients that reveal some deviation from the E −1 decay. For the
case of sample B, the fit coefficients show a much larger deviation to that
behavior. In fact, the data-set from sample B shows rather a linear behav-
ior where χmin decreases only slightly with increasing beam energy. From
both curves it can be concluded that in the case of sample A, dechannel-
ing occurs mainly due to interstitial defects and/or amorphous clusters. In
the case of sample B, dechanneling seems to be caused mostly by stacking
Fig. 6.55: Dechanneled fraction for different 4 He+ -beam energies of samples A
and B. In both cases a fitting function a × E b was applied to the data set.
faults, as suggested by figure 6.54, where the dechanneling factor is inde-

pendent of the beam enegy (linear relation with slope zero). However, as
seen in figure 6.55, a negative slope is observed for the sample B. As such,
for both sample A and B there seem to be deviations from the ∝ E −1 and
∝ E behavior, respectively. Such deviations are possibly due to the contri-
bution of other sorts of defects that counteract the exponential decay and
constant behavior of the χmin with increasing beam energy. For example,
the presence of a considerable concentration of interstitials and other point
defects in sample B might contribute to deviate the energy independent
trend set by a majority population of stacking faults and applying a slight
negative slope to it. This approach was used by Wenzel et al. in [121] to in-
vestigate with RBS/C the nature of structural defects in 2.5×1015 Mg/cm2
implanted GaN at 550o C. Here, a fitting curve following a E −1 trend was
applied to the experimental results indicating that point defects (displaced
atoms) constitute the majority of the defects found in this sample.
6.11 Conclusion 199
6.11 Conclusion
In this chapter, the crystalline structure of Eu-implanted nitride thin layers

has been assessed. Mainly two techniques have been used to characterize the
implanted nitrides, namely RBS/C and HRXRD. Structural information
was often complemented with luminescence measurements by PL and CL.
The influence of several experimental parameters on the doped material
properties has been investigated: ion fluence ranging from 1×1014 to 1×1016
ions/cm2 ; direction of implantation with respect to the main crystalline
axis (0 and 10o ); substrate temperature during implantation from RT to
800o C; ion energies between 60 and 140 keV; host material composition, in
particular, main differences between AlInN and GaN; and the mass of the
incoming ion.
Visual inspection of implanted material reveals a change of color in the
area of implantation. Depending on the implantation fluence, the mate-
rial becomes yellow-brown (and eventually black for very high fluences),
whereas initially it was light opaque. This color change is a manifesta-
tion of the implantation-induced lattice disorder. RBS/C indicates that
such disorder is distributed in depth through the crystal into two regions,
one closer to the surface and another coinciding with the implanted ion
projected range. The incident ions can experience several collisions with
host atoms along their inwards trajectory. The generated energetic host
recoils will, on their turn, collide with other host atoms and generate more
recoils in a cascade-like manner. HRXRD reveals that implantation in-
duces strain: the lattice is expanded in the region of implantation due to
crystalline disorder.
Lattice disorder increases sigmoidally with increasing dopant fluence.
For low fluences (≤ 3 × 1014 ) damage concentration is low and limited to
the surface. No EOR damage region is observed as strong in-cascade defect
recombination occurs. The remaining damage is mainly composed of point
defects (Ga, N interstitials and vacancies) which are mobile and migrate to
accumulate at the surface. Intermediate fluences (> 3 × 1014 − 1 × 1015 )
generate more defects. Also their complexity increases: larger defect clus-
ters, dislocations, etc. Besides the increasing accumulation of defects at

the surface region, the level of structural defects in the RE EOR region
increases as well for this range of fluences. However, unlike the surface
damage region (that becomes amorphous), the level of EOR damage seems
to saturate below the amorphization level. An efficient dynamic annealing
mechanism is responsible for this behavior. With increasing fluence, amor-
phization will proceed from the surface inwards in direction of the bulk
material.
Room temperature implantation generates an elevated concentration of
structural defects, in particular luminescence quenching defects - no RE-
related emission is observed on as-implanted samples. Thermal annealing
is required to (at least) partly recover such defects. Total recovery demands
extreme temperature conditions which lead to material decomposition. An-
nealing at 950o C under N2 flow during 30 minutes allows to considerably
reduce the concentration of defects and obtain RE-related luminescence.
Despite the fact that more RE ions are introduced at higher implantation
fluences, luminescence was observed to be stronger for lower fluences, for
which less luminescence quenching defects are introduced.
The density of structural defects is drastically reduced when implanting
along the c-axis of GaN. Fewer head-on collisions with host atoms will occur
as ions are gently steered along the channels bordered by the rows of atoms
generating the steering potential. Channeled implantation allows implant-
ing higher dopant fluences while keeping the level of lattice defects lower, as
compared to random implantation. Furthermore, for the same concentra-
tion of lattice damage as measured by RBS/C, HRXRD shows less lattice
expansion for channeled implantation. After annealing, luminescence inten-
sity is considerably stronger for the case of channeled implantation. This
implantation geometry generates a higher number of optically active cen-
ters, as compared to random implantation that introduces a considerably
higher level of luminescence quenching structural defects.
In order to attempt to further reduce luminescence quenching, associ-
ated to implantation structural defects, the substrate temperature during
implantation was increased. Results showed that already at only about
6.11 Conclusion 201
200o C, a considerable reduction of lattice disorder is achieved. Above

400o C no further reduction is observed and even a slight increase of de-
fect concentration was found to take place. Concerning differences related
to implantation geometry, not only the general level of structural defects
is significantly lower for channeled implantation, it has also been observed
that the EOR damage region is strongly suppressed for that geometry.
Since less defects are, per definition, generated along that direction, dy-
namic annealing is more efficient in recovering defects while being gener-
ated. Furthermore, increasing the substrate temperature during implan-
tation considerably enhances dynamic annealing. Therefore, elevating the
substrate temperature during implantation is an efficient method for intro-
ducing higher dopant fluences while keeping structural damage at reduced
levels. This method also allows to enhance luminescence: after annealing,
RE-related emission is much stronger in samples implanted at elevated sub-
strate temperatures, as compared to RT implantations. The reduction of
structural defect levels by elevated temperature implantations has a direct
impact on the population of luminescence hindering defects: the concen-
tration of such defects decreases. Such effect is noticeable through the
observation of luminescence in as-implanted (not annealed) samples. Weak
luminescence is observed for samples implanted at temperatures as low as
50o C. Interestingly, this “as-implanted” luminescence is about one order of
magnitude stronger for the case of random implantation, as compared to
channeled. This can be explained by a higher concentration of structural
defects (luminescence quenching + optically active) introduced during ran-
dom implantation. As the substrate temperature during implantation is
increased, more defects are recombined. However, due to the higher defect
mobility at such elevated temperatures, it is possible that a larger amount
of stable optically active RE-defect complexes are formed. Consequently,
the population of luminescence hindering defects decreases while the popu-
lation of optically active increases. Comparing to channeled implantation,
the random geometry introduces a higher concentration of both kinds of
defects. However, while potential luminescence hindering defects are recom-
bined, optically active complexes are formed. Nevertheless, it is important
to emphasize that the intensity of “as-implanted” luminescence is at least

one order of magnitude lower that that of RT-implanted followed by an-
nealing. This indicates that still a large fraction of luminescence hindering
defects are present in high temperature implanted samples. In contrast
with “as-implanted” luminescence, the intensity of RT+annealed samples
is stronger for the channeled geometry of implantation. Even though less
defects are introduced (quenching+active), after annealing the population
of luminescence quenching defects is substantially more reduced for that
geometry, as compared to random implantation. Therefore, luminescence
in channeled RT-implanted and subsequently annealed samples is stronger.
Structural characterization results further indicate that the composition
of the nitride layer strongly influences the implantation damage build-up
mechanism, as well as the optical emission properties of RE-implanted lay-
ers. It has been observed that implantation through an AlN protective
cap results in the suppression of the usual surface amorphous region. Dur-
ing implantation, ion-beam induced mixing occurs at the interface between
GaN and AlN. It is possible that the introduction of small amounts of Al
in the GaN interface region generates locally an alloy that prevents GaN
surface amorphization. In the case of other alloys, where the Ga-atom has
been replaced by a combination of Alx In1−x , with x in the range of 82%,
changes in the RE-luminescence characteristics are observed. Although as
compared to RE:GaN the luminescence intensity is much higher, the lines
become significantly broader and a slight red-shift is observed. Further-
more, “as-implanted” luminescence is observed for RT implanted samples
indicating that the level of luminescence quenching defects after implan-
tation is smaller than in GaN under similar conditions. This is likely to
be related to the elevated Al concentration in these alloys. As discussed,
Al host atoms not only will generate smaller recoil cascades but seem to
enhance the efficiency of defect recombination during implantation. This
would also allow to explain the suppression of surface amorphization in
AlN-coated GaN, as mentioned above.
The energy and mass of the implanted ions are two other parameters
that also strongly affect the host damage build-up upon implantation. By
6.11 Conclusion 203
increasing the energy of the incident ions, their range in the target will
accordingly increase. Monte Carlo simulations based on ballistic collision
physics predict equally an increase of the structural damage caused by im-
plantation. Nevertheless, such simulations do not take into account the
effects of dynamic annealing. The experimental results here presented (in
the range of 60 to 140 keV) indicate that the EOR damage region ap-
pears indeed progressively deeper, however the in-depth integrated damage
concentration does not considerably change with increasing ion energy. In
fact, contrary to what would be expected, the lattice damage level slightly
decreases with increasing energy for both implantation geometries. Such
behavior is possibly explained by differences in deposited energy density.
As discussed, a more energetic beam will have a larger range straggling and
consequently the density of deposited energy will be lower. Less energetic
ions will locally deposit a higher energy density and therefore generate lo-
cally more defects. On the other hand, increasing ion energy has the effect
of enhancing dynamic annealing. As such, the efficiency of implantation
defects recombination increases with increasing ion fluence.
Concerning the effect of the incident ion mass, it has been observed
that the lighter Xe-ions generate a much lower concentration of lattice
defects than the heavier RE-ions. Since, for the same energy, less defects
are generated by lighter ions, less defects have to be recombined while being
generated (dynamic annealing) and therefore the crystalline quality after
implantation will be higher.
Finally, since different sorts of structural defects will affect the trajec-
tory of incoming ions in a different manner, depending on the incident
beam energy, it is possible to infer the type of the dominant species of
defects present, by studying how the RBS/C minimum yield varies with
the incident beam energy. It was possible to conclude that point defects
and stacking faults constitute the majority of structural defects in RE-
implanted GaN, as confirmed by TEM analysis.
So far, the structural properties of Eu-implanted GaN have been inves-

tigated. It could be concluded that doping by means of ion implantation
introduces structural defects in the host crystalline lattice. Moreover, op-

tical characterization studies have shown that structural defects have a
strong impact on the typical RE luminescence output observed from the
doped nitride films. However, the effect of RE doping on the band structure
of GaN still remains to be discussed. How do structural defects influence
the material band-gap? are there electrical defects introduced in the doped
material that lead to the introduction of band-gap states, as discussed in
chapter 2? Are those electrical defects caused by implantation structural
defects or are they RE-related? In fact, as previously discussed, theoret-
ical calculations predict that RE-defect complexes, such as REGa VN , are
responsible for the appearance of carrier traps in the GaN band-gap. Some
of these traps are thought to be involved in the energy transfer mecha-
nism between the host material and the RE dopants. Such transfer is also
thought to be responsible for excitation of the RE 4f electrons yielding the
typical RE luminescence. Therefore, it is important to understand the role
of structural defects and the dopants themselves on the electrical properties
of the doped material.
Chapter 7
Electrical characterization of
Eu-implanted GaN
The focus of the two previous chapters was the use of ion beams for both
modifying and characterizing the properties of materials. GaN has been
doped with RE ions through ion implantation, and the structural properties
of the doped material were studied by RBS/C employing 4 He+ .
As discussed in section 2.5.3, RE-ions are implanted in GaN for the
purpose of optical doping. However, the energy transfer mechanism be-
tween the GaN host and the RE-ions, responsible for the light emission
from intra 4f transitions in the RE electronic structure, is still far from
understood. The kinetics model developed by Lozykowski in 1993 [55],
intends to explain the energy transfer from III-V host semiconductors to
the localized core excited states of RE isoelectronic traps. RE-ion in the
3+ state will replace the group-III cation in III-V semiconductors. Due to
differences in size and electronegativity the impurity may produce bound
states in the band gap. For example, Yb replacing In in InP is known to
create an electron trap at 30 meV below the bottom of the conduction band
[151]. The RE isoelectronic impurity bound states can attract both elec-
trons and holes, and consequently bound excitons can be formed at these
states. The model described by Lozykowski predicts that energy can be
transferred from the host material to the RE 4fn electron system through
205
206 Electrical characterization of Eu-implanted GaN
three possible mechanisms.

The first mechanism consists on the energy transfer from an exciton
bound to the isoelectronic center to the RE 4f electrons.
In the second mechanism, the transfer of energy to the core electrons
involves a trapped electron (hole) at the isoelectronic center, and a free
hole (electron) in the valence (conduction) band.
Finally, in the third mechanism, transfer of energy is mediated by an
inelastic scattering process, through which the energy of a free exciton near
the RE-related trap is transmitted to the RE localized core excited states.
In this scenario, if the energy of the initial and final states is not the same,
the mismatch in energy must be accommodated by, for example phonon
emission or absorption.
According to Lozykowski, it is not strictly necessary that the RE ions
occupy a “pure” group-III ion substitutional position. If the RE-ion is very
chemically active, it might induce more complex centers, in combination
with defects. This last situation is in agreement with the RENiBEl the-
oretical calculations ([46]). In fact, according to these calculations, the
simple REGa defect does not introduce levels in the band gap of GaN. Nev-
ertheless, while considering other configurations involving defects, such as
vacancies and interstitials, electrically active centers are introduced in the
band gap, as was illustrated in figure 2.11. However, not all the introduced
active defects will be involved in the host-4f energy transfer that leads to
the typical RE luminescence emission.
Due to their similar nature (size and electronegativity), it is reasonable
to assume that all RE-ions will induce a similar level in the band gap of
GaN. Filhol et al. reasoned that such a level must be located not deeper
than 0.2 eV below the conduction band, since an energy of at least 3.249
eV is necessary to populate the 5 D3 →7 F6 transition of Tb in GaN, the
most energetic luminescence observed from RE ions in GaN. In fact, their
theoretical calculations for Eu, Er and Tm yielded that these all induce an
electrically active level at about 0.2 eV below the conduction band, in the
REGa VN configuration.
Bearing the above arguments in mind, it is fundamental to experimen-
7.1 Sample preparation 207
tally investigate the band-gap properties of RE-implanted GaN. As such,

the focus of this chapter will be on the electrical characterization of such
samples. In particular, the Deep Level Transient Spectroscopy (DLTS)
technique (described in chapter 4) will be employed to investigate the ex-
istence of carrier traps in the band-gap before and after implantation; to
assess whether the introduced implantation structural defects generate elec-
trical defects in the material; if the chemical nature of the implanted species
has an impact on band-gap level formation; if there are RE-related electrical
defects; which of those could be related to the RE 4f electrons excitation?
The results described in this chapter were obtained from measurements
performed during visits to two laboratories abroad, namely, the Labora-
toire d’Etudes et de Recherche sur les Matériaux at the École Nationale
Supérieure D’Ingénieurs de Caen (ENSICAEN), France; and at the De-
partment of Physics of the University of Pretoria in South Africa.
The first results presented in this chapter refer to the measurements
performed in ENSICAEN. In a later section a more systematic study will
be presented on the measurement results obtained at the University of
Pretoria.
7.1 Sample preparation

Before measuring the samples, diodes have to be prepared. Sample prepa-
ration includes chemical cleaning, metallic contact deposition and thermal
treatment to improve the contact resistance.
Chemical cleaning [152] starts by degreasing the samples by boiling
them in tricholorethylene (TCE) followed by boiling in isopropanol and
then rinsing in de-ionized water. In the next step the samples are boiled in
aqua regia and rinsed again in de-ionized water. Finally, the samples are
etched in a solution of HCl:H20 (1:1) for 10 s.
After the cleaning procedure, ohmic and Shottky contacts were de-
posited. The ohmic contact deposition was performed by conventional
electron-beam or thermal evaporation. Firstly a 150 Å Ti layer was de-
posited to lower the resistance of the ohmic contact, by forming a thin TiN
Fig. 7.1: Left: schematic view of ohmic and Schottky contacts deposited on GaN.
Right: picture of Schottky diodes deposited on GaN
layer, as described in ref. [153]. After this layer, Al, Ni and Au layers were
deposited, yielding a Ti(150Å)/Al(2200Å)/Ni(400Å)/Au(500Å) ohmic con-
tact structure. After deposition, the samples were annealed at 500o C for
5 minutes in an argon atmosphere. Thereafter, 2000 Å thick Au Schottky
contacts were resistively evaporated at a rate of 0.3 Å/s on the GaN sur-
face through a metal contact mask containing circular holes of 0.6 mm in
diameter as close as possible to the ohmic contacts in order to minimize the
diode series resistance [152]. Figure 7.1 illustrates the deposited contacts
on GaN.
7.2 DLTS measurements at ENSICAEN

A set of seven GaN samples were implanted with 153 Eu and 166 Er ions
at fluences ranging from 1 × 1014 to 6 × 1014 /cm2 , at 80 keV along both
implantation geometries (random and channeled) and at room temperature.
The 3 × 1014 Er/cm2 samples were annealed at 950o C and then prepared
for DLTS measurements. No annealing was performed on Eu-implanted
samples. Chemical cleaning was performed as described above and contact
deposition was performed employing rf sputtering at room temperature
to obtain Ti(250Å)/Al(2500Å)/Ti(250Å)/Au(1500Å) Ohmic contacts and
6000 Å thick Au Schottky contacts.
Prior to DLTS characterization, current-voltage (I/V ) and capacitance-
voltage (C/V ) measurements were performed to assess the quality of the
7.2 DLTS measurements at ENSICAEN 209
Schottky barrier diodes (SBD) and obtain further information about the
electrical properties of the samples, such as the carrier concentration. The
results of I/V-C/V characterization are important to select which samples
can further be measured by DLTS. In fact, if the diodes on a sample exhibit
elevated values of series resistance and elevated leakage currents, then the
probability of obtaining a reliable DLTS measurement is low, as the value
of the diode capacitance will not sufficiently change as the DLTS excitation
pulse is applied. Such measurements were performed on unimplanted GaN
control samples [118] and the Schottky diodes showed good C/V charac-
teristics and low leakage current densities (≤ 10 mA/cm2 ) under a reverse
bias of 4 V. Figure 7.2 shows the I/V curves of two Schottky diodes on the
unimplanted GaN control sample.
Attending to the fact that the space charge Qsc per unit of area of the
semiconductor and the depletion layer capacitance C per unit of area are
given by [63]
s
kB T
Qsc = qND W = 2q²s ND (Vbi − V − ), (7.1)
q
and s
|∂Qsc| q²S ND ²s
C= = = , (7.2)
∂V 2(Vbi − V − kT /q) W
where q is the electron charge, ND the defect density, W the depletion layer
width as in equation 4.3 defined in section 4.1, Vbi the built-in potential, V
the applied potential, kB T the thermal energy and ²S the semiconductor
dielectric constant, equation 7.2 can be solved to obtain ND , yielding
· ¸
2 1
ND = − . (7.3)
q²S d(1/C 2 )/dV
As such, from the C/V plot, it is possible to deduce the total density of
shallow donors. By measuring the slope of the C/V curves (not shown here)
for the unimplanted sample, a donor concentration of about 5.0×1015 /cm3
was determined.
On the other hand, the Er-implanted and annealed samples showed
very high leakage currents and neither I/V nor C/V characteristics could
Fig. 7.2: Typical forward and reverse current-voltage characteristics for two dif-
ferent Schottky contacts deposited on unimplanted GaN [118]
be recorded. Surprisingly, the Eu as-implanted samples (not annealed)

produced better results [154] (not shown here), although their behavior
was also not satisfactory compared to other published DLTS measurements
reports on heavy ion implanted GaN.
The I/V and C/V behavior of the RE implanted samples can be at-
tributed to the considerable surface disorder after ion implantation, which
is not totally removed even after annealing at 950o C. Furthermore, the
reason why it was not possible to measure the Er-implanted and annealed
samples (whereas measurements on Eu as-implanted was possible) is prob-
ably related to material surface decomposition during annealing at 950o C.
Unrecovered surface disorder and decomposition prevent the fabrication of
proper Ohmic and Schottky contacts on these samples. Consequently, no
DLTS measurements were possible on the Er-implanted samples, and only
the samples implanted at a Eu fluence of 3 × 1014 Eu/cm2 demonstrated
sufficient quality to be measured by DLTS.
Fig. 7.3: DLTS spectra of unimplanted GaN [curve (a)] and 80 keV Eu implanted
GaN to a fluence of 3 × 1014 Eu/cm2 for the random and channeled implantation
geometries [curves (b) and (c)], respectively. All spectra were recorded employing
a repetition rate of 220 s−1 , a filling pulse width of 2 ms, a quiescent reverse bias
Vr of 1 V, and a filling pulse Vp of 1.2 V [155].
The DLTS measurements performed at ENSICAEN were carried out

using a 1MHz Boonton 7200 capacitance meter. The process is computer
driven and allows to sample the diode capacitance at ten different times
(t1 , t2 , ..., t10 ). Therefore, several DLTS spectra (corresponding to several
rate windows) can be obtained in one temperature scan, to obtain the
Arrhenius plot, as described in chapter 4. The temperature scans were
performed in the range of 77 to 400 K employing pulses with a width of 2
ms, quiescent reverse bias Vr of 1 V and a filling pulse Vp of 1.2 V.
Figure 7.3 shows the DLTS spectra of the unimplanted control GaN
sample, and Eu implanted GaN for both implantation geometries - random
and channeled. As seen by curve (a), prior to implantation there are two
major electron levels, namely D1 and D2. Such peaks have been previously
observed by other authors [156]-[159] in as grown MOCVD n-GaN samples.
Concerning the Eu-implanted samples, the spectra of both samples (ran-
dom and channeled implanted) show considerably different features, as com-
pared to the unimplanted control sample. The spectrum region between 250
and 400 K, for the random implanted sample shows two partly overlapping
peaks. The first one, centered at about 340 K coincides with the D2 defect
observed in the unimplanted sample. Interestingly, defect D1 observed at
390 K in the control sample is not present in the spectrum of the random
implanted sample. Instead another defect, labeled Dx, is observed at about
360 K. In the case of the channeled implanted sample, the spectrum char-
acteristics in the same temperature range differ even more from the ones of
the control sample. Neither D1 nor D2 defects are observed for this implan-
tation geometry. Instead, a defect labeled Dy, appearing at 327 K is now
observed. Furthermore, a small intensity negative peak, labeled Dz, is ob-
served at about 370 K. Such negative peak normally indicates the presence
of a hole trap (opposite signal in the spectrum, as discussed in chapter 4).
However, it cannot be excluded that such a peak results from a measure-
ment artifact due to inhomogeneous doping leading to a local distortion of
the band-gap structure. Due to such local bands distortion effect, some
deep levels that would normally be located above the Fermi level, can be
found at energy levels below the Fermi level, appearing thus as hole traps
in the DLTS spectrum. Besides these two features in the DLTS spectrum
of the channeled implanted sample, another one is observed at about 270
K, namely a slight shoulder on the lower temperature side of the Dy peak.
This possibly indicates the presence of another electron trap, identified in
figure 7.3 as Eu1.
It was not possible to obtain the DLTS signatures of defects D1, Dx,
Dy, Dz and Eu1 either due to the low resolution of the signals or due to
overlap with other peaks. As to the D2 defect, its DLTS signature points to
an electron trap located at Ec − 0.67 eV with an apparent electron capture
cross-section σna = 6.6 × 10−14 cm2 . These values are in good agreement
with those determined by Auret et al. for defect “EO5”, reported in ref.
[158] as being similar to the “D2” level measured by Haase et al. [160] in
nitrogen-implanted MOCVD n-GaN and attributed to N-interstitials.
Furthermore, considering now the region of the spectra between 150
and 200 K, a small peak is to be seen in curve (b), centered at about 175
K - Eu2. The implantation geometry has a direct influence on the concen-
tration of this defect: as can be seen by curves (a) and (c) of figure 7.3,
the defect is absent for the case of channeled implantation and unimplanted
samples. As discussed in section 6.4 of chapter 6, there are significant differ-
ences concerning structural lattice damage introduced during implantation
in different geometries. The concentration of lattice defects is consider-
ably reduced by channeled implantation and even for the same level of
disorder, as measured by RBS/C, HRXRD shows a slightly better crystal
structure in the region of implantation (figures 6.15 b) and 6.17 b)), for the
case of channeled implantation. As such, Eu2 seems to be associated with
Fig. 7.4: Arrhenius plot of Eu2 defect measured on the Eu randomly implanted
GaN sample. The DLTS signature is obtained from the slope and y-axis intercep-
tion of linear fit to the experimental data points.
implantation-induced lattice damage. The DLTS signature of this defect

was obtained by measuring its emission rate en at different temperatures,
as described in section 4.2 of chapter 4. Figure 7.4 shows the Arrhenius plot
2 ) versus 1000/T for this defect. The band-gap level associated
of ln(en /Tm m
with Eu2 is located 0.36 eV below the conduction band edge and it has an
apparent electron capture cross-section of σna = 8 × 10−13 cm2 .
It should be noticed that, prior to our report in ref. [155], such a DLTS
signature had not yet been reported in the existing literature concerning
DLTS assessment of electrical defects in particle irradiated GaN. Being
so, it can not be excluded that this defect is Eu related - possibly a Eu-
defect complex, such as EuGa − N, Gai , as described in the introduction of
the current chapter. Such defect complex is consistent with the observation
that Eu2 is absent (or at least in much smaller concentration) for channeled
implantation, which induces much less lattice damage.
7.3 DLTS at the University of Pretoria

7.3.1 Current- and capacitance-voltage measurements
As described in section 7.1, after the chemical cleaning procedure, contact
deposition resulted in the fabrication of several SBD on all samples. The
next step consisted of the electrical characterization of these samples, by
measuring their I/V and C/V characteristics prior to the DLTS measure-
ments. At least three diodes on each sample were measured, in order to
evaluate the homogeneity along each sample. Figure 7.5 shows the C/V
behavior of an unimplanted control GaN sample. From the slope of the
1/C 2 vs. V it is possible to determine that for this sample, the total donor
density is ND ∼ 5×1016 /cm3 . In the case of a 5×1014 Eu/cm2 random im-
planted and annealed sample (not shown here), ND ∼ 2 × 1017 /cm3 . This
increase in the electrical defect density is likely to be related to the higher
structural defect concentration, as observed by RBS/C. Nevertheless, other
factors, such as contact quality and resistivity, might considerably influence
the measured values.
Concerning the SBD I/V behavior, figure 7.6 shows the typical I/V
7.3 DLTS at the University of Pretoria 215
Fig. 7.5: Plot of 1/C 2 as function of the applied voltage for an unimplanted
(reference) GaN sample.
diode curve obtained from an unimplanted GaN control sample. Plotting

the same data in a semi-log scale shows deviations from exponential be-
havior. The I/V characteristic curve of a Schottky diode evidencing series
resistance differs from the ideal diode curve [161] by a factor −I ×RS inside
the exponential argument, yielding
qφB
· q(V −IRS )
¸
∗ 2 −k
I = AD A T e BT e ηkB T
−1 , (7.4)
where AD is the diode area (= πd2 /4 - d is the contact diameter), A∗

is the Richardson constant, φB the Schottky barrier height, T the temper-
ature, kB Boltzmann’s constant, RS the series resistance and η the ideality
factor.
As seen by equation 7.4, the deviation from the ideal I/V behavior
introduced by the series resistance depends on the current I, which depends
on the applied voltage V . Consequently the equation cannot be analytically
solved. However, it is crucial to estimate the SBD series resistance in order
Fig. 7.6: Top: I/V diode curve for unimplanted GaN sample. Bottom: Log(I)/V
plot for the same sample.
Fig. 7.7: Simulation of factors affecting the deviation from linearity (a)) of the
diode characteristic I/V plot [162]: b) - recombinations in the depletion layer; c)
- high carrier injection; and d) - series resistance.
to decide whether or not it can be measured by DLTS, as elevated series

resistances limit the diode’s response to applied pulses and can compromise
the reliability of the DLTS measurement. As a rule-of-thumb diodes with
series resistance higher than 10 kΩ were excluded for DLTS measurement.
The SBD series resistance can be obtained from the I/V plot for each
diode. Several factors can affect the linearity of this curve, as illustrated
on figure 7.7. Plot a) on figure 7.7 shows the ideal diode curve [162]. Plot
b) shows a deviation at the region for lower values of the applied voltage.
In this region the current is dominated by the trap-assisted recombination
in the depletion region. In plot c), the current becomes limited by high
injection effects. High injection occurs in a forward biased p-n diode when
the injected minority carrier density exceeds the doping density. However,
high-injection region rarely occurs, as the series resistance tends to limit
the current first. Finally, plot d) includes the effect of the series resistance
in the deviation to linearity of the I/V curve.
The procedure to obtain the series resistance of the measured diode
([163]) consists of plotting ∆V as a function of the measured current I for
the log(I)/V region where the series resistance contributes to the deviation
from linearity (figure 7.7 d)). Here, ∆V is the difference in voltage between
the measured value and the ideal value at a certain current value (top figure
7.8).
Once the metallic electrodes are placed over the Schottky and ohmic
contacts of a chosen diode, both C/V and I/V measurements are performed
in an automated manner with the help of a computer. As well as the values
of ND and RS , the analysis program also outputs the values of the Schottky
barrier height φB and the ideality factor η. This automated process allows
rapid measurements of the electrical properties of the fabricated diodes,
with I/V − C/V measurement times of the order of a few minutes. I/V
and C/V measurements are then a quick way to check the quality of diodes
before characterizing them by DLTS. Not only a low series resistance is
desirable, but also the diode’s rectifying properties and low leakage current.
For example, the analyzed diode on the control unimplanted sample (figure
7.6) showed rectifying linear behavior for three decades of current and a
value of current at 1 V reverse bias, IR , of about 3.2 × 10−10 A. These
values are less good than the ones reported by Auret et al. in reference
[164], namely linearity over at least seven decades of current and IR < 10−11
A, for resistively deposited Au SBDs.
7.3.2 Deep level transient spectroscopy

Two sets of samples were prepared to be analyzed by DLTS during two
consecutive visits to the University of Pretoria. The first set consisted of
samples implanted at medium-high fluences in the range of 1 × 1014 to
1 × 1015 Eu/cm2 at RT, 70 and 90 o C. All the samples were annealed at
950 o C either in a RTA unit or a conventional annealing furnace for 2 and 30
Fig. 7.8: Top: deviation from ideal diode curve due to the effect of series resistance.
Bottom: plot of ∆V vs. I to obtain the value of the series resistance.
Fig. 7.9: Top: non-homogeneity of the first batch of samples. Bottom: the prob-
lem of lack of homogeneity was improved in the second set of samples.
minutes, respectively. The majority of the SBD fabricated on the samples

from this set showed elevated series resistance (∼ M Ω) and irregular I/V-
C/V behavior. The reason for this appears to be related to the relatively
high dopant fluences employed. These high fluences generate considerably
high concentrations of dislocations and other defects (as seen in section
6.3) and modify the native free carrier concentration possibly leading to
compensation of the material. Also, the fact that the implanted areas
on the samples were not perfectly homogeneous due to beam fluctuations
during implantation, contributed strong variations in results obtained from
different diodes on the same sample.
Figure 7.9 compares the implantation homogeneity between the two
sets of samples, by observing the pattern of color change in the samples
after implantation, an indication of the structural damage as discussed

in the introduction to chapter 6. As can be seen by the pictures of the
second set of samples (bottom of figure 7.9), the problem of homogeneity
has been tackled. These samples have been implanted in a chamber closer to
the implanter avoiding the need of employing extra focusing and sweeping
elements. As a consequence the beam was more stable during implantation
resulting in more homogeneous implanted samples. Also, in an attempt
to obtain better SBD for DLTS measurements, these samples have been
implanted with lower fluences, in the range between 5 × 1012 and 5 × 1014
Eu/cm2 , also at RT. I/V and C/V measurements performed on the second
batch of samples (not shown here) confirm that these samples present better
homogeneity from diode to diode and lower RS and IR , and thus are more
suitable for DLTS measurements, than the ones from the first batch.
Besides Eu-implanted samples, the second set of samples also contained
some Gd and Xe implanted samples. The purpose of the DLTS measure-
ment on such sample is to attempt to assess whether observed deep levels in
the band gap of implanted GaN derive from implantation-induced damage
or if they originate from rare earth isoelectronic traps of the kind described
in references [46] and [55]. This distinction can best be done by implanting
an inert ion of comparable mass, such as Xe (ref. [165]). In the case of Xe,
due to its chemical nature, only ballistic effects are responsible for defect
formation and eventual band-gap levels. Xe-implanted samples will serve
as reference to conclude which band-gap levels are caused by ion implanta-
tion, and which might be RE-specific.
After choosing the best diodes (lowest series resistance and largest ∆C
response to bias changes) on each sample by I/V − C/V measurements,
both sets of samples were characterized with DLTS, employing the lock-in
amplifier method (section 4.2.2). As described in section 4.3, DLTS mea-
surements were performed employing a Stanford Research lock-in amplifier
(model SR830). Unless specifically mentioned, all DLTS signatures (acti-
vation energy, Et and apparent capture cross section, σna ) were determined
using a filling pulse width of tp = 0.2 ms, pulse delay time td = 0.3 ms,
quiescent reverse bias (Vr ) of 2 V, and a filling pulse (Vp ) of 2.2 V. In order
to obtain Et and σna , temperature scans ranging from 50 to 400 K were
performed at several lock-in amplifier frequencies in the range of 1 Hz to 5
KHz.
The next three subsections described the results obtained from the char-
acterization of control unimplanted GaN samples, the first set of samples
and the second set of samples.
Control GaN sample

In order to have a reference for comparison, measurements were performed
on unimplanted GaN samples. Eventual electrical defects observed on these
samples are due to structural defects introduced during growth. Samples
from several wafers were measured. All wafers were grown by MOCVD as
described in section B, under similar growth conditions.
Figure 7.10 shows the DLTS spectra of three as-grown unimplanted
control GaN samples. The spectra show two prominent peaks, which are
common to all samples. The spectrum of the unimplanted sample mea-
sured at ENSICAEN is shown below on figure 7.10, for comparison. The
observed differences between measurements in ENSICAEN and University
of Pretoria are most probably due to the different measurement conditions
and equipment, as the measurements performed at the University of Pre-
toria in samples from three different wafers show the same features.
The DLTS signature of the gap states from the as-grown samples can
be determined by measuring the temperature at which each peak occurs at
several LIA frequencies (lock-in amplifier (LIA) method - section 4.2.2). By
externally fixing the emission rate window while setting the LIA frequency,
each peak reveals a trap that is being emptied at a certain emission rate, at
a particular temperature region. As shown in figure 4.10, each peak tends
to shift to higher temperatures as the LIA frequency is increased, indicating
more rapid decay at higher temperatures. Due to the established relation
between the LIA frequency and the trap emission rate en (equation 4.13,
with en = 1/τ ) and taking into account the expression defining en (equation
4.7 here reproduced for convenience),
Fig. 7.10: Top: DLTS spectra of as-grown (unimplanted) GaN measured on wafers
#473 (a)), #463 (b)) and #459 (c)) from GES-Montpellier. Bottom: DLTS
spectrum of as-grown GaN sample measured at ENSICAEN.
Fig. 7.11: DLTS scans of control sample #473 measured at LIA frequencies of 1,
10, 46 and 220 Hz.
−Et
en = KT 2 σn e kB T , (7.5)
by measuring the temperature position of each trap for each LIA fre-
¡ ¢
quency, one can build the Arrhenius plot of ln Ten2 vs. 1/T . From the
linearized plot, the slope allows obtaining the activation energy Et of the
band gap level (with respect to the conduction band), whilst from its in-
tersection with the y-axis one obtains the capture cross section σn .
Figure 7.11 shows four spectra measured on sample #473 at LIA fre-
quencies of 1, 10, 46 and 220 Hz. In order to have more data points on the
Arrhenius plot, other measurements were performed at 2, 4.6, 22 and 110
Hz (not shown for the sake of clarity). Also, for each LIA frequency two
temperature scans were performed at a rate of 4 K/min, one from high to
low temperature and another back in the direction of high temperatures.
At the end of each upwards scan, another LIA frequency was set, and the
Fig. 7.12: Arrhenius plot for the two levels found in the band gap of control
sample GaN #473.
scans repeated. It was done so in order to take instrument-intrinsic tem-

perature shifts into account. In fact, in general the temperature position
of the same peak differ up to 3 K in upwards and downwards temperature
scans. As a result, the average value obtained from the two scans is taken
to be the peak position for the Arrhenius plot.
Figure 7.12 shows the Arrhenius plots of the two defects found in control
sample #473. The DLTS signatures of the defects in sample #473 are, D3:
EC − Et = 0.28 ± 0.01 eV, σna = 2 × 10−14 cm2 , and D2’: EC − Et =
0.61 ± 0.01 eV, σna = 7 × 10−15 cm2 , for the lower and higher temperature
peaks, respectively.
It should be noticed from figures 7.10 and 7.11 that the peak at higher
temperatures is considerably broader than the peak at lower temperatures.
The broader peak possibly results from the presence of extended defects
that lead to the formation of a band of states in the host band-gap. Such
Fig. 7.13: DLTS spectra on GaN control sample #459 as-grown and annealed at
950 o C for 30 minutes.
peak is present in all of the unimplanted samples, although the DLTS sig-
nature shows some variation between samples: for sample #459 it yields
EC − Et = 0.65 ± 0.01 eV, σna = 6 × 10−14 cm2 , similar values to the ones
of defect D2 measured in the ENSICAEN control sample (EC − Et = 0.67
eV and σna = 6.6 × 10−14 cm2 ); for samples #463 and #473 the signature
of this defect is EC − Et = 0.61 ± 0.01 eV, σna = 7 × 10−15 cm2 (D2’).
All these defects in as-grown GaN are known and have previously been
reported. The D3 defect is quite similar to defect E1 reported by Hacke et
al. [166] and by Haase et al. [160], observed in both metalorganic vapor-
phase epitaxy (MOVPE) and hydride vapor-phase epitaxy as-grown GaN.
Neither report assigns a specific origin to this defect, merely presenting
it as a growth defect. Concerning the higher temperature DLTS peak, it
can be associated with defects E2, D2 and E3, D3 reported by Hacke and
Haase, respectively. Hacke suggests that these defects are related to NGa
anti-sites and Haase attributes the origin of defect D3 to nitrogen intersti-

tials. On the other hand, ab initio molecular dynamics studies reported by
BogusÃlawski et al. [26] indicate that the dominant defect in n-type GaN
is the nitrogen vacancy, depending on the material stoichiometry. Never-
theless these authors suggest that the large number of extended defects
present in even state-of-the-art samples also plays an important role. In
fact, since point defects are mobile and much less stable with increasing
temperature than extensive defects, one would expect that after annealing
at high temperatures (∼900 o C), drastic changes would be observed on any
peak associated to native point defects on a DLTS spectrum. However, as
shown on the spectra of figure 7.13, both peaks (low and high temperature)
remain almost unaltered after annealing at 950 o C. This fact indicates that
indeed those two defects are related to complex stable structural defects and
not to simple point defects.
After characterizing the unimplanted control samples and knowing which
defects are material intrinsic, the attention is now focused on the charac-
terization of the RE ion-implanted samples.
Measurements on the first set of samples

As mentioned in section 7.3.2, the first analyzed batch consists of several
samples implanted with medium-high fluences, in the range of 1 × 1014 to
1 × 1015 Eu/cm2 at room temperature and 70 and 90 o C. Due to the
relatively high implanted fluences, the majority of the SBD showed too
high series resistance (M Ω) to allow DLTS measurements. Furthermore,
as seen on figure 7.9 the implanted area on some of these samples is spa-
tially inhomogeneous. Nevertheless, it was still possible to perform DLTS
measurements in some diodes on each sample.
Starting with the measurements on the samples implanted with the
lowest fluences, 1 × 1014 Eu/cm2 , both random and channeled implanted
at RT, figure 7.14 shows the DLTS spectra measured at a LIA frequency
of 46 Hz, under the pulse conditions previously specified.
Despite the difference in pulse conditions and instrumentation, these
spectra show similarities with the ones measured on samples of the same
Fig. 7.14: DLTS spectra of GaN #225 implanted at RT with nominal fluence of
1 × 1014 Eu/cm2 along the channeled and random implantation direction. Both
samples have been annealed at 950 o C.
GaN wafer (#225) at ENSICAEN (figure 7.3), namely, intense features at

high temperatures and features of much less intensity at the lower temper-
ature region. As in those samples, these spectra reveal differences between
the two implantation geometries. Those differences are better observed by
magnifying the region of lower temperatures in the spectra by a factor 20,
as shown in the inset of figure 7.14. The random implanted sample shows
two small peaks in this region. Both peaks have been measured at differ-
ent LIA frequencies in temperature scans up and downwards, as previously
described. This allowed identifying the defects responsible for those peaks.
The lowest peak is caused by a defect creating a level at 0.181 ± 0.004 eV
below the conduction band, showing an apparent carrier capture cross sec-
tion of about 1 × 10−15 cm2 - defect D4. The second defect on this sample
shows a DLTS signature of E − EC = 0.267 ± 0.002 eV and σna = 4 × 10−15
cm2 .
Concerning the channeled implanted sample, in the same region a defect

with E − EC = 0.249 ± 0.002 eV and σna = 7 × 10−14 cm2 is seen (defect
D5). Neither the energy of the level on the band gap nor the apparent cross
section match the values measured for the defects observed on the random
implanted sample. Furthermore, it is intriguing to observe that the lower
temperature defect as observed in the unimplanted samples appears to have
disappeared in the case of the channeled implanted sample, while it is still
present (in small concentration) in the random implanted sample. In fact,
the defect at E−EC = 0.267±0.002 eV is likely to be the same as the D3 de-
fect observed in all measured control samples. The differences between the
spectra of random and channeled implanted samples must be attributed to
the different implantation geometry, even though no significant differences
have been observed at this low fluence, concerning the characterization of
structural defects by RBS/C (figure 6.14). Concerning the strong suppres-
sion (and disappearance for channeled implantation) of the intrinsic GaN
defect responsible for the peak at the lower temperature region of the spec-
trum, it is possible that interactions between the native defects and incident
ions upon implantation, as well as dynamic annealing effects are responsi-
ble for decreasing the concentration of such native defects. Interestingly,
as seen in figure 7.13, attempting to decrease the concentration of native
defects upon annealing at 950o C was not successful. This fact leads to
conclude that structural modification of native defects during implantation
takes place, resulting in a smaller concentration of the electrical defect in
the low temperature region of the spectrum.
Concerning the temperature region above 200 K, both samples show
similar features, namely a steep increase of the dC/C ratio composed by the
superposition of (at least) two broad peak structures. Due to the spectrum
shape it was only possible to determine the DLTS signature of the peak
centered at 340 K, yielding E − EC = 0.593 ± 0.013 eV and σna = 1 × 10−15
cm2 . Such defect has a similar signature to the one of D2/D2’ defect found
at higher temperatures on the control samples.
It should be further mentioned that, unlike the intrinsic GaN defect
peak in the lower temperature part of the DLTS spectrum, the peak at
Fig. 7.15: DLTS spectrum of 5 × 1014 Eu/cm2 RT channeled implanted GaN.
higher temperature (∼ 250 K) does not decrease in intensity after ion im-
plantation. This is an indication that the intrinsic structural defects as-
sociated to this electrical defect are not considerably modified during ion
implantation.
Figure 7.15 shows the DLTS spectrum measured at 46 Hz of a sample

implanted with a fluence of 5×1014 Eu/cm2 at room temperature along the
c-axis of GaN. The main features in this spectrum are quite similar to the
ones from the 1×1014 Eu/cm2 channeled implanted. In fact on this sample,
there is also one defect causing a peak at around 120 K. The DLTS signature
of this level is E − EC = 0.236 ± 0.004 eV, σna = 1 × 10−13 cm2 showing
that this defect is the same as D5 found in the channeled implanted sample
with 1 × 1014 Eu/cm2 . Interestingly this peak shows a higher intensity for
the 5 × 1014 Eu/cm2 , as compared to the lower fluence implanted sample.
Two factors can be responsible for this increase: on one hand, the higher
implantation fluence can be responsible for the increase of intensity of a

defect that is Eu-related; on the other hand, as seen from RBS/C the
concentration of lattice disorder considerably increases with increasing ion
fluence and consequently could lead to an increase of intensity of a related
electrical defect.
Also, above 200 K similar structure is found on this spectrum, namely
3 small smeared bumps on the slope of dC/C followed by an intense and
broad peak at about 350 K. It was not possible to resolve the first two
structures well enough to determine their DLTS signatures, however the
signature of the third one yielded E − EC = 0.58 ± 0.03 eV, σna = 3 × 10−13
cm2 . It should be noticed that the DLTS signature of this defect, herein
labeled as D6, is not very accurately determined as the previous defects, due
to the spectrum shape, namely a small intensity broad “peak” on a slope
background. The DLTS signature of the broad peak at 340 K is E − EC =
0.593 ± 0.013 eV, σna = 1 × 10−15 cm2 , as also measured in the 1 × 1014
Eu/cm2 channeled implanted sample and unimplanted samples - D2/D2’.
Interestingly, the intensities of these two last broad peaks, as compared to
the other features in the respective spectra, remain approximately the same
for both fluences of implantation (1 and 5 × 1014 Eu/cm2 ). This fact does
not correlate with the increase of lattice damage concentration, as observed
from RBS/C comparing both samples. As such, it is unlikely that these
electrical defects are associated with implantation damage.
Figure 7.16 shows the spectrum measured at 4.6 Hz of the sample ran-
dom implanted with a fluence of 5×1014 Eu/cm2 . This spectrum is consid-
erably different from the previous one. In particular, the presence of a very
intense peak centered at about 130 K in the 4.6 Hz scan that dominates the
structure of the spectrum. Although this peak is quite similar to defect D3
observed in the control samples their DLTS signatures differ quite a lot, in-
dicating that indeed these are two distinct defects: the analysis of this peak
yielded a signature E − EC = 0.231 ± 0.006 eV, σna = 1 × 10−15 cm2 (D7),
whereas for D3 the signature is E − EC = 0.28 ± 0.01 eV, σna = 2 × 10−14
cm2 .
Below this peak, there is a much less intense one at about 110 K (better
Fig. 7.16: DLTS spectrum of 5 × 1014 Eu/cm2 RT random implanted GaN. The
inset illustrates the effect of subtracting a linear background to the region between
200 and 320 K.
pronounced on the spectra recorded at higher LIA frequencies). The DLTS

signature of this defect (D8) is E − EC = 0.204 eV, σna = 1 × 10−14 cm2 .
This defect is similar to D4 measured on the 1 × 1014 Eu/cm2 random
implanted sample, however their signatures are considerably different (D4:
E − EC = 0.181 ± 0.004 eV, σna = 1 × 10−15 cm2 ) indicating that these are
likely to be two different defects. Nevertheless, D8 appears in a region where
the spectrum rapidly changes, as a consequence of the low temperature
(< 100 K). As such, the uncertainty associated to its DLTS signature is
very high.
It should be further mentioned that the linear variation of the baseline
(in general observed for all spectra along the entire temperature range)
is due to the background capacitance of the diode, which intrinsically de-
creases as the sample is cooled down. Temperature inhomogeneities along
the sample due to its size might contribute to further accentuate this effect.
Such effect might contribute to the measurement inaccuracy of DLTS sig-
nature of low intensity peaks, as the background slope has to be taken into
account. As an example, the spectrum region between 170 and 320 K re-
veals that some features are present in this region. By subtracting a linear
background in this region it is possible to distinguish three peaks of low in-
tensity, as shown on the inset of figure 7.16. Due to difficulties in resolving
the first peak at higher LIA frequencies, it was not possible to determine
its signature. Concerning the following peaks, it was possible to determine
their signatures however the uncertainty is quite high (up to 10%). As
such, the signature of the following peaks is E − EC = 0.500 ± 0.026 eV,
σna = 2 × 10−14 cm2 and E − EC = 0.643 ± 0.046 eV, σna = 5 × 10−14 cm2 .
The first signature indicates that this defect is likely to be the same as D6,
previously observed. The signature of the following defect is similar to the
one of D2/D2’ defect. Finally, at about 340 K a peak was observed in the
spectrum, with DLTS signature E −EC = 0.773±0.025 eV, σna = 6×10−14
cm2 (D9). It is likely that D9 is the same as the D1 growth defect as mea-
sured in the ENSICAEN batch, however, as mentioned before, it was not
possible to determine the signature of D1.
Figure 7.17 superimposes the spectra of samples implanted along both
geometries at RT with a fluence of 5 × 1014 Eu/cm2 . As can be seen, above
200 K in the spectra measured at 46 Hz the features in both spectra are very
similar. Even in the lower temperature region of the spectra, it is interesting
to observe the position coincidence of defects D5 and D8. As previously
mentioned, the DLTS signature of D8 could not be accurately determined,
and for this reason (and the fact that their temperature maximum position
is the same) it is likely that these are the same defect. However striking
differences are also observed in the lower temperature region of the spectra,
namely the absence of the 140 K peak on the channeled implanted sample.
Effect of Eu implantation fluence

Interestingly, the 140 K peak is also absent on a channeled implanted sam-
ple with a nominal fluence of 1 × 1015 Eu/cm2 , as can be seen on the
Fig. 7.17: DLTS spectra of 5×1014 Eu/cm2 RT random and channeled implanted
GaN.
spectra in figure 7.18 a). The three spectra show similar structure along
the entire range of temperatures and all show the absence of a peak at
about 140 K. This fact might be an indication that this peak is not related
to implantation damage, as it is also absent on the sample implanted with
a considerably high fluence of europium. RBS/C characterization shows a
progressively strong degradation of the lattice structure with increasing ion
fluence also in the case of channeled implantation. In fact, the backscatter-
ing minimum yield increases from about 3% for the case of 1 × 1014 to 14%
for 5 × 1014 and 53% for 1 × 1015 Eu/cm2 . Moreover, as discussed in chap-
ter 6, at such elevated fluences the degree of structural damage as obtained
from both implantation geometries is quite similar, and still the DLTS peak
is absent in the spectra of all the channeled implanted samples. However,
the flatness of this region on these three spectra as compared to the spec-
tra from random implanted samples might be an indication that certain
Fig. 7.18: Comparison between DLTS spectra of channeled (top) and random
(bottom) implanted samples at fluences of 1, 5 and 10 × 1014 Eu/cm2 .
measurement artifacts are affecting the spectra. The presence of similar

artifacts on channeled implanted samples has already been observed in the
high temperature region of the spectra of samples measured at ENSICAEN
- defect Dz.
Also to be observed from figure 7.18 a) is the change in magnitude of
the peak at about 120 K. This defect appears to be fluence dependent, as
it progressively increases with the implanted Eu fluence. However, it is so
far unclear if this defect is Eu or implantation damage related. In order
to assess the origin of such defect, these results should be compared with
the ones of samples implanted with another ion with similar mass, and
preferentially different chemical nature, for example 132 Xe as discussed in
section 6.9. DLTS results on such samples will be later discussed.
The spectra in figure 7.18 b) were obtained from samples implanted
in the same fluence range but along the random implantation geometry.
Concerning the region below 200 K, as before, the sample implanted with
1 × 1014 Eu/cm2 shows only two small peaks, one centered at 115 and an-
other at about 140 K. The intensity of the first peak considerably increases
as the fluence is increased to 5 × 1014 Eu/cm2 but does not further increase
with increasing fluence. On the other hand, the intensity of the second peak
appears to be strongly dependent on the implanted fluence, even causing
the saturation of the LIA signal as can be seen by the truncated peak on
figure 7.18 b), for the sample implanted with 1 × 1015 Eu/cm2 . Concerning
the origin of such defects, it remains unclear whether they are implanta-
tion damage or Eu related. However, the absence of D7 defect (140 K)
on the channeled implanted samples suggests an implantation geometry
correlation.
Effect of substrate temperature during implantation

The effect of the substrate temperature during implantation was next in-
vestigated. As shown in section 6.5, increasing the substrate temperature
during implantation to only about 90 o C allows to considerably suppress
the implantation related structural damage by enhancing the dynamic an-
nealing process. Figure 7.19 illustrates the effect of rising the substrate
Fig. 7.19: DLTS spectra of 5 × 1014 Eu/cm2 channeled implanted GaN at RT, 70
and 90 o C. After implantation all samples were annealed at 950 o C.
temperature to 70 and 90 o C during the channeled implantation of Eu in

GaN. Once again, similar features are observed for all the spectra. A peak
at lower temperatures is present at all implantation temperatures, however
the DLTS signature of this peak for the 70 and 90 o C implanted samples is
E − EC = 0.203 ± 0.003 eV, σna = 3 × 10−14 cm2 , coinciding with the signa-
ture of defect D8. In the case of the RT implanted sample a slightly different
defect signature has been identified for defect D5 (E − EC = 0.236 ± 0.004
eV, σna = 1 × 10−13 cm2 ). However, once again the D8 peak appears in a
rapid-changing region of the spectrum and therefore measurement artifacts
might contribute to the inaccuracy of the signature measurement. In any
case it can be observed that the intensity of this peak in relation to the
remaining regions of each spectrum, increases with increasing implantation
temperature. This may be related to the structural changes observed by
RBS/C - at 90 o C only the surface damage peak is present, whereas the
EOR damage region is suppressed (figure 6.22 of section 6.5). Moreover,

in the spectrum temperature region between 125 and 175 K of the 90 o C
implanted sample spectrum, a small feature is observed. It was not possi-
ble to determine the signature of this feature however it occurs in the same
region as defect D7 (140 K) on the random implanted samples. Taking into
account the discussion of section 4.5 concerning the effect of the samples’
series resistance on the intensity and signal of DLTS peaks ([72]), it is pos-
sible that the diode series resistance affects the quality factor of the series
circuit composed by that resistance and the capacitor, Q = Rs Cs ω. As
seen, when the value of Q equals 1, a DLTS signal can be canceled out,
and when Q is greater than 1, the signal can even be reversed. Such effect
can be tested by increasing the value of RS , and this can be accomplished
by connecting a resistor in series with the diode. Figure 7.20 illustrates
the effect of increasing the value of a resistor connected in series with a
diode fabricated on the sample implanted at 90 o C along the channeling
geometry at a fluence of 5 × 1014 Eu/cm2 . As can be seen, by changing
the value of RS , not only the amplitude of the feature in this region is can-
celed out, but its sign is eventually reversed. This is an indication that one
cannot definitively exclude the presence of the D7 defect in the channeled
implanted samples.
Concerning the effect of the substrate temperature during random im-

plantation, figure 7.21 shows the DLTS spectra of samples randomly im-
planted with a nominal fluence of 5×1014 Eu/cm2 at RT, 70 and 90 o C. At
70 and 90 o C the first peak on the spectrum is characterized by its DLTS
signature E − EC = 0.188 ± 0.003 eV, σna = 3 × 10−15 cm2 . This defect
is the same as defect D4 in the sample implanted at RT with a fluence of
1 × 1014 Eu/cm2 . D4, D5 and D8 have similar characteristics: appear at
the same region in the spectrum and generate an electron trap at about
200 meV below the CB. It can be speculated that these defects are vari-
ants of the same defect, possibly associated to slightly different structural
defect configurations. Interestingly, similar to what was observed for the
case of channeled implantation, as the implantation temperature increases
(RT → 70o C → 90o C), the amplitude of this peak increases relatively to
Fig. 7.20: Effect of the diode series resistance on the magnitude and signal of
the DLTS spectrum of the sample channeled implanted at 90 o C with 5 × 1014
Eu/cm2 , in the region between 100 and 180 K.
the remaining spectrum features. This indicates that the concentration of

such defects increases with increasing temperature.
With respect to the second peak on the spectrum of the sample im-
planted at 90 o C, while constructing the Arrhenius plot to obtain the de-
fect’s DLTS signature, instead of obtaining a linear slope as usually ob-
tained from all other peaks, two distinct slopes were obtained, depending
on the LIA frequency. This is illustrated on figure 7.22.
Performing linear fits separately to the two sets of data points, one ob-
tains two distinct DLTS signatures: E − EC = 0.253 ± 0.026 eV, σna =
5×10−14 cm2 (same as D3); and E −EC = 0.226±0.003 eV, σna = 1×10−15
cm2 (same as D7). A possible explanation for this effect is that indeed this
peak results from the convolution of two components associated to two dif-
ferent defects originating DLTS signals in this region. Depending on the
LIA frequency employed to probe the diode, one of the components domi-
Fig. 7.21: DLTS spectra of 5 × 1014 Eu/cm2 random implanted GaN at RT, 70
and 90 o C. After implantation all samples were annealed at 950 o C.
nates the buildup of this peak. By changing that frequency, the intensity
of one of the components decreases while the other increases. Further ev-
idence of the dual character of this peak is given on figure 7.23. As can
be seen by the DLTS spectrum region between 80 and 170 K, the peak
centered at 140 K is much broader that the one at 110 K. Also a shoulder
is visible at the higher temperature side of the peak centered at 140 K. A
first approximation gaussian fit (as shown in figure 4.9 of section 4.2.2) to
this region of the spectrum allows comparing the fit quality obtained by
considering one or two components for the 140 K peak. A much better fit
is obtained with two components for this peak revealing that it is likely to
be caused by two distinct electrical defects.
The analysis of this batch of samples revealed several defects creating

levels in the band gap of GaN. At a first sight, differences were observed
Fig. 7.22: Arrhenius plot for the defect causing the peak at 140 K on the DLTS
spectrum of 90 o C random implanted sample.
in spectra of samples implanted along different geometries, and even the

implantation temperature appears to play a role in the formation of such
band gap levels. However, since all the samples were implanted with the
same dopant (Eu), and despite the fact that some defects appear to be
related to the doping fluence, it was not possible to assess whether the levels
induced by those defects are dopant related, or implantation structural
damage related instead. In an attempt to clarify this issue, a new batch
of GaN samples was implanted, not only with 153 Eu but also with 158 Gd -
another RE ion with similar mass, and 132 Xe - an inert ion with comparable
mass. Since RE 3+ ions all have the same electronic structure, they are
expected to generate similar defects in the host material [46, 55]. On the
other hand, any levels found in the band gap of GaN after Xe implantation
will most probably be related to structural damage introduced during the
implantation process.
Fig. 7.23: Gaussian fit of the peak centered at about 140 K on the DLTS spectrum
of 90 o C random implanted sample. Top: one component fit; bottom: two gaussian
component fit.
Measurements on the second set of samples (better spatial

homogeneity and lower implantation fluence range)
As pointed out previously, the majority of the samples from this batch
were implanted with lower ion fluences (5 × 1012 /cm2 to 5 × 1014 /cm2 ).
As mentioned in section 4.5, the doping level of samples might impose
sensitivity limitations. As such, by implanting lower fluences, the level of
structural damage is smaller, reducing the concentration of larger/complex
defects. This allows to detect certain defects that, due to their low con-
centrations, would otherwise not been able to be detected. Furthermore,
less implantation surface damage allows to obtain better SBD, reduce their
series resistance,and improve the measurement result. All these samples
have been implanted at room temperature. Also, as previously mentioned,
extra care was taken concerning the homogeneity of the implanted region.
Figure 7.24 shows the DLTS spectrum of the sample implanted with
a nominal fluence of 5 × 1012 Eu/cm2 along the channeled geometry and
annealed at 950 o C. The spectrum measured at LIAf req. = 46Hz shows ev-
idence of six defects present in the range between 50 and 400 K, although
it was only possible to obtain the DLTS signature of four of them. The
first peak indicates the presence of the defect E − EC = 0.190 ± 0.007 eV,
σna = 2 × 10−15 cm2 . This defect is the same as D4 observed in (random
implanted) samples from the first batch. The second defect observed on
this sample is characterized by E − EC = 0.252 ± 0.004 eV, σna = 2 × 10−15
cm2 . The DLTS signature of this defect defect is very similar to the one
of defect D3 (or D7). It is interesting to observe this second peak on the
channeled implanted sample, as it was not directly observed in samples
implanted along the same geometry with higher fluences of Eu. This is an
indication that due to the lower implantation fluence, the resulting SBD
series resistance RS is smaller and thus, the Q factor, as previously dis-
cussed, is inferior to 1 (Q < 1) and thus there is no canceling-out nor signal
reversion of this peak.
To obtain the DLTS signature of the defects in the range between 200
and 275 K, a linear slope was subtracted to better resolve the features
Fig. 7.24: DLTS spectrum at 46 Hz of the sample channeled implanted with

5 × 1012 Eu/cm2 .
in this region, as shown in the figure inset. This approach yielded two
structures on the 46 Hz spectrum. However, for other LIA frequencies, it
was not possible to clearly resolve the first peak and consequently it was
not possible to identify its signature. Concerning the structure at about
280 K, spectra acquired at higher frequencies (not shown) revealed that
it is possible to decompose this feature into two components and both of
them could be identified. E − EC = 0.43 ± 0.01 eV, σna = 3 × 10−16 cm2 is
associated with the first peak. This defect is likely to be the same as D6,
observed in samples from the first batch. The second peak on the structure
yielded E −EC = 0.661±0.014 eV, σna = 4×10−13 cm2 , a signature similar
to that of defect D2/D2’ attributed to intrinsic GaN defects.
All the results so far discussed refer to implanted and annealed samples.
Indeed as previously mentioned, implantation damage affects the electrical
properties of the SBD as it introduces generation and recombination within
the material band-gap. This will influence the current transport processes
Fig. 7.25: DLTS spectra of 5 × 1012 Eu/cm2 implanted samples along the chan-
neled direction, both as-implanted and after annealing at 950 oC .
and result in non-ideal Schottky behavior. In particular, the material sur-

face (on top of which de diodes are fabricated) might be problematic since
material amorphization starts here already at intermediate fluences. As
such, in an attempt to (partly) recombine the structural damage, the sam-
ples of the first batch were annealed at about 950o C, as previously de-
scribed. However, at the low fluences implanted for this (second) batch
of samples (5 × 1012 Eu/cm2 ) structural damage should not be drastically
high. For this reason an attempt was made to measure the DLTS spectrum
of an as implanted sample. Figure 7.25 shows part of the spectrum of the
as-implanted sample. The spectrum reveals a peak at about 100 K that
has not previously been observed in the already measured samples. This
defect is characterized by E − EC = 0.129 ± 0.006 eV, σna = 4 × 10−17
cm2 (D10). Interestingly this defect is not present on the annealed sample,
indicating that this defect is likely to be associated with structural point
defects (vacancies and interstitials) that are removed upon annealing. Still
neled and random implantation geometries. Both samples have been annealed at
950 o C after implantation.
on the spectrum of the as-implanted sample, a feature is to be seen at

around 120 K. By measuring DLTS spectra at lower and higher frequen-
cies, the DLTS signature of this feature was identified to be the same as
the D4 defect. The fact that this defect is present in both samples (as-
implanted and annealed) indicates that this defect is either dopant related
or temperature-stable structural defect related.
The next step consisted of comparing the influence of the implantation
geometry, for progressively increasing implantation fluence. Figure 7.26
shows the spectra acquired at LIAf req. of 400 Hz of 5 × 1013 Eu/cm2 im-
planted samples along the channeled and random implantation geometries.
Not only the spectrum features of the 5 × 1013 Eu/cm2 channeled im-
planted sample are essentially the same as for the 5 × 1012 Eu/cm2 chan-
neled implanted sample (fig. 7.25) but also the same DLTS peaks are
visible in the spectrum of the 5 × 1013 Eu/cm2 random implanted sam-
ple. The first peak on both spectra can be attributed to the D4 defect
(E − EC = 0.168 ± 0.006 eV, σna = 1 × 10−15 cm2 ) already measured in the
previous batch of samples. The DLTS signature of the next peak, which
dominates the spectra of both samples, is E − EC = 0.267 ± 0.004 eV,
with σna = 9 × 10−15 cm2 . Such signature is close to the one of defect
D3 observed in the low fluence implanted and in the unimplanted samples.
It is interesting to observe such defect again for a low fluence implanted
sample while it was not measured for samples implanted at fluences twice
as high and above, as observed with the samples of the first batch. This
once more seems to reinforce the idea that the implantation damage does
strongly influence the electrical characteristics of the SBD’s.
It was not possible to determine the signature of the defect responsible
for the low intensity feature centered around 220 K, for the channeled im-
planted sample however the DLTS signature of the defect responsible for
the same peak on the spectrum of the random implanted sample resulted
in E − EC = 0.340 ± 0.013 eV, σna = 3 × 10−15 cm2 . This defect will be
labeled as D11, even though its energy is close to the one of Eu2 defect
measured in the random implanted sample at ENSICAEN. Concerning the
remaining features in both spectra, it was not possible to determine their
DLTS signatures.
Figure 7.27 compares the DLTS spectra of 1 × 1014 Eu/cm2 implanted

samples, along the two implantation directions. The striking characteristic
of this figure is the absence (once again) of the second peak for the case
of channeled implantation, confirming the effect of increasing implantation
structural damage on the SBD series resistance, as the implantation fluence
increases. Essentially four defects could be identified on the spectrum of this
sample. Measurements on the first peak resulted on the DLTS signature
E − EC = 0.219 ± 0.017 eV, σna = 1 × 10−13 cm2 . This signature is close to
the one of D8, observed in the spectra of channeled implanted samples from
the first batch. In the region where the D3 and D7 defects appear in the
neled and random implantation geometries. Both samples have been annealed at
950 o C after implantation.
case of low fluence channeled implanted and random implanted samples, a

flat signal is now visible. However at the signal edge where the D8 peak
starts a small signal below the baseline is observed. Once more, this seems
to indicate the presence of a hole trap. As previously discussed such signal
might be a measurement artifact that influences the DLTS signals in this
region. Indeed it is possible that such artifact influences the DLTS signature
of the D8 defect and that in fact D8 is the same defect as D4 measured
in the random implanted sample. For this last sample the D3 defect is
present, as also observed on the sample of the first batch implanted with
the same fluence. In the temperature region above 175 K both spectra
show the same structure. The previously measured D11 defect appears to
be present also in these samples for both implantation geometries. Also,
both samples show the presence of defect D6 and another defect with DLTS
signature E −EC = 0.63±0.03 eV, σna = 2×10−13 cm2 (D2?). It should be

mentioned that the measurement uncertainty of these low intensity peaks is
considerably higher than for the case of well defined peaks in the spectrum.
Returning to the spectrum of the channeled implanted sample, as can
be seen in the spectra measured at 200 Hz, a small feature arises at around
165 K, slightly above the region where a second peak is suppressed, as dis-
cussed before. This is to be seen inside the dashed-line circle. By measuring
the DLTS spectrum of this sample at frequencies above 200 Hz, this feature
turns into a well defined and intense peak in the spectrum, as can be seen on
the spectra on top of figure 7.28 where DLTS spectra in the region between
90 and 210 K were measured at 200, 400 and 1000 Hz. The appearance of
this extra peak in this region of the spectra, seems to confirm the hypothe-
sis that the peak observed in the 90 o C 5 × 1014 Eu/cm2 random implanted
peak, as shown in figure 7.23 could indeed have two components. By mea-
suring the temperature position of this new peak (labeled D12) at higher
frequencies its DLTS signature was observed to be E − EC = 0.369 ± 0.043
eV, σna = 5 × 10−12 cm2 , as shown in the Arrhenius plot of the defects
measured on the 1 × 1014 Eu/cm2 channeled implanted sample - bottom of
figure 7.28. However, it must be mentioned that the high values of energy
and capture cross section are an indication of the poor measurement quality
of this defect’s signature.
So far, apart from the D7 (or/and D3) defect peak that is absent in the
spectra of channeled implanted samples with Eu fluences above 5 × 1013
Eu/cm2 , the spectra of samples implanted at both geometries are quite
similar. As such, it is at this moment not possible to attribute the presence
of any trap levels to either implantation structural damage or the RE-ions.
In order to clarify the origin of the measured defects on Eu-implanted
GaN, measurements were performed on samples implanted with the same
conditions but employing Xe and Gd. Figure 7.29 shows the DLTS spec-
trum measured at 46 Hz of a 1 × 1014 Xe/cm2 random implanted sam-
ple, measured with similar pulse conditions as the measurements on Eu-
implanted samples (fig. 7.27). Similar features are seen on this spectrum,
namely two peaks in the lower temperature region of the spectrum, and
Fig. 7.28: Top: DLTS spectra at 80, 200, 400 and 1000 Hz of the 1 × 1014 Eu/cm2
channeled implanted sample. Bottom: Arrhenius plots of the defects observed on
the 1 × 1014 Eu/cm2 channeled implanted sample.
Fig. 7.29: DLTS spectrum of 1 × 1014 Xe/cm2 implanted sample. Similarly to

the Eu-implanted samples, after implantation this sample has been annealed at
950o C.
two structures on a increasing linear slope background followed by the ap-

pearance of a strong intensity peak (only partly shown on the spectrum at
46 Hz). The DLTS signature of the defect associated to the first peak on
the spectrum is E − EC = 0.195 ± 0.006 eV, σna = 1 × 10−15 cm2 . This
defect has a similar signature to the D4 defect in Eu samples implanted at
both geometries at several fluences. As such, it can be concluded that this
is an implantation-damage-related defect. Similar defects were observed
by S. F. Song et al. in Er and Pr-implanted GaN films and attributed to
the RE-ions rather than to implantation induced defects [167]. However,
given the evidence here presented that such defect is also observed in the
case of Xe-implantation, it must be concluded that this defect is caused by
implantation damage.
Concerning the second peak in the spectrum, its DLTS signature was
measured to be E − EC = 0.334 ± 0.018 eV, σna = 6 × 10−13 cm2 . This

signature is remarkably similar to the signatures of defects Eu2 and D12.
Observing this defect on the Xe-implanted sample eliminates the ambiguity
of such defect, providing evidence that also this defect is implantation-
damage related.
Considering the temperature region comprised between 200 and 300 K,
the subtraction of a linear increasing background and amplification of that
region (inset in figure 7.29) reveals the presence of two features, in contrast
with the three features present in the Eu-implanted spectra as shown, for
example in figure 7.24 at the same frequency (LIAf req. = 46 Hz). Due to
resolution difficulties, it was not possible to obtain the DLTS signature
of the first feature in this region. The DLTS signature of the following
feature was measured as E − EC = 0.554 ± 0.018 eV, σna = 1 × 10−13
cm2 . This signature is similar to the one of D6 observed in the majority of
Eu implanted samples independently of the implantation geometry. It can
be concluded that this defect is likely to be another implantation damage-
related defect. Following these two defects, an intense peak is observed in
the higher temperature region of the spectrum (well defined for lower LIA
frequencies). Its DLTS signature was found to be E − EC = 0.723 ± 0.056
eV, σna = 1×10−14 cm2 . This signature is close to the one of defect D1/D9
observed in several other measured samples, including unimplanted GaN.
This is an indication that this defect is a native GaN defect.
Figure 7.30 shows the DLTS spectrum (LIAf req. = 46 Hz) of a Xe-
implanted sample with a fluence about 50 times higher (5 × 1015 Xe/cm2 )
than the previous. Despite the difference in fluence, the spectrum char-
acteristics remained similar to the ones of figure 7.29, namely two peaks
below 200 K, and two peaks between 200 and 300 K. However, the inten-
sity ratios between the two first peaks have now been reversed, indicating
that the concentration ratio of these two electrical defects changes with
increasing dopant fluence. As Xe is an inert species, the electrical defects
on Xe-doped GaN are exclusively due to structural defects introduced in
the lattice upon Xe implantation. As such the observed amplitude reversal
of the first two peaks is likely to be associated with a change in relative
Fig. 7.30: DLTS spectrum of 5 × 1015 Xe/cm2 implanted sample.
concentration of two different sorts of structural defects with increasing ion

fluence, for example, increasing relative concentration (and eventually vol-
ume) of amorphous clusters at the expense of reducing the concentration
of simple point defects. Once again, the DLTS signatures of these defects
match (within uncertainty) the ones of D4 and Eu2/D12, respectively. The
same is valid for the fourth feature in the spectrum, centered around 270
K (D6). Concerning the feature centered about 220 K, once more it was
not possible to determine its signature. Such defect is also observed at the
same position in the case of certain Eu-implanted samples, where it has
been possible to measure its signature - defect D11. Assuming that these
are the same, such defect is another implantation damage related defect.
Figure 7.31 shows the Arrhenius plots of the three defects identified on
the 5 × 1015 Xe/cm2 implanted sample.
With respect to the defects on Gd-implanted GaN, figure 7.32 shows

the 200 Hz DLTS spectrum of the 5 × 1014 /cm2 channeled implanted
Fig. 7.31: Arrhenius plots of the defects identified in sample 5 × 1015 Xe/cm2
implanted sample.
and annealed Gd:GaN sample. Similarly to the Eu-implanted samples, five

peaks were observed on this sample. Also, as in the case of higher fluences
(> 5×1013 /cm2 ) Eu-implanted samples, the second (very intense) peak has
been suppressed. Interestingly, as also observed in the spectrum of the Eu
1 × 1014 /cm2 channeled implanted sample of figure 7.27, a small negative
peak is seen at the upper temperature side of the D8 defect peak. Such
negative peak (possibly due to the presence of a hole trap, as previously
discussed) will affect the shape (and DLTS signature determination) of
peaks in this region. This is probably the case for D8 and the peak at
about 160 K in the spectrum. The DLTS signature of such defect was
measured to be E − EC = 0.472 ± 0.021 eV, σna = 9 × 10−9 cm2 . The very
high values of the energy and capture cross section for this defect indicates
that indeed such signature values are unlikely to be correct. Nevertheless,
due to the similarities with the defect found in the Eu channeled implanted
Fig. 7.32: DLTS spectrum of 5 × 1014 Gd/cm2 channeled implanted sample. This
sample has been annealed at 950o C after implantation.
sample (figure 7.27) this defect will also be labeled as D12.

The third measured defect is associated to the low intensity feature
centered about 220 K in the spectrum. Its signature was measured to be
E − EC = 0.376 ± 0.007 eV, σna = 1 × 10−14 cm2 . These values are close to
the ones of defect D11 measured in the Eu channeled and random implanted
samples and possibly also in the Xe-implanted samples, as discussed above.
As such, this electrical defect is probably related to implantation damage
as it is observed for all the implanted species. The next defect on the Gd
DLTS spectrum occurs at about 280 K, and its broad shape suggests that
more than one components might be present, however it was not possible
to clearly distinguish them. Finally, the signature of the last peak on the
spectrum matches the one of defect D9: E − EC = 0.787 ± 0.048 eV,
σna = 1 × 10−12 cm2 .
Figure 7.33 compares the DLTS spectra of Gd and Eu channeled im-
Fig. 7.33: DLTS spectra of 5 × 1014 Gd/cm2 and 1 × 1014 Eu/cm2 both channeled
implanted and annealed at 950o C.
planted GaN. Apart from intensity differences of the peaks in the high-
temperature range, both spectra are quite similar. Furthermore, the DLTS
signatures of the defects found in both samples are in good agreement
(within the values or uncertainty). This fact is not surprising considering
that all RE ions have the same electrical behavior and approximately the
same size. Concerning the observed differences, these are probably asso-
ciated with the higher implantation fluence for the Gd sample (5 times
higher).
7.4 DLTS results summary and conclusions

The DLTS results here presented allow to clarify and even answer some of
the questions initially posed within the scope of this thesis. As such, it
has been observed that certain band-gap levels are already present in the
unimplanted host. Such native defects are believed to be introduced during
7.4 DLTS results summary and conclusions 257
material growth. D1/D9, D2 and D3 compose this group of defects. Some

of these defects are also observed in implanted samples.
It has further been observed that Eu implantation in GaN further in-
troduces additional levels in the host band-gap. Moreover, differences have
been observed between the spectra of channeled and random implanted
samples indicating that the implantation geometry does play a role on the
formation of electrical defects. Indeed, the absence of the D3(D7) defect
peak in the case of channeled implanted samples (at fluences higher that
5 × 1013 Eu and Gd/cm2 ), while present for the random implantation ge-
ometry provides evidence for that assumption. Nevertheless, the fact that
the D3(D7) defect has been observed also for channeled implanted sam-
ples at lower fluences indicates that possibly other effects (artifacts, hole
traps, SBD series resistance) prevent the observation of those defects at
higher implantation fluences. Other observed defects are also influenced
by the fluence: the intensities of the D5 and D8 defect peaks have visibly
increased with increasing fluence.
Similarly to what has been observed in chapter 6 for the case of struc-
tural lattice damage, the implantation temperature also affects the electri-
cal defects in Eu-implanted GaN. In particular, defects D4, D5 and D8 (for
both implantation geometries) seem to be the most influenced. This fact
and the facts that these three defects appear (mutually exclusively) in the
same region of the spectrum and generate levels at about 0.2 eV below the
CB can be combined to speculate that such defects are possibly caused by
the same structural defect.
The Eu-implanted GaN DLTS data interpretation has demonstrated
to be a complicated task. Not only the spectra are composed of multiple
peaks on a temperature-dependent background, but also peak superposition
occurs. By scanning at several LIA frequencies it was sometimes possible
to separate superposed peaks. The analysis of the second peak at the lower
temperature side of the spectra is such an example. A careful analysis of
the behavior of this peak has indicated that it is likely to be composed by
the superposition of the peaks of defects D3 and D7. Defect D3 has been
identified as a GaN growth defect, whereas D7 seems to be present only in
Table 7.1: List of electrical defects measured by DLTS on the Eu, Gd and Xe
implanted GaN samples. ∗ D6 defect is associated to a weak intensity peak in a
region where peak superposition occurs; ¦ D7 appear in a region where D3 is also
often present; † the signal of D8 is affected by the presence of a hole trap.
Defect E [eV] σna [cm2 ] samples origin

D1 − − unimplanted growth
D2 0.67 7 × 10−14 unimpl./implant. growth
D3 0.28 2 × 10−14 unimpl.(implant.?) growth
D4 0.18 1 × 10−15 implant. (Eu, Xe) implant. damage
D5 0.25 7 × 10−14 implanted implant. damage
D6∗ 0.58 3 × 10−13 implant. (Eu, Xe, Gd?) implant. damage
D7¦ 0.23 1 × 10−15 Eu (Gd?) but not Xe possibly RE-related
D8† 0.21 1 × 10−14 implant. (Eu, Gd, Xe(?)) implant. damage
D9(D1) 0.75 6 × 10−14 unimpl./implant. growth
D10 0.13 4 × 10−17 implant. no anneal implant. damage
D11 0.35 5 × 10−15 possibly all implant. implant. damage
D12/Eu2 0.36 5 × 10−13 Eu/Xe implanted implant. damage
Eu and Gd implanted samples - and not in Xe:GaN. Besides the defects

so far mentioned, other defects have been observed in the majority of the
measured samples, including Xe-implanted. This fact indicates that such
defects can be attributed to implantation induced structural defects. This
is the case of D4(D5 and D8), D6, D11 and D12/Eu2.
Finally, the comparison of DLTS spectra of two RE-ions (Eu and Gd)
implanted in GaN indicates that, as expected, both dopants introduce the
same defects in the host band-gap.
The DLTS results presented in this chapter are summarized in table 7.1,
where the defects have been ordered in twelve groups, according to their
DLTS signatures.
It can be concluded that the majority of the electrical defects measured
by DLTS in Eu-implanted GaN are caused by implantation structural de-
fects, since they were observed in the Eu and Xe implanted samples. Some
of the defects were already present in unimplanted samples, indicating the
presence of electrical defects even before implantation. Such defects are at-
7.4 DLTS results summary and conclusions 259
tributed to structural defects introduced during material growth. Finally,

concerning the effect of RE-ions in the band-gap of GaN, unfortunately it
has not been possible to provide clear evidences of the existence RE-related
levels in the band-gap. However, as mentioned above, defect D7 has only
been observed in Eu-implanted samples, and not in the case of Xe. The
DLTS signature of this defect indicates that it generates an electron trap at
about 0.23 eV below the conduction band of GaN. This value is strikingly
close to the one predicted by the Density Functional Theory calculations
for the REGa − VN defect in Eu, Er and Tm-doped GaN: 0.2 V below the
conduction band. As such, it is possible that such defects is involved in the
excitation mechanism of the RE 4f electrons resulting in the typical sharp
luminescence of RE:GaN. However, due to the fact that D7 appears in the
same region of the spectrum as D3 (a growth defect), no clear conclusion
could be taken and further work is necessary to investigate such defects.
Chapter 8
Conclusions
This work consisted of a study of defects introduced in GaN during Eu-

doping by ion implantation. For that purpose Eu has been implanted in
GaN thin films at several experimental conditions (fluence, implantation
direction and substrate temperature).
After implantation, the structural properties of the doped films have
been investigated by Rutherford backscattering and channeling spectrom-
etry. Structural characterization was often complemented with other tech-
niques, namely X-ray diffraction, and optical studies performed by photo
and cathodoluminescence. To complete the study the doped films were
electrically characterized by Deep Level Transient Spectroscopy in order to
investigate the effect of structural defects and the RE-dopant on the GaN
band-gap.
RBS/C indicates that Eu-implantation introduces disorder in the GaN
lattice. This disorder is distributed in depth through the crystal into two
regions, one closer to the surface and another coinciding with the implanted
ion projected range. The surface damage region is characterized by an
elevated degree of structural disorder. The second damage region (EOR),
is characterized by a considerable degree of lattice disorder without however
reaching the levels of the surface damaged region.
Even though the integrated lattice disorder level (surface+EOR) in-
creases sigmoidally with increasing dopant fluence, the disorder level of
261
262 Conclusions
both regions increases at different paces with increasing Eu fluence. While

the surface disorder region reaches amorphous levels already at intermedi-
ate fluences, the disorder intensity at the EOR region appears to saturate
at intermediate-high fluence values. An efficient dynamic annealing mecha-
nism assures that point-defects formed during implantation are immediately
recombined (or diffuse away from this region) resulting in the saturation
behavior at the EOR region. As the amorphization of the surface region
proceeds in the direction of the bulk, the EOR disorder level proceeds until
it too reaches the amorphous level and meets the surface, now amorphous,
region.
RBS/C further revealed that aligning the Eu-beam with the c-axis of
GaN allows to considerably reduce the degree of structural damage. Along
that direction the Eu beam is channeled through the crystal and the indi-
vidual ions experience far less collisions with host atoms and thereby create
considerably less structural damage along their path inside the crystal, until
they finally come to a stop.
In any case, room temperature implantation in both geometries gen-
erates substantial levels of structural defects that hinder the luminescence
output of the doped material: no RE-related luminescence is observed after
implantation. Annealing at temperatures of the order of 1000o C is required
to - only partly - recover the structural damage, and observe RE-related
luminescence. After annealing, RE-luminescence is stronger for the chan-
neled implantation geometry as this geometry generates a higher number
of optically active centers, as compared to random implantation that in-
troduces a considerably higher level of luminescence quenching structural
defects.
Complete lattice damage recovery requires extreme annealing condi-
tions that are not practical, requiring special equipment and conditions in
order to avoid material degradation. Indeed at only about 1000o C surface
degradation of GaN starts to occur under conventional ambient. Hence,
it is necessary to prevent the formation of damage rather than attempt to
recover it afterwards. We have observed that implantation damage can be
strongly reduced by elevating the substrate temperature during implanta-
263
tion. Results here presented indicate that the level of structural disorder
measured by RBS/C on a film implanted at 180o C is inferior to the level
observed in a RT implanted and subsequently annealed film at 950o C. More-
over, considering that at 950o c only partial recovery of lattice damage is
achieved and that higher annealing temperatures will lead to surface de-
composition, it can be concluded that implanting at substrate temperatures
of about 200o C is a more efficient method of introducing higher dopant flu-
ences while keeping structural damage at reduced levels.
Surprisingly, even without post-implantation annealing, weak RE-related
luminescence is observed for samples implanted at temperatures as low as
50o C. Interestingly, it has been observed that this “as-implanted” lumi-
nescence is considerably stronger for the case of random implantation, for
which RBS/C shows a much higher level of structural damage as compared
to channeled implantation. A plausible explanation for this fact is that not
all structural defects quench the RE-luminescence. Considering that some
defects will be involved in the RE excitation mechanism and that more de-
fects of both kinds (quenching and optically active) are introduced by ran-
dom implantation, higher “as-implanted” luminescence is expected for that
geometry. Further, if defects involved in luminescence form temperature
stable complexes with the implanted RE-ions and luminescence quenching
defects are recombined upon annealing, stronger luminescence is expected
from channeled implanted and annealed samples. Indeed defect recombi-
nation upon annealing is more efficient for channeled implanted samples.
As a result, after annealing more quenching defects are still present for the
random implanted samples and therefore luminescence is weaker for this
implantation geometry.
Besides GaN, AlInN films have also been implanted with Eu. PL and
CL studies have shown that the host composition strongly affects the lumi-
nescence output of the RE-implanted films. On one hand, much stronger
RE-related luminescence was observed for AlInN, as compared to GaN. On
the other hand, the measured luminescence lines are considerably broader
and slightly red-shifted as compared to RE:GaN.
The influence of the mass of the implanted ion on the formation of
264 Conclusions
damage was investigated by comparing the effects of implanting 132 Xe,

153 Eu, 158 Gd and 166 Er. Results indicate that little difference is found in
the level of structural damage caused by the implantation of the three RE

ions, but that, as expected, the level of damage caused by Xe implantation
is considerably inferior.
Deep Level Transient Spectroscopy was used to investigate the role of
structural defects on the formation of electrical defects in the band-gap of
RE-implanted GaN. Characterization of as-grown control GaN films has
revealed the presence of two major defects generating two electron trap
levels in the band-gap of GaN. Measurements on Eu-implanted films shows
that several band-gap levels are introduced during implantation. To tenta-
tively determine whether some of those defects are Eu-related or implanta-
tion damage related, two other ion species have been implanted in similar
films, namely Gd (another RE-ion) and Xe (an inert ion). By compar-
ing the DLTS signatures of defects measured in all samples it was possible
to conclude that the majority of the defects are most probably caused by
structural defects introduced during implantation, as they were observed
in all samples, including Xe-implanted. Not all defects were present in all
samples. One particular defect was only observed in Eu-implanted sam-
ples (and not for Xe). Such defect introduces a level in the band-gap at
about 230 meV below the conduction band of GaN. This value is close to
the RENiBEl calculated value from Density Functional Theory studies for
the REGa − VN defect in Eu, Er and Tm-doped GaN: 200 meV below the
conduction band. Such defect is thought to be involved in the excitation
mechanism of the RE 4f electrons resulting in the typical sharp lumines-
cence of RE:GaN.
Even though the work here presented provides experimental evidence
for the theoretical predictions, further investigation is necessary in order to
confirm that such defect is involved in the the RE:GaN luminescence mech-
anism. In order to clearly conclude whether such band-gap level is indeed
RE-related a conceptually simple experiment can be executed, namely the
implantation of a RE radioisotope. Such isotope should have a suitable
half-life (∼ hours) in order to allow implantation and subsequent DLTS
265
characterization. By acquiring DLTS spectra at different time intervals

during the RE parent-isotope half-life, it should be possible to conclude
whether certain defects are indeed RE-related. If the amplitude (concen-
tration) of a certain defect decreases with time and if the decay constant
matches that of the isotope half-life then clear evidence is given of the origin
of that particular defect.
To gain further insight on the role of structural defects on the RE-
luminescence, a more extensive study is required. All samples implanted at
several implantation conditions should be characterized by all of the tech-
niques employed in this work: RBS/C, HRXRD, PL, CL and (radioactive)
DLTS. By gathering information from all these techniques, and by inves-
tigating the same parameters on similar samples implanted with other RE
ions, such as Tm and Er, it should be possible to further clarify the mecha-
nism responsible for the energy transfer between host and RE-ions leading
to the typical luminescence. Such knowledge would allow to optimize the
doping conditions in order to maximize light emission of fabricated devices.
266 Conclusions
Appendix A
Rutherford Backscattering
and Channeling
Spectrometry (RBS/C)
Rutherford backscattering spectrometry is a powerful non-destructive an-

alytical technique employed in the characterization of materials, allowing
to quantitatively assess the elemental composition and structure of the an-
alyzed material. This technique finds its roots on the famous experiment
of Ernest Rutherford who in 1911 first explained Geiger and Marsden’s ex-
perimental results for alpha particle scattering from a very thin gold foil in
a backward direction by using the Coulomb electrostatic force between the
positively charged nucleus and the positively charged alpha particle. This
allowed Rutherford to propose the first correct description of the atom as
a tiny positive nucleus surrounded by negatively charged electrons (essen-
tially the Bohr atom).
The popularity and success of this technique for almost 100 years is to be
attribute to its elegance: simply with base on the principles of conservation
of energy and momentum, elemental composition, depth distribution and
concentrations can be accurately determined in a non destructive fashion.
It is the purpose of this appendix to briefly describe the technique. A
more thorough description can be found in references [94] and [95].
267
268Rutherford Backscattering and Channeling Spectrometry (RBS/C)
Fig. A.1: Top: schematic illustration of the RBS principle from the point of
view of a classical two-particle collision event [94]. Bottom: Experimental setup
employed in RBS [96].
A.1 Basic concepts
The basic RBS experimental setup is shown in figure A.1. The He ion beam
is produced in a RF ion source and accelerated through a tandem Van de
Graaff accelerator to MeV energies. A well collimated beam is obtained
by focusing and steering the beam through collimating elements along the
beam line. The beam reaches then the target mounted on a high preci-
sion 3-axis goniometer. The backscattered fraction of the 4 He+ beam is
then collected in surface barrier detectors (bottom of figure A.1), generat-
ing there electrical signals proportional to the energy they kept after being
scattered. The signal e shaped and amplified in pre-amplifiers and ampli-
fiers and is then passed to a multichannel analyzer (MCA). To each channel
A.2 Physical background 269
in the MCA, a certain value of energy will be associated in a way that each
time a particle with an energy Ex is detected, a unit is incremented in the
channel Cx corresponding to that energy value. This allows displaying in
a spectroscopic fashion, the yield of backscattered ions as function of the
detected He ion energy.
A.2 Physical background

RBS allows to obtain answers to the questions “Which elements are present
in a material?”, “How are they distributed through the material?” and
“How much of each element is present?”. Simply be measuring the energy
of the detected backscattered ions, it is possible to identify the element
at which the He ion was backscattered in the target, and the depth in
the target at which the collision took place. Also, from the amount of
backscattered ions with a particular energy it is possible to quantify the
concentration of an element in the target material.
Three physical concepts at the base of RBS allow answering the above
questions, namely the kinematic factor K, the stopping cross section ² and
the scattering cross section σ(θ).
A.2.1 Kinematic factor K

Considering the schematic illustration of a two-particle elastic collision as
shown on top of figure A.1, simply by applying the energy and linear mo-
mentum conservation principles, it is possible to determine the amount of
energy transferred during the collision. E0 is the initial energy of the in-
coming particle of mass M1 , M2 the mass of the target particle at rest,
and E1 and E2 the energies after the collision of the incident and target
particles, respectively. For an elastic collision, the conservation laws of en-
ergy and linear momentum allow to write the ratio between E1 and E0 , for
M1 < M2 as being
q 2
M 2 − M 2 sin2 θ + M cos θ
E1  2 1 1
 .
K= = (A.1)
E0 M1 + M2
Fig. A.2: Enegy loss of an incoming ion that is scattered at depth t on a target
atom [104]. ∆Ein is the energy loss due to electronic stopping during the inwards
path, ∆Es is the energy loss due to the scattering event, and ∆Eout is the energy
loss due to electronic stopping during the outwards path. The final energy is then
E1 = E0 − ∆Ein − ∆Es − ∆Eout .
This ratio is called the kinematic factor K. During a backscattering experi-

ment, the mass M1 of the incident projectile, as well as the detection angle
θ, are fixed. As such, K is only dependent on M2 , the target mass. By
measuring E1 at the detector, M2 can be obtained from equation A.1 and
the target mass identified. K is a monotonously increasing function with
decreasing angle and increasing mass. As such, to resolve between two ele-
ments in the target with close masses, that is to obtain the largest variation
in K for the two masses, the scattering angle θ should be the largest possi-
ble, ideally θ = 180o . In practice, the detector is placed at 170o , as can be
seen for the annular detector at the bottom of figure A.1.
A.2.2 Stopping cross section ²
Collisions between the incoming He ions and target atoms will not only
take place at the surface of the material, but also inside the target at a
A.2 Physical background 271
depth t. In this last situation, the energy loss due to collisions with atomic
electrons in the target, as discussed in section 5.1, has to be considered.
Figure A.2 schematically represents the energy loss steps of an incident He
ions that is scattered at a depth t inside the target. The energy loss occurs
via three steps:
1. Electronic energy loss during the inwards path due to inelastic scat-
tering with electrons. As referred in section 5.1, the energy loss per
length unit dE
dx is a function of the target material and the energy of
the incoming He ions.
2. Nuclear energy loss due to the scattering with a target atom. It is

described by the kinematic factor K.
3. Electronic energy loss along the outwards path.
With these three factors accounted, the energy loss can be related to
the depth at which the backscattering event occurred, and energy can be
converted to a depth scale, as illustrated in figure A.3. As such, the total
energy loss ∆E is related to the depth t, as
∆E = [S] × t. (A.2)
∆E is then the energy difference between a scattering event at the sur-

face and scattering at a depth t inside the target. [S] is the backscattering
energy loss factor, given by
¯ ¯
K dE ¯¯ 1 dE ¯¯
[S] = in + . (A.3)
cos θ1 dx ¯ cos θ2 dx ¯out
As seen by this expression, in order to increase the depth resolution in
a RBS spectrum, the path length of the He ions along both the incoming
and outgoing trajectories should be increased. This can be accomplished
by tilting the sample (increasing θ1 ) or by placing the detector (θ2 ) at a
glancing angle.
Fig. A.3: Energy and target depth scale relation [97].
A.2.3 Scattering cross section σ(θ)
Finally, the scattering cross section σ(θ) gives the probability that a particle
is scattered into a solid angle Ω of a detector placed at an angle θ, as
illustrated in figure A.4.
The amount of backscattered particles that fall inside the solid angle Ω
of the detector is given by
Y = σ(θ)ΩQNs (A.4)
being Q the total number of incident particles in the beam, and Ns

the number of target atoms per cm2 . For RBS, in the regime of M1 ¡M2 ,
the scattering cross section can be approximated by the Rutherford cross
section
A.3 RBS/Channeling 273
Fig. A.4: Backscattering of particles on the target and detection within the de-
tector solid angle dΩ.
µ ¶2
Z1 Z2 e2 1
σ(θ) = . (A.5)
4E sin4 ( 2θ )
From this equation one concludes that σ(θ) ∼ Z22 , being Z2 the atomic
number of the target atom. The scattering probability of an incoming He
ion on a heavy ion is much higher than for a lighter atom. As such, on
a RBS spectrum of an LH compound, where L is a light and H a heavy
element, the signal from H will be much stronger than the one of L.
A.3 RBS/Channeling
As seen on section 5.3, the incidence angle of the incoming ions with re-
spect to a major crystal direction can strongly change the outcome of ion
implantation. The same is valid for an RBS experiment. By aligning the
beam with a crystal axis, the backscattering yield is dramatically reduced
as compared to the outcome of a random orientation of the beam with re-
spect to the crystal. Figure A.5 illustrates two possible orientations for the
Fig. A.5: Top: random and c-axis aligned (channeled) directions for an hexagonal
crystalline structure [94]. Bottom: random and c-axis aligned RBS spectra of
unimplanted GaN.
incoming beam with the target crystal.

As explained in section 5.3, the decrease in the backscattering yield is

due to the channeling effect - the ions penetrate in the open regions between
the rows or planes of atoms and are gently steered by the potential caused
by the periodically displayed lattice atoms. The theoretical description
of this phenomenon was presented in 1965 by Lindhard [93]. Lindhard
established that there are three essential conditions to be met, in order to
observe the channeling of incoming ions in a crystal, namely,
1. Transparency - there must exist an open channel between the rows of

atoms;
2. Steering - there must be a force present, steering the particles towards

the center of the channel;
3. Stability - the channeled ion must not come too close to the atomic
rows, otherwise dechanneling will occur.
As a consequence of this formalism, in order for an ion to remain chan-

neled it must approach the rows of atoms constituting the walls of the
channel, at an angle inferior to the, so called, critical angle for channeling
ψC . Depending on the mass and energy of the incoming ions, the charac-
teristic angles for the high energy low mass regime ψ1 and for low energy
high mass regime ψ2 are given by
r
2Z1 Z2 e2
ψ1 = , (A.6)
Ed
and
s
Ca
ψ2 = √ ψ1 , (A.7)
d 2
being Z1 and Z2 the atomic numbers of the particle and the target atom,
respectively, e the electron charge, E the particle energy, d the interatomic
distance along the row of atoms, a the Thomas-Fermi screening radius
0.8853a
a= q 1 0 1, (A.8)
2/3
Z12 + Z22
√
a0 is the Bohr radius (0.529Å) and C = 3 is an integration constant.
Both expressions for the critical channeling angle do not take into ac-
count the effect of thermal vibrations of the lattice atoms. For the case
of low mass high energy, this effect can be included by writing the critical
angle as
v  
u Ã √ !2
u
ψ1 u 3a
L
ψC (ρ) = √ tln  + 1, (A.9)
2 ρ
where ρ is the two-dimensional thermal vibration amplitude, which can be

calculated from the one-dimensional vibration amplitude < ux >,
ρ2 = 2 < u2x > . (A.10)
< ux > can be obtained from the Debye model as described, for example
in reference [98].
Concerning the high mass low energy regime, typically employed in ion
implantation, the tendency has always been to avoid the channeling effect
by tilting the sample. To our knowledge, no detailed study exists on the
effect of the substrate temperature on the critical angle, for this regime.
Also, experimentally such study would face difficulties, since the heavier
ions do not backscatter at the target, as in the case of RBS. Furthermore,
the formalism developed by Lindhard does not take the effect of tempera-
ture, in this regime, into consideration.
Since the critical angle A.6 derived from Lindhard’s formalism usually
overestimates the experimentally obtained value by about 20%, Barrett [99]
proposed a refinement for the regime of low mass high energy ions, based
on results obtained from Monte-Carlo simulations. Barrett’s critical angle
is given by
ψ B = 0.8FRS (ξ)ψ1 , (A.11)
where ξ is the normalized distance of closest approach

Fig. A.6: Plot of FRS as function of ξ as proposed by Barrett in reference [99].
ρ
ξ = 0.85 . (A.12)
a
The value of FRS (ξ) is generally obtained graphically from the plot in
figure A.6.
Appendix B
High Resolution X-ray

Diffraction (HRXRD)
Due to their wavelike character, X-ray photons with wavelength in the

range of 0.5 to 5 Å are often employed to study the crystalline structure of
solids, as their wavelength is of the same order of interatomic distances in
the material. When a beam of X-rays impinges on a crystal, the photons
are scattered in all directions by the atoms in the crystal, however in some
particular directions the scattered photons interfere constructively giving
rise to diffraction patterns. W. L. Bragg presented an explanation to this
diffraction phenomenon. Considering the crystal to be composed of several
equidistant atomic planes, when the X-rays impinge on such planes under an
angle θ with respect to the surface normal, the conditions for constructive
interference between two of such rays, diffracted at two different planes are,
that both rays leave the sample under the same angle and that the path
difference between the two diffracted X-rays is an multiple integer of the
X-rays wavelength. This situation is illustrated in figure B.1.
Those two conditions can be summarized in the Bragg law, as follows
2d sin(θ) = nλ, (B.1)
being d the distance between two adjacent crystalline atomic planes, λ

the wavelength of the X-rays, n a positive integer number representing the
279
280 High Resolution X-ray Diffraction (HRXRD)
Fig. B.1: Diffraction of the X-ray beam at the atomic planes in the crystal [100].
order of the diffraction and θ the angle between the perpendicular to the
atomic plane and the incident beam direction.
Being λ a known constant during an X-ray diffraction measurement,
and measuring the angle θ at which the diffraction is maximal, applying
the law of Bragg (eq. B.1) allows obtaining the value of the interplanar
spacing d.
By performing angular scans and obtaining diffraction peaks along dif-
ferent geometries, it is possible to obtain information on the crystalline
structure, lattice parameters and strain, among others. In this work, mainly
the planes parallel to the sample surface were investigated. Occasionally
planes tilted with respect to the surface, were also studied in order to ob-
tain further structural information. For such studies, θ − 2θ scans were
performed. During such scan, the movements of the sample holder and the
X-ray detector are coupled in such a way that the angle θ between the in-
cident beam and the sample surface always equals the beam exiting angle.
281
Fig. B.2: Source, sample and detector configuration during a θ − 2θ scan [101].
This situation is illustrated on figure B.2.

The value of the angular position θ at which the maximum of diffraction
occurs can be replaced in equation B.1 to obtain the value of d. When the
incident beam first passes through a set of monochromating crystals, in
order to only allow a certain value of wavelength x-rays to pass to the
sample, and the exit diffracted beam passes through a set of slits cutting
the scattered beam, one speaks of high resolution X-ray diffraction.
282 High Resolution X-ray Diffraction (HRXRD)
Nederlandstalige
samenvatting
Inleiding
Gallium nitride (GaN) en gerelateerde halfgeleiders spelen het laatste de-

cennium een belangrijke rol in verschillende doorbraken in de elektronica en
opto-elektronica. Sinds de ontwikkeling van de eerste op GaN-gebaseerde
blauwe, violette en ultraviolette LED’s (Light Emitting Diodes) door Naka-
mura in het begin van de jaren ’90, hebben deze materialen steeds meer
wereldwijde aandacht gekregen. Zelfs in de nieuwe generatie optische op-
slagmedia, zoals de Blu-ray Disc en de HD-DVD, wordt gebruik gemaakt
van lasers die op GaN gebaseerd zijn.
Het succes van GaN is voornamelijk te danken aan zijn fysische eigen-
schappen. Door zijn zeer hoge weerstand tegen stralingsschade, zijn ther-
mische stabiliteit en zijn brede directe bandkloof is GaN (en gerelateerde
halfgeleiders) een zeer gepast gastmateriaal voor optische doperingsele-
menten. Wegens hun scherpe emissielijnen van het ultraviolet tot het infra-
rood gedeelte van het spectrum, zijn zeldzame aardmetalen (ZA) een goed
voorbeeld van zulke doperingselementen. Door GaN met europium (Eu),
erbium (Er) en thulium (Tm) te doperen is het mogelijk om respectievelijk
rood, groen en blauw licht uit te zenden.
Een van de meest gebruikte methoden om doperingselementen in een
gastrooster in te brengen, is ionenimplantatie. Deze methode maakt het
mogelijk om het gastmateriaal te doperen met isotopische zuiverheid en
283
284 Nederlandstalige samenvatting
zelfs voorbij de oplosbaarheidslimiet. Hiernaast biedt deze methode de mo-

gelijkheid om doperingspatronen te vormen en dit alles gebeurt met een
nauwkeurige controle over de geı̈mplanteerde dosis. Ondanks deze belan-
grijke voordelen, heeft ionenimplantatie een groot nadeel: door botsingen
tussen de invallende doperingselementen en de atomen uit het gastrooster,
zal er schadevorming zijn aan het kristalrooster. Enerzijds zal deze schade
ervoor zorgen dat Auger-processen bevorderd worden, hetgeen resulteert in
een verhindering van de lichtemissie van de ZA-ionen in GaN. Anderzijds is
uit theoretische studies gebleken dat bepaalde soorten van roosterdefecten
betrokken zijn in het energie-overdrachtsmechanisme tussen het gastmate-
riaal en het ZA-ion. Complexen van zulke defecten en ZA-elementen zouden
elektronentoestanden in de bandkloof van het gastmateriaal genereren die
bemiddelaars zijn in het excitatiemechanisme van de interne elektronische
structuur van de ZA-ionen, hetgeen de typische lichtemissie veroorzaakt.
Het is dus belangrijk om meer inzicht te krijgen in de rol van de ver-
schillende implantatieparameters op het schadevormingsmechanisme en hoe
structurele defecten de optische en elektrische eigenschappen van het gast-
materiaal beı̈nvloeden.
Structurele karakterisatie van de Eu-geı̈mplanteerde

GaN
Voor dit werk zijn GaN-monsters geı̈mplanteerd met 153 Eu waarbij verschil-
lende implantatieparameters werden gevarieerd, zoals de geı̈mplanteerde
dosis, de invalshoek ten opzichte van de h0001i-as (c-as) van het GaN-
rooster en de substraattemperatuur tijdens de implantatie.
Om de invloed van de implantatieparameters op de roosterschade te
bepalen, zijn de geı̈mplanteerde monsters met Rutherfordterugverstrooiings-
en kanalisatie-spectrometrie (RTS/K) bestudeerd. De structurele karakter-
isatie werd meermaals met hoge-resolutie X-stralen diffractie aangevuld.
Verder zijn er bepaalde specifiek gekozen en relevante monsters onder-
zocht met behulp van foto- en kathodeluminescentie aan de Universiteit
van Strathclyde (V.K.)
285
Implantatieschade
De resultaten van de strukturele karakterisatie met behulp van RTS/K to-

nen aan dat er twee schaderegio’s aanwezig zijn na implantatie: een eerste
regio aan het oppervlak en een tweede regio op een bepaalde diepte in het
gastrooster, daar waar de Eu-ionen het meeste van hun energie verliezen
in botsingen met gastatomen en bijgevolg tot stilstand komen. Door die
botsingen worden verschillende gastatomen uit hun oorspronkelijke roost-
erposities verplaatst. Deze atomen zullen op hun beurt ook andere gas-
tatomen verplaatsen en dit alles resulteert in de zogenaamde botsingscas-
cades. X-stralen diffractie toont aan dat de geı̈nduceerde implantatieschade
zorgt voor een lokale uitzetting van het kristalrooster langsheen de h0001i-
as.
Geı̈mplanteerde Eu-dosis
De verandering van de geı̈nduceerde roosterschade ten gevolge van een ver-

hoogde Eu-implantatiedosis volgt een sigmoı̈daal verband. Na implantaties
met een lage dosis (≤ 3 × 1014 Eu/cm2 ) is de defectconcentratie relatief
klein en voornamelijk aanwezig aan het oppervlak, terwijl dieper in het
monster geen meetbare schade aanwezig is.
Bij hogere implantatiedosissen ( 3 × 1014 − 1 × 1015 Eu/cm2 ) worden
steeds meer defecten gevormd, hetgeen gepaard gaat met een verhoging van
de complexiteit van de defecten. Behalve de schade aan het oppervlak zijn
er nu ook veel defecten aanwezig dieper in het monster waar de Eu-ionen
tot stilstand komen. Bij deze dosissen wordt het oppervlak geamorfiseerd,
terwijl de defectconcentratie dieper in het monster satureert bij een waarde
lager dan de amorfisatiedrempel. Dit saturatiegedrag is te wijten aan de
hoge efficiëntie van het dynamische herstelproces in GaN: een groot deel van
de gegenereerde defecten zijn mobiel en zullen bijgevolg diffunderen, recom-
bineren en annihileren. De defecten die niet annihileren zullen zogenaamde
defectgroepen of clusters vormen. Wanneer de implantatiedosis toeneemt,
zal de efficiëntie van het dynamische herstelproces verlagen. De amorfisatie
van het materiaal begint aan het oppervlak en zal zich van daaruit verder
doorzetten dieper in het monster.

Na implantatie op kamertemperatuur is er, onafhankelijk van de Eu-
dosis, geen Eu-gerelateerde luminescentie opgemeten. Na uitgloeiing van
het monster op 1000o C gedurende 30 minuten, zien we een (gedeeltelijk)
herstel van de kristallijne roosterkwaliteit en een gedeeltelijke verwijdering
van de defecten die de luminescentie tegenwerken (of quenchen), hetgeen
resulteert in de observatie van Eu-gerelateerde luminescentie. Een volledig
herstel van de de structurele roosterschade treedt pas op bij uitgloeitemper-
aturen rond 1600o C, hetgeen sterk bemoeilijkt wordt door de decompositie
van het GaN-oppervlak bij temperaturen rond 1000o C.
Invalshoek
Implantatie in de richting van de c-as van het GaN-rooster zorgt voor een
drastische verlaging van de dichtheid aan structurele defecten. De roost-
erpotentiaal zorgt ervoor dat de ionen die in de richting van een kristalas
in zogenaamde ’kanalen’ invallen (kanalisatie), doorheen het rooster geleid
zullen worden, hetgeen resulteert in een verminderde hoeveelheid botsingen
met de roosteratomen. In vergelijking met de niet-gekanaliseerde implan-
tatie, kan op deze manier het gastmateriaal met een hogere dosis gedopeerd
worden, terwijl de defectconcentratie toch laag gehouden wordt. Bij een
even grote defectconcentratie, opgemeten met RTS/K, werd zelfs een ver-
minderde roosterexpansie (met hoge-resolutie X-stralen diffractie opgeme-
ten) waargenomen na gekanaliseerde implantatie.
Na uitgloeiing werd ook een verhoogde luminescentie intensiteit opgeme-
ten bij gekanaliseerde implantatie ten opzichte van de niet-gekanaliseerde
implantatie (waarbij geı̈mplanteerd wordt onder een invalshoek van 10o ten
opzichte van de c-as).
De gekanaliseerde implantatie genereert een groter aantal optisch ac-
tieve centra ten opzichte van niet-gekanaliseerde implantatie. Deze laatste
genereert een verhoogde hoeveelheid structurele defecten die voor lumines-
centie quenching zorgen.
287
Substraattemperatuur tijdens implantatie

Implantatie bij een verhoogde substraattemperatuur zorgt voor een ver-
hoogde mobiliteit van de gegenereerde defecten en leidt dus tot een ver-
hoogde kans op recombinatie.
In vergelijking met implantaties op kamertemperatuur, wordt de de-
fectdichtheid na een implantatie op 200o C gereduceerd met een factor vijf.
Door de hogere substraattemperatuur wordt het dynamisch herstelproces
sterk bevorderd. Op deze manier kan een veel hogere doperingsdichtheid
verkregen worden, terwijl de defectdichtheid laag gehouden wordt. Een ex-
tra voordeel is de verhoogde luminescentie: in vergelijking met implantaties
op kamertemperatuur, wordt bij een verhoogde substraattemperatuur een
veel sterkere ZA-gerelateerde luminescentie waargenomen.
Implantaties bij hogere substraattemperatuur zorgen voor minder de-
fecten die de luminescentie tegenwerken. Implantatie bij 50o C resulteert
reeds in een verminderde luminescentie opgemeten zonder uitgloeiing. Deze
zogenaamde “as-implanted”-luminescentie is een grootte-orde sterker bij
niet-gekanaliseerde ten opzichte van gekanaliseerde implantatie. Mogelijk
is dit te wijten aan de hogere concentratie aan structurele defecten (op-
tisch actief + luminescentie quenching) die geı̈nduceerd worden bij niet-
gekanaliseerde implantatie. Bij hogere substraattemperaturen kunnen meer
defecten recombineren tijdens de implantatie, hoewel het ook mogelijk is
dat de verhoogde defectmobiliteit resulteert in een grotere hoeveelheid sta-
biele en optisch actieve ZA-defect complexen. Hieruit volgt dat er minder
defecten zullen zijn die de luminescentie tegenwerken, samen met een ver-
hoogd aantal optisch actieve centra.
In tegenstelling tot de “as implanted”-luminescentie, is de luminicentie
van de uitgegloeide kamertemperatuur gekanaliseerd geı̈mplanteerde mon-
sters sterker. Een mogelijke uitleg hiervoor is dat desondanks de kleinere
hoeveelheid gecreëerde defecten (optisch actief + luminescentie quench-
ing), zullen er na uitgloeiing bij gekanaliseerde implantatie veel minder
defecten overblijven die de luminescentie tegenwerken, ten opzichte van
niet-gekanaliseerde implantatie. Hierdoor is de luminescentie bij monsters
die gekanaliseerd geı̈mplanteerd zijn bij kamertemperatuur, gevolgd door
een uitgloeiing, het sterkst.
Andere implantatieparameters
De optische eigenschappen van de nitridelagen na Eu-implantatie hangen

sterk af van de samenstelling van de lagen. Luminescentie afkomstig van
Eu-atomen in een Al0.82 In0.18 N -laag is veel intenser dan in een GaN-laag,
terwijl de emissielijnen echter breder worden en roodverschoven zijn. Hi-
ernaast is er zogenaamde “as implanted”-luminescentie geobserveerd bij
op kamertemperatuur geı̈mplanteerde AlInN-lagen, hetgeen wijst op een
kleinere hoeveelheid defecten die de luminescentie tegenwerken in vergeli-
jking met GaN-lagen geı̈mplanteerd onder dezelfde omstandigheden. Dit is
hoogstwaarschijnlijk te wijten aan de hoge Al-concentratie, aangezien deze
atomen voor kleinere terugverstrooiingscascades zorgen en ook de defectre-
combinatie sterk bevorderen tijdens de implantatie.
Uit de bestudering van de invloed van de massa op de gecreëerde schade
is het duidelijk geworden dat de lichtere Xe-ionen voor een lagere defect-
concentratie zorgen dan de zwaarde ZA-ionen. Dit volgt uit het feit dat de
lichtere atomen (bij gelijke implantatie-energieën) minder defecten zullen
creëren, waardoor minder defecten gerecombineerd moeten worden tijdens
de implantatie en uiteindelijk zal de kristallijne kwaliteit van het rooster
na implantatie beter zijn.
Elektrische karakterisatie van de Eu-geı̈mplanteerde

GaN
Het is algemeen geweten dat de luminescentie afkomstig van ZA-ionen van
gedopeerde nitridelagen sterk afhangt van de structurele defecten in de
laag. Nochtans is er weinig informatie te vinden in de literatuur over
de invloed van ZA-implantaties op de elektronische bandstructuur van
GaN. Hoe wordt de bandkloof beı̈nvloed door de structurele defecten?
Worden er elektrische defecten gecreëerd met energieniveaus in de band-
kloof? Zijn er ZA-gerelateerde energieniveaus in de bandkloof? Volgens
289
theoretische berekeningen zullen enkele van deze energieniveaus belangrijk

zijn in het energie-transfermechanisme tussen het gastmateriaal en de ZA-
doperingsatomen die voor de specifieke ZA-luminescentie zorgt. Daarom
is het belangrijk de invloed van de structurele defecten (en doperingsele-
menten) op de elektrische eigenschappen van het gedopeerde materiaal te
begrijpen.
Om de elektrische eigenschappen van GaN-lagen na Eu-implantatie te
bestuderen, hebben we gebruik gemaakt van Deep Level Transient Spec-
troscopy (DLTS). Om na te gaan of de geı̈nduceerde defecten na de Eu-
implantatie schadegerelateerd ofwel Eu-gerelateerd zijn, zijn er ook Xe-
implantaties uitgevoerd in de GaN-lagen.
DLTS resultaten
Ook in niet-geı̈mplanteerde GaN-lagen zijn er elektrische defecten opgeme-
ten, dewelke meestal te wijten zijn aan structurele defecten gevormd tij-
dens het groeiproces van de lagen. Na de Eu-implantatie zijn verschillende
nieuwe elektrische defecten opgemeten, waarvan de meerderheid te wijten
zijn aan implantatie-geı̈nduceerde structurele defecten, aangezien deze ook
aanwezig zijn na Xe-implantatie. Eén specifiek energieniveau werd enkel
geobserveerd in de Eu-geı̈mplanteerde monsters. Uit de DLTS-metingen is
gebleken dat dit defect een elektronenval is met een energieniveau van 0.23
eV onder de conductieband van GaN. Deze waarde ligt in de buurt van het
theoretisch (Density Function Theory) berekende ZAGa − VN defect in Eu,
Er en Tm-gedopeerde GaN-lagen: 0.2 eV onder de conductieband.
Besluit
In dit werk zijn de structurele en elektrische defecten in GaN bestudeerd
na ionenimplantatie met Eu-ionen.
Eu-implantatie creëert een aanzienlijke hoeveelheid schade in het GaN-
rooster, hetgeen resulteert in de verhindering van de Eu-gerelateerde lumi-
nescentie. De concentratie aan structurele defecten hangt sterk af van de
verschillende implantatieparameters. De meest cruciale parameters zijn de
geı̈mplanteerde dosis, de implantatierichting ten opzichte van de c-as van

het GaN-rooster en de substraattemperatuur. Meer bepaald is er aange-
toond dat implantaties bij 100 − 200o C minder roosterschade toebrengen in
vergelijking met een implantatie op kamertemperatuur, gevolgd door een
uitgloeiing op 950o C.
Na uitgloeiing is de Eu-gerelateerde luminescentie intenser voor mon-
sters die op hogere temperatuur geı̈mplanteerd zijn. In tegenstelling tot
de kamertemperatuur “as implanted”-monsters, er is Eu-gerelateerde lu-
minescentie opgemeten van hogere substraattemperatuur “as-implanted”
lagen. Verder, deze zogenaamde “as-implanted”-luminescentie is sterker
bij niet-gekanaliseerde implantatie waardoor een grotere hoeveelheid struc-
turele defecten is genereert. Hieruit blijkt dat niet alle defecten voor een
verminderde luminescentie zullen zorgen en dat sommige zelfs een rol in
het luminescentie excitatiemechanisme kunnen spelen.
De elektrische karakterisatie van de geı̈mplanteerde GaN-lagen heeft
tot de observatie van verschillende geı̈nduceerde bandkloof energieniveaus
geleid. Terwijl de meerderheid van deze defecten gerelateerd zijn aan struc-
turele defecten ten gevolge van de ionenimplantatie, er is één specifiek Eu-
gerelateerd defect geobserveerd. Dit defect creëert een energieniveau in
de bandkloof van ongeveer 230 meV onder de GaN-conductieband. Deze
waarde ligt dicht bij de theoretisch berekende waarde voor het ZAGa − VN
defect in Eu, Er and Tm-gedopeerd GaN: 200 meV onder de conductieband.
Waarschijnlijk heeft dit defect te maken met het excitatiemechanisme van
de ZA 4f -elektronen die zorgen voor de typische scherpe luminescentie in
ZA-gedopeerd GaN.
Bibliography
[1] P. N. Favennec, H. L’Haridon, M. Salvi, D. Moutonnete, Y. Le

Guillou, Luminescence of Erbium implanted in various semi-
conductors: IV, III-V and II-VI materials, Elec. Lett. 25, 11
(1989), 718-719
[2] S. J. Pearton, J. C. Zolper, R. J. Shul, F. Ren, GaN: Processing,

defects, and devices, J. Appl. Phys., 86, 1 (1999), 1-78
[3] M. Morkoç, S. Strite, G. B. Gao, M. E. Lin, B. Sverdlov, and M.

Burns, Large-band-gap SiC, III-nitride, and II-VI ZnSe-based
semiconductor device technologies, J. Appl. Phys., 76, 3 (1994),
1363-1398
[4] J. Wu, W. Walukiewicz, K . Yu, J. W. Ager III, E E. Haller, Hai

Lu, William J. Schaff, Yoshiki Saito, Yasushi Nanishi, Unusual
properties of the fundamental band gap of InN, Appl. Phys.
Lett. 80, 21 (2002) 3967-3969
[5] V. Yu. Davydov, A. A. Klochikhin, V. V. Emtsev, S. V. Ivanov,

V. V. Vekshin, F. Bechstedt, J. Furthmüller, H. Harima, A. V.
Mudryi, A. Hashimoto, A. Yamamoto, J. Aderhold, J. Graul,
and E. E. Haller, Band Gap of InN and In-Rich Inx Ga1−x N
alloys (0.36¡x¡1), Phys. Stat. Sol. (b) 230, 2, (2002) R4-R6
[6] W. C. Johnson, J. B. Parsons, and M. C. Crew, Nitrogen com-

pounds of gallium, J. Phys. Chem. 36 (1932), 2651-2654
291
[7] H. P. Maruska and J. J. Tietjen, The preparation and properties
of vapor-deposited single-crystalline GaN, Appl. Phys. Lett. 15
(1969), 327
[8] H. Amano, N. Sawaki, I. Akasaki, and Y. Toyoda, Metalorganic

vapor phase epitaxial growth of a high quality GaN film using
an AlN buffer layer, Appl. Phys. Lett. 48 (1986), 353-355
[9] B. Monemar, Basic III-V nitride research - past, present and

future, J. Crys. Growth 189/190 (1998), 1-7
[10] H. Amano, M. Kito, K. Hiramatsu, I. Akasaki, p-type conduc-

tion in Mg-doped GaN treated with low-energy electron beam ir-
radiation(LEEBI), Jpn. J. Appl. Phys. 28 (1989), L2112-L2114
[11] S. Nakamura, M. Senoh, and T. Mukai, Jpn. J. Appl. Phys.,

Part 2 30 (1991), L1708
[12] S. Nakamura, N. Iwasa, M. Senoh, and T. Mukai, Jpn. J. Appl.

Phys., Part 2 31 (1992), L1258
[13] M. Shur, M. Khan, GaN/AlGaN Heterostructure devices: pho-

todetectors and field-effect transistors, MRS Bul. (Feb. 1997),
44-50
[14] S. Nakamura, M. Senoh, S. Nagahama, N. Iwasa, T. Yamada, T.

Matsushita, H. Hiyoku, and Y. Sugimoto, InGaN-based multi-
quantum-well-structure laser diodes, Jpn. J. Appl. Phys. 35
(1996), L74
[15] http://www.sei.co.jp/news e/press/02/02/16.html
[16] “The last of the format wars? Blu-Ray vs HD-DVD drives blue
lasers”, Elsevier III-Vs Review 19, Feb. 2006, 9
[17] http://compoundsemiconductor.net/articles/magazine/12/7/5/1
[18] O. Briot, RENiBEl Training: Growth of Nitrides and rare

earths doped nitrides, RENiBEl meeting Lisbon, March 2004
292
[19] J. H. Edgar, S. Strite, I. Akasaki, H. Amano, C. Wetzel, Proper-
ties, processing and applications of Gallium Nitride and Related
Semiconductors, INSPEC, 1999
[20] J. H. Edgar, Properties of group III nitrides, INSPEC, 1994
[21] J. W. Orton and C. T. Foxon, Group III nitride semiconductors

for short wavelength light-emitting devices, Rep. Prog. Phys. 61
(1998),1
[22] S. Strite and H. Morkoç, GaN, AlN and InN: a review, J. Vac.
Sci. Technol. B 10 (1992), 1237
[23] http://www.lightemittingdiodes.org/
[24] http://www.ioffe.rssi.ru/SVA/NSM/Semicond/
[25] M. Suzuki, T. Uenoyama, and A. Yanase, First-principles cal-

culations of effective-mass parameters of AlN and GaN, Phys.
Rev. B 52 (1995), 8132 - 8139
[26] P. BogusÃlawski, E. L. Briggs and J. Bernholc, Native defects in

gallium nitride, Phys. Rev. B 51, 23 (1995), 17 255-17 258
[27] C.C. Van de Walle and J. Neugebauer, First-principles calcula-

tions for defects and impurities: Applications to III-nitrides, J.
Appl. Phys. 95 (2004), 3851
[28] K. A. Gschneidner and L. R. Eyring, Handbook on the physics

and chemistry of rare earths, vol. 1 - Metals, North-Holland
Publishing Company, 1978
[29] J. M. Zavada, D. Zhang, Luminescence properties of erbium in

III-V compound semiconductors, Sol. Stat. Elec. 38, 7 (1995),
1285-1293
[30] A. J. Steckl and J. M. Zavada, Optoelectronic properties and

applications of rare-earth-doped GaN, Mate. Res. Bulletin 24
(1999), 33
293
[31] A. J. Steckl, J. C. Heikenfeld, D. S. Lee, M. J. Garter, C. C.
Baker, Y. Wang and R. Jones, Rare-earth-doped GaN: growth,
properties, and fabrication of electroluminescent devices, IEEE
J. Sel. Top. Quantum Electron. 8 (2002), 749
[32] A. J. Steckl, J. Heikenfeld, D. S. Lee, M. Garter, Multiple color

capability from rare earth-doped gallium nitride, Mat. Sci. Eng.
B81 (2001), 97-101
[33] J. H. Park, A. J. Steckl, Demonstration of a visible laser on sil-

icon using Eu-doped GaN thin films, J. Appl. Phys. 98, 056108
(2005) 1-3
[34] S. W. Choi, S. Emura, S. Kimura, M. S. Kim, Y. K. Zhou, N.

Teraguchi, A. Suzuki, A. Yanase, H. Asahi, Emission spectra
from AlN and GaN doped with rare earth elements, J. Alloys
and Compounds 408-412, (2006) 717-720
[35] P. Clauws, Halfgeleiders - Syllabus bij de cursus Halfgeleiders,

Academiejaar 2000-2001 (2000)
[36] K. Krane, Modern Physics, John Wiley and Sons, second edi-
tion, 1996
[37] N. W. Ashcroft, N. D. Mermin,Solid State Physics, Saunders

College 1976
[38] http : //people.seas.harvard.edu/ ∼

jones/ap216/lectures/ls2 /ls2u 7/ls2u nit7 .html
[39] C. Kittel, Introduction to Solid State Physics, John Wiley and

Sons, 1996
[40] http://en.wikibooks.org/wiki/Semiconductors/
[41] S. O. Kucheyev, J. S. Williams, S. J. Pearton, Ion implantation

into GaN, Mat. Sci. Eng. 33 (2001), 51-107
294
[42] A. Shikanai,H. Fukahori, Y. Kawakami, K. Hazu, T. Sota, T.
Mitani, T. Mukai, and Sg. Fujita, Optical properties of Si-, Ge-,
and Sn-doped GaN, Phys. Stat. Sol. (b) 235 (2003), 26
[43] D. G. Kent, M. E. Overberg,Co-implantation of Be+O and

Mg+O into GaN, J. Appl. Phys. 90 (2001), 3750
[44] U. Gerstmann, A. T. Blumenau, H. Overhof, Transition metal

defects in group-III nitrides: An ab initio calculation of hyper-
fine interactions and optical transitions, Phys. Rev. B 63 (2001)
75204
[45] J. A. Chisholm, P. D. Bristowe, The electrical activity of GaN

doped with transition metal impurities, Modelling Simul. Mater.
Sci. Eng. 9 (2001) 249-258
[46] J. -S. Filhol, R. Jones, M. J. Shaw, P. R. Briddon, Structure

and electrical activity of rare-earth dopants in GaN, Appl. Phys.
Lett., 84, 15 (2004) 2841-2843
[47] J. I. Pankove, Luminescence of GaN, J. Luminescence 7 (1973),

114
[48] S. A. Wolf, D. D. Awschalom, Spintronic: A spin-based elec-

tronics vision for the future, Science 294 (2001), 1488
[49] N. Theodoropoulous, A. F. Herbard, M. E. Overberg, C. R.

Abernathy, S. J. Pearton, S. N. G. Chu, R. G. Wilson, Magnetic
and structural properties of Mn-implanted GaN, Appl. Phys.
Lett. 78, 22 (2001), 3475-3477
[50] S. Dhar et al., , Appl. Phys. Lett. 82 (2003), 2077
[51] M. Hashimoto, A. Yanase, R. Asano, H. Tanaka, H. Bang,

K. Akimoto, H. Asahi, Magnetic properties of Eu-doped GaN
grown by molecular beam epitaxy, Jpn. J. Appl. Phys, 42 (2003),
L1112-L1115
295
[52] S. Dhar, O. Brandt, M. Ramsteiner, V. F. Sapega, K. H. Ploog,
GaN:Gd: A superdilute ferromagnetic semiconductor with a
Curie temperature above 300K, Cond. Matt. 0412564, (2005)
[53] J. I. Pankove, J. A. Hutchby, Photoluminescence of ion-

implanted GaN, J. Appl. Phys. 47 (1976), 5387
[54] J. -S. Filhol, S. Petit, R. Jones, B. Hourahine, Th. Frauenheim,

H. Overlof, J. Coutinho, M. J. Shaw, P. R. Briddon, S. Öberg,
Structure and electrical activity of rare-earth dopants in selected
III-Vs, Mat. Res. Soc. Proc. Vol. 798, 2004, Y5.3.1-Y5.3.6
[55] H. J. Lozykowski, Kinetics of luminescence of isoelectronic

rare-earth ions in III-V semiconductors, Phys. Rev. B, 48(24),
(1993) 17 758- 17 769
[56] V. Katchkanov, J. F. W. Mosselmans, S. Dalmasso, K. P.

O’Donnell, R. W. Martin, O. Briot, N. Rousseau, and G. Ha-
lambalakis, Mater. Res. Soc. Symp. Proc. 798, Y5.10 (2004)
[57] H. Föll, “Defects in Crystals”, Faculty of Engineering, Uni-

versity of Kiel, http://www.tf.uni-kiel.de/matwis/amat/def
en/index.html
[58] http://www.uccs.edu/ tchriste/courses/PHYS549/549lectures/defects.html
[59] A. Stesmans, C. Claeys, Course on Fundamentals of defects in

materials, KULeuven/IMEC 2001-2002
[60] C. Ronning, E. P. Carlson, and R.F. Davis, Ion implantation

into gallium nitride, Phys. Rev. 351 (2001) 349-385
[61] http://www.tulane.edu/ sanelson/eens211/twinning.htm
[62] D. V. Lang, Deep-level transient spectroscopy: A new method

to characterize traps in semiconductors, J. Appl. Phys. 45, 7
(1974) 3023-3031
296
[63] S. M. Sze, Physics of Semiconductor Devices, John Wiley and
Sons New York (1981) 245-250
[64] A. B. Conibear, Deep level transient spectroscopy by digital

methods, Ph.D. thesis
[65] W. Shockley, W. T. Read Jr., Statistics of the Recombinations

of Holes and Electrons, Phys. Rev. 87, 5 (1952) 835-842
[66] G. L. Miller, D. V. Lang and L. C. Kimerling, Capacitance

Transient Spectroscopy, Ann. Rev. Mat. Sci. 7 (1977) 377-448
[67] P. Blood and J. W. Orton, The electrical characterization of

semiconductors, Rep. Prog. Phys., vol 41, 1978
[68] D. V. Lang, Thermally Stimulated Relaxation in Solids,

Springer-Verlag, Germany, Ed. P. Bräunlich, (1979) 93-132
[69] Y. Zohta and M. O. Watanabe, On the determination of the

spatial distribution of deep centers in semiconducting thin films
from capacitance transient spectroscopy, J. Appl. Phys. 53, 3
(1982) 1809-1811
[70] F. D. Auret, M. Nel, Single scan defect identification by deep

level transient spectroscopy using a two-phase lock-in amplifier
(IQ-DLTS), J. Appl. Phys. 63 (3), 1988
[71] J. H. Scofield, A frequency-domain description of a Lock-in Am-

plifier, American Journal of Physics 62(2), 1994
[72] A. Broniatowski, A. Blosse, P. C. Srivastava and J. C. Brour-

goin, Transient capacitance measurements on resistive samples,
J. Appl. Phys., 54, 6 (1983), 2907-2910
[73] J. R. Bird and J. S. Williams, Ion beams for materials analysis,

Academic Press, 1989
[74] H. Ryssel and I. Ruge, Ion implantation, John Wiley & Sons
Ltd., 1986
297
[75] A. Vantomme, Physics of Beam-Solid Interactions, B-KUL-
H0G10A course, K.U. Leuven, 2002
[76] J. Lindhard, M. Scharff and H. E. Schiøtt, Range concepts and

heavy ion ranges. (Notes on atomic collisions, II.), Mat. Fys.
Medd. Dan. Vid. Selsk., 33, No. 14 (1963).
[77] H. A. Bethe, Zur Theorie des Durchgangs schneller Korpusku-

larstrahlen durch. Materie, Annalen der Physik 5 (1930), 325-
400
[78] K. Nordlund, Molecular dynamics simulations of atomic colli-

sions for ion irradiation experiments., Acta Polytechnica Scan-
dinavica, Applied Physics Series 202 (1995)
[79] J. P. Biersack and J. F. Ziegler, SRIM - The Stopping and

Range of Ions in Matter, http://www.srim.org/
[80] J. S. Williams and J. M. Poate, Ion implantation and beam

processing, Academic Press, 1984
[81] C. Liu, A. Wenzel, B. Rauschenbach, E. Alves, A.D. Sequeira,

N. Franco, M.F. da Silva, J.C. Soares, and X.J. Fan, Amor-
phization of GaN by ion implantation, Nucl. Instrum. Methods
Phys. Res. B 178, 200 (2001)
[82] J. Nord, K. Nordlund, and J. Keinonen, Molecular dynamics

study of damage accumulation in GaN during ion beam irradi-
ation, Phys. Rev. B 68, (2003) 1841041- 1841047
[83] S.O. Kucheyev, J.S. Williams, J. Zou, C. Jagadish, G. Li, The

effect of ion mass, energy, dose, flux and irradiation tempera-
ture on implantation disorder in GaN, Nucl. Instrum. Methods
Phys. Res. B 178, (2001) 209-213
[84] W. Jiang, W.J. Weber, L.M. Wang, K. Sun, Amorphization

processes in Au ion irradiated GaN at 150-300K, Nucl. Instrum.
Methods Phys. Res. B 218, (2004) 427-432
298
[85] E. Wendler, A. Kamarou, E. Alves, K. Gärtner, W. Wesch,
Three-step amorphisation process in ion-implanted GaN at 15
K, Nucl. Instrum. Methods Phys. Res. B 206, (2003) 1028-1032
[86] K. Lorenz, U. Wahl, E. Alves, S. Dalmasso, R.W. Martin, K.P.

O’Donnell and the RENiBEl Network, High temperature im-
plantation of Tm in GaN, Mat. Res. Soc. Symp. Proc. 798,
(2003) Y5.4
[87] A. Vantomme, S.M. Hogg, M.F. Wu, B. Pipeleers, M. Swart,

S. Goodman, D. Auret, K. Iakoubovskii, G.J. Adriaenssens, K.
Jacobs, I. Moerman, Suppression of rare-earth implantation-
induced damage in GaN, Nucl. Instrum. Methods Phys. Res. B
175-177, (2001) 148-153
[88] C. Liu, A. Wenzel, K. Volz, B. Rauschenbach, Influence of sub-

trate temperature on the damage buildup and removal of ion
implanted gallium nitride, Nucl. Instrum. Methods Phys. Res.
B 148, (1999) 396-400
[89] M.F. Wu, A. Vantomme, H. Pattyn, G. Langouche, Importance

of channeled implantation to the synthesis of erbium silicide
layers, Appl. Phys. Lett. 67, 26 (1995) 3886-3888
[90] S.M. Hogg, B. Pipeleers, A. Vantomme, M. Swart, Channeling

of low energy heavy ions: Er in Si< 111 >, Appl. Phys. Lett.
80, 23 (2002) 4363-4365
[91] B. Pipeleers, S.M. Hogg, A. Vantomme, Influence of the im-

plantation angle on the generation of defects for Er implanted
GaN, Nucl. Instrum. Methods Phys. Res. B 206, (2003) 95-98
c
[92] W. Brandt, Channeling in Crystals, Copyright °1968 by Sci-
entific American, Inc.
[93] J. Lindhard, Influence of crystal lattice on motion of ener-

getic charged particles, Mat. Fys. Medd. Dan. Vid. Selsk. 34,
14(1965), 1-64
299
[94] L.C. Feldman and J.W. Mayer, Fundamentals of surface and
thin film analysis, Elsevier Science Publishers B.V., 1986
[95] W. -K. Chu, J. W. Mayer, and M. -A. Nicolet, Backscattering

spectrometry, Academic Press, 1978
[96] J. E. Westmoreland, J. W. Mayer, F. H. Eisen, and B. Welch,

Analysis of disorder distribution in boron implanted silicon, Ra-
diation effects, 6 (1970), 161-174
[97] E. Bøgh, Defect studies in crystals by means of channeling,

Canadian Journal of Physics, 46 (1968), 653-662
[98] S. M. Hogg, Ph.D. thesis, Channeled Implantation of Rare-

Earth Ions into Si - Fundamental Aspects and Silicide Forma-
tion, Katholieke Universiteit Leuven (2000)
[99] J. H. Barrett, Monte Carlo channeling calculations, Phys. Rev.

B 3(1971), 1527-1547
[100] E. P. Bertin, Introduction to X-ray spectroscopic analysis,

Plenum Press, New York, 1978
[101] An introduction to X-ray diffraction, Bede scientific, reference

guide, 1998
[102] B.R. Appleton and G. Foti, Channeling - Ion Beam Handobook

for Material Analysis, edited by J.W. Mayer and E. Rimini,
Academic Press, Inc. 1977, 67-107
[103] K. Schmid, Some new aspects for the evaluation of disorder

profiles in silicon by backscattering, Radiat. Eff. 17 (1973), 201
[104] B. Pipeleers, Defect accumulation in erbium implanted gallium

nitride, Ph.D. thesis, Katholieke Universiteit Leuven (2005)
[105] J.F. Ziegler, J.P. Biersack, and U. Littmark, The stopping and
range of ions in solids, Volume 1, Pergamon Press, New York,
1985
300
[106] D. Schroyen, Ionenimplantatie, bestudeerd met ionenbundelka-
nalisatie en Mössbauerspektroskopie, Ph.D. thesis, Katholieke
Universiteit Leuven (1987)
[107] A. Yoshiasa, K. Koto, H. Maeda, and T. Ishii, The mean-square

relative displacement and displacement correlation functions in
tetrahedrally and octahedrally coordinated AN B 1−N crystals,
Jpn. J. Appl. Phys. 36 (1997), 781
[108] U. Wahl, E. Alves, K. Lorenz, J.G. Correia, T. Monteira, B. De

Vries, A. Vantomme, R. Vianden, Lattice location and optical
activation of rare earth implanted GaN, Mat. Sci. Eng. B 105
(2003), 132-140
[109] P. J. M. Smulders and D. O. Boerma, Computer simulation

of channeling in single crystals, Nucl. Instrum. Methods Phys.
Res. B 29 (1987), 471-489
[110] B. De Vries, U. Wahl, A. Vantomme, J.G. Correia, and The

ISOLDE Collaboration, Emission Channeling experiments from
the decay of 149 Gd to 149 Eu in GaN, Mat. Sci. Eng. B105
(2003), 106-110
[111] B. De Vries, Lattice site location of impurities in group III

nitrides using Emission Channeling, Ph.D. thesis, Katholieke
Universiteit Leuven (2006)
[112] Lawrence R. Doolittle, Algorithms for the rapid simulation

of Rutherford Backscattering spectra, Nucl. Instrum. Methods
Phys. Res. B 9 (1985), 344-351
[113] S. Decoster, Private communication
[114] M. Mamor, V. Matias, P. Marie, P. Ruterana, A. Vantomme,

Defects Induced in GaN by Europium implantation, Appl. Phys.
Lett., 85 (2004), 2244-2246;
301
[115] G. Bai and M.-A. Nicolet, Defect production and annealing in
self-implanted Si, J. Appl. Phys. 70 (1991), 649
[116] E. Alves, M.F. da Silva, J.C. Soares, J. Bartels, R. Vianden,

C.R. Abernathy and S. Pearton, MRS Int. J. Nitride Semicond.
Res. 4S1 (1999) G11.2
[117] W. Jiang, W.J. Weber, S. Thevuthasan, and V. Shutthanadan,

Channeling study of lattice disorder and gold implants in gal-
lium nitride, Nucl. Instrum. Methods Phys. Res. B 191 (2002),
509-513
[118] A. Colder, T. Wojtowicz, P. Marie, P. Ruterana, V. Matias, M.

Mamor, A. Vantomme, S. Eimer, L. Méchin, Deep level tran-
sient spectroscopy and TEM analysis of defects in Eu implanted
GaN, Phys. Stat. Sol. (c) 2, (2005) 2450-2453
[119] J. S. Williams, Ion implantation of semiconductors, Mat. Sci.

Eng. A 253 (1998), 8-15
[120] C. Liu, B. Mensching, K. Volz, and B. Rauschenbach, Lattice

expansion of Ca and Ar ion implanted GaN, Appl. Phys. Lett.
71, 16 (1997) 2313-2315
[121] A. Wenzel, C. Liu, B. Rauschenbach, Effects of implantation pa-

rameters on the structural properties of Mg-ion implanted GaN,
Mat. Sci. Eng. B 59 (1999), 191-194
[122] I. Usov, N. Parikh, D. B. Thomson, and R. F. Davis, Ef-

fect of implantation temperature on damage accumulation in
Ar-implanted GaN, MRS Internet J. Nitride Semicond. Res. 7
(2002), 9
[123] W. Jiang, W. J. Weber, Effect of irradiation temperature on

dynamic recovery in gallium nitride, Nucl. Instrum. Methods
Phys. Res. B 242 (2006), 431-433
302
[124] N. Parikh, A. Suvkhanov, M. Lioubtchenko, E. P. Carlson, M.
D. Bremser, D. Bray, R. F. Davis, and J. Hunn, Ion implan-
tation of epitaxial GaN films: Damage, doping and activation,
Nucl. Instrum. Methods Phys. Res. B 127/128 (1997), 463-466
[125] J. A. Van Vechten, Quantum dielectric theory of electronega-

tivity in covalent systems. III. Pressure-temperature phase dia-
grams, heat of mixing, and distribution coefficients, Phys. Rev.
B 7 (1973), 1479
[126] E. Alves, M. F. da Silva, J. C. Soares, J. Bartels, R. Vianden,

C. R. Abernaty, and S. J. Pearton, RBS lattice site location
and damage recovery studies in GaN, MRS Internet J. Nitride
Semicond. Res. 4S1 (1999), G11.2
[127] S. J. Rhee, S. Kim, C. W. Sterner, J. O. White, and S. G.

Bishop, Excimer laser annealing of Er-implanted GaN, J. Appl.
Phys. 90 (2001), 2760-2763
[128] W. T. Young, S. R. P. Silva, J. M. Shannon, Laser annealing of

low temperature grown gallium nitride, Diamond and Related
Materials 10 (2001), 1311-1313
[129] S. J. Pearton, J. C. Zolper, R. J. Shul, and F. Ren, GaN: Pro-

cessing, defects, and devices, J. Appl. Phys. 86 (1999), 1-78
[130] J. C. Zolper, J. Han, R. M. Biefeld, S. B. Van Deusen, W.

R. Wampler, D. J. Reiger, S. J. Pearton, J. S. Williams, H. H.
Tan, R. F. Karlicek, J. R. Stall, and R. A. Stall, Si-implantation
activation annealing of GaN up to 1400o C, J. Electron. Mater.
27 (1998), 179-184
[131] K. Lorenz, U. Wahl, E. Alves, S. Dalmasso, R. W. Martin,

K. P. O’Donnell, S. Ruffenach and O. Briot, High-temperature
annealing and optical activation of Eu-implanted GaN, Appl.
Phys. Lett. 85, 14 (2004) 2712-2714
303
[132] S. O. Kucheyev, J. S. Williams, C. Jagadish, J. Zou and G. Li,
Damage buildup in GaN under ion bombardment, Phys. Rev. B
62 (2000), 7510-7522
[133] S. Degroote, private communication (2007)
[134] S. O. Kucheyev, J. S. Williams, J. Zou, G. Li, C. Jagadish,

M. O. Manasreh, M. Pophristic, S. Guo and I. T. Ferguson,
Structural disorder in ion-implanted Alx Ga1−x N , Appl. Phys.
Lett. 80, 5 (2002) 787-789
[135] S. O. Kucheyev, J. S. Williams, J. Zou and C. Jagadish, Dy-

namic annealing in III-nitrides under ion bombardment, J.
Appl. Phys., 95, 6 (2004), 3048-3054
[136] E. Nogales, R. W. Martin, K. P. ODonnell, K. Lorenz, E. Alves,

S. Ruffenach and O. Briot, Failure mechanism of AlN nanocaps
used to protect RE-implanted GaN during high temperature an-
nealing, Appl. Phys. Lett. 88, 031902 (2006), 1-3
[137] S. O. Kucheyev, Ion-beam processes in group-III nitrides ,

Ph.D. thesis, The Australian National University (2002)
[138] L. C. Feldman, J. W. Mayer, S. T. Picraux, Material Analysis

by Ion Channeling, Academic Press, New York, (1982) 88-116
[139] K. Lorenz, E. Alves, T. Monteiro, A. Cruz, M. Peres, Struc-

tural and Optical characterization of Eu Implanted Alx Ga1−x N ,
Nucl. Instrum. Methods Phys. Res. B 257 (2007), 307-310
[140] S. Yamaguchi, M. Kariya, S. Nitta, H. Kato, T. Takeuchi, C.

Wetzel, H. Amano, I. Akasaki, Structural and optical properties
of AlInN and AlGaInN on GaN grown by metalorganic vapor
phase epitaxy, J. Crys. Growth 195 (1998), 309-313
[141] R. W. Martin, D. Rading, R. Kersting, E. Tallarek, E. No-

gales, D. Amabile, K. Wang, V. Katchkanov, C. Trager-Cowan,
304
K. P. O’Donnell, I. M. Watson, V. Matias, A. Vantomme, K.
Lorenz and E. Alves, Depth profiling of ion-implanted AlInN us-
ing time-of-flight secondary ion mass spectrometry and cathodo-
luminescence, Phys. Stat. Sol. (c) 3, 6, (2006) 1927-1930
[142] J. F. Carlin, C. Zellweger, J. Dorsaz, S. Nicolay, G. Christmann,

E. Feltin, R. Butté, N. Grandjean , Progresses in III-nitride
distributed Bragg reflectors and microcavities using AlInN/GaN
materials, Phys. Stat. Sol. (b) 242, 11, (2005) 2326-2344
[143] R. W. Martin, private communication (2005)
[144] K. Lorenz, N. Franco, E. Alves, I. M. Watson, R.W. Martin, and

K. P. ODonnell, Anomalous Ion Channeling in AlInN=GaN
Bilayers: Determination of the Strain State, Phys. Rev. Lett.
97 (2006), 085501
[145] B. D. Cullity, Elements of X-ray diffraction, Addison-Wesley,

1967
[146] F. Priolo, G. Franzò, F. Iacona, D. Pacifici, V. Vinciguerra, Ex-

citation and non-radiative de-excitation processes in Er-doped
Si nanocrystals, Mat. Sci. Eng. B81 (2001), 9-15
[147] K. P. O’Donnell, V. Katchkanov, K. Wang, R. W. Martin, P.

R. Edwards, B. Hourahine, E. Nogales, J. F. W. Mosselmans,
B. De Vries, and the RENiBEl Consortium, Site multiplicity of
Rare Earth ions in III-nitrides, Mater. Res. Soc. Symp. Proc.
Vol. 831 (2005), E9.6.1
[148] V. Katchkanov, K. P. O’Donnell, S. Dalmasso, R. W. Martin,

A. Braud, Y. Nakanishi, A. Wakahara, and A. Yoshida, Pho-
toluminescence studies of Eu-implanted GaN epilayers, Phys.
Stat. Sol. B, 1-6 (2005)
[149] A. Braud, J. L. Doualan, R. Moncorge, B. Pipeleers, A. Van-

tomme, Er-defect complexes and isolated Er center spectroscopy
in Er-implanted GaN, Mat. Sci. Eng. B105 (2003), 101-105
305
[150] MARLOWE 15b, Computer Simulation of Atomic Collisions in
Crystalline Solids, http://www.nea.fr/abs/html/psr-0137.html
[151] D. Seghier, T. Benyattou, G. Bremond, F. Ducroquet, J. Gre-

goire, G. Guillot, C. Lhomer, B. Lambert, Y. Toudic, and A.
Le Corre, Appl. Phys. Lett. 60, 983 (1992)
[152] F. D. Auret, S. A. Goodman, F. K. Koschnick, B. Beaumont,

and P. Gibart, Proton bombardment-induced electron traps in
epitaxially grown n-GaN, Appl. Phys. Lett. 74, 3 (1999), 407-
409
[153] S. Ruvimov, Z. Liliental-Weber, J. Washburn, K. J. Duxs-

tad, E. E. Haller, Z. -F. Fan, S. N. Mohammed, W. Kim, A.
E. Botchkarev, and H. Morkoc, Microstructure of Ti/Al and
Ti/Al/Ni/Au Ohmic contacts for n-GaN, Appl. Phys. Lett. 69,
11 (1996) 1556-1558
[154] T. Wojtowicz, V. Matias, P. Marie, M. Mamor, B. Pipellers,

P. Ruterana and A. Vantomme, Microstructural and electrical
characterization of Er and Eu implanted gallium nitride, Mat.
Sci. Eng. B 105 (2003), 122-125
[155] M. Mamor, V. Matias, A. Vantomme, A. Colder, P. Marie, and

P. Ruterana, Defects induced in GaN by europium implantation,
Appl. Phys. Lett. 85, 12 (2004), 2244-2246
[156] F. D. Auret, S. A. Goodman, F. K. Koschnick, J. M. Spaeth, B.

Beaumont, and P. Gibart, Proton bombardment-induced elec-
tron traps in epitaxially grown n-GaN, Appl. Phys. Lett. 74
(1999), 407-409
[157] W. Götz, N. M. Johnson, H. Amano, and I. Akasaki, Deep level

defects in n-type GaN, Appl. Phys. Lett. 65 (1994), 463-465
[158] F. D. Auret, S. A. Goodman, F. K. Koschnick, J. M. Spaeth,

B. Beaumont, and P. Gibart, Electrical characterization of two
306
deep electron traps induced in epitaxially grown n-GaN during
He-ion irradiation, Appl. Phys. Lett. 73 (1998), 3745-3747
[159] Z. -Q. Fang, D. C. Look, P. Visconti, D. -F. Wang, C. -Z. Lu,

H. Morkoç, S. S. Park, and K. Y. Lee, Deep centers in a free-
standing GaN layer, Appl. Phys. Lett. 78 (2001), 2178-2180
[160] D. Haase, M. Schmid, W. Kürner, A. Dörnen, V. Härle, F.

Scholz, M. Burkard, and H. Schweizer, Deep-level defects and
n-type carrier concentration in nitrogen implanted GaN, Appl.
Phys. Lett. 69, 17 (1996), 2525-2527
[161] D. K. Schroder, Semiconductor material and device character-

ization, 2nd edition, John Wiley and Sons (1998), 200-204
[162] B. Van Zeghbroeck, Principles of Semiconductor Devices,

http://ece-www.colorado.edu/ bart/book/, 2004
[163] P. J. Janse van Rensburg and F. D. Auret, Private communi-

cation, 2006
[164] F. D. Auret, S. A. Goodman, F. K. Koschnick, J. -M. Spaeth, B.

Beaumont and P. Gibart, Electrical characterization of sputter
deposition induced defects in n-GaN, MRS Internet J. Nitride
Semicond. Res. 4S1, G6.13 (1999), 1-6
[165] F. D. Auret, Private communication, 2005
[166] P. Hacke, T. Detchprohm, K. Hiramatsu, N. Sawaki, K.

Tadatomo, and K. Miyake, Analysis of deep levels in n-type
GaN by transient capacitance methods, J. Appl. Phys. 76, 1
(1994), 304-309
[167] S. F. Song, W. D. Chen, C. Zhang, L. Bian, C. C. Hsu, L.

W. Li, Y. H. Zhang, and J. Zhu, Electrical characterization of
Er and Pr implanted GaN films, Appl. Phys. Lett. 86, 152111
(2005), 1-3
307
[168] F. D. Auret, S. A. Goodman, F. K. Koschnick, J.-M. Spaeth,
B. Beaumont, and P. Gibart, Sputter deposition-induced elec-
tron traps in epitaxially grown n-GaN, Appl. Phys. Lett. 74, 15
(1999), 2173-2175
308
Publications
1. Matias, V., Öhl, G., Soares, J. C., and Barradas, N. P., Vieira, A.,
Cardoso, S. and Freitas, P. P., Determination of the composition of
light thin films with artificial neural network analysis of Rutherford
backscattering experiments, Phys. Rev. E 67, 046705 (2003);
2. Öhl, G., Matias, V., Vieira, A., Barradas, N. P., Artificial neu-
ral network analysis of RBS data with roughness: Application to
T i0.4 Al0.6 N/M o multilayers, Nucl. Instrum. Methods Phys. Res.
B 211 (2003) 265273;
3. Mamor, M., Matias, V., Marie, P., Ruterana, P., Vantomme, A.,
Defects Induced in GaN by Europium implantation, Applied Physics
Letters, 85 (2004), 2244-2246;
4. De Vries, B., Matias, V., Vantomme, A., Wahl, U., Rita, E.M.C.,
Alves, E., Lopes, A.M.L., Correia, J.G. and the ISOLDE Collabora-
tion, Influence of O and C co-implanted on the lattice site of Er in
GaN, Applied Physics Letters, 84, ( 2004) 4304-4307;
5. Wojtowicz, T., Matias, V., Marie, P., Mamor, M., Pipeleers, B.,
Ruterana, P., Vantomme, A., Microstructural and electrical charac-
terization of Er and Eu implanted gallium nitride, Material Science
and Engineering B105 (2003) 122-125;
6. Dalmasso, S., Martin, R.W., Edwards, P.R, Katchkanov, V., O’Donnell,

K.P., Lorenz, K., Alves, E., Wahl, U., Pipeleers, B., Matias, V.,
Vantomme, A., Nakanishi, Y., Wakahara, A., Yoshida, A., Electron
309
Micro-Probe Analysis and cathodoluminescence spectroscopy of rare
earth - implanted GaN, MRS Symp. Proc. 798, Y5.2 (2004);
7. Colder, A., Marie, P., Wojtowicz, T., Ruterana, P., Eimer, S., Mchin,
L., Lorenz, K., Wahl, U., Alves, E., Mamor, M., Matias, V., Pipeleers,
B. Characterization of defects in rare earth implanted GaN by deep
level transient spectroscopy, Superlattices and Microstructures 36 (2004)
713-719;
8. Colder, A., Marie, P., Ruterana, P., Matias, V., Mamor, M., Eimer
S., Mchin, L., Deep Level Transient Spectroscopy and TEM analysis
of defects in Eu implanted GaN, phys. stat. sol. (c) 2, No. 7, 2450
(2005);
9. Auret, F. D., van Rensburg, P. J. Janse, Hayes, M., Nel, J. M., Meyer,
W. E., Decoster, S., Matias, V., Vantomme, V., Electrical charac-
terization of defects introduced in n-type Ge during indium implanta-
tion, Applied Physics Letters, 89 (2006), 152123;
10. Martin, R. W., Rading, D., Kersting, R., Tallarek, E., Nogales, E.,
Amabile, D., Wang, K., Katchkanov, V., Trager-Cowan, C., O’Donnell,
K. P., Watson, I. M., Matias, V., Vantomme, A., Lorenz K, and
Alves, E., Depth profiling of ion-implanted AlInN using time-of-flight
secondary ion mass spectrometry and cathodoluminescence, phys. stat.
sol. (c) 3, No. 6, 19271930 (2006);
11. Wang, K., Martin, R.W., Amabile, D., Hernandez, S., Nogales, E.,
O’Donnell, K.P., Lorenz, K., Alves, E., Matias, V., Vantomme, A.,
Wolverson, D., Watson, I.M., Optical energies of AlInN epilayers, J.
Appl. Phys. 103, 073510 (2008).
12. Matias, V., Vantomme, A., van Rensburg, P. J. J., Kassier, G.,
Auret, F. D., Defects in Eu implanted GaN, In preparation.
310

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Instituut voor

Defect characterization of Europium

Promotor: Proefschrift ingediend tot

Vasco Miguel Matias Serrão

“Perfection has one grave defect: it is apt to be dull! ”

1 Properties of III-nitrides and RE in GaN 1

2 Energy band structure of semiconductors 19

4 Deep Level Transient Spectroscopy 51

5 Ion beams for materials modification and characterization 73

6 Structural characterization of Eu-implanted GaN 109

7 Electrical characterization of Eu-implanted GaN 205

A Rutherford Backscattering and Channeling Spectrometry

B High Resolution X-ray Diffraction (HRXRD) 279

Nederlandstalige samenvatting 283

Gallium nitride and related semiconducting materials are in the center

emission lines with wavelengths virtually independent of the host material.

The work summarized in this thesis is performed in the context of

El ectroluminescent emitters. The main goal of this network was to under-

1.1 III-nitrides historical background and their

optoelectronic devices operating in this energy region.

locations by forming inverse-pyramidal pits on the surface of the grown

1.2 Growth of crystalline III-nitrides

1.2.1 Nitride growth techniques

1.2.2 Buffer layer

Fig. 1.1: MOCVD growth steps of III-nitrides [18]

stacking faults formed at boundaries will proceed up to the film surface.

Fig. 1.2: Mosaic growth of the III-nitride film

1.3 Brief overview of III-nitride properties

1.3.1 Structural properties

1.3.2 Thermal properties

Fig. 1.3: Wurtzite structure of group III nitrides

temperature for the range of 300-900 K. They found a mean coefficient

1.3.3 Optical properties and band structure

Fig. 1.5: Band structure of wurtzite GaN [24].

1.3.4 Electrical properties

As discussed in section 1.1, as-grown heteroepitaxial wurtzite GaN has an

GaN AlN InN

thereby have a strong influence on the electronic properties of GaN, such

1.4 Rare-earth elements

Fig. 1.6: The rare-earth elements

1.4.1 Properties of rare-earths

1.4.2 RE in GaN for luminescence emission

It is their electronic charge distribution that makes RE very interesting for

[29]. When the RE3+ is integrated in the matrix of a III-V semiconductor,

diffusivity and III-nitrides have relatively low decomposition temperatures

necessary to deepen this discussion into the electronic band structure of

Energy band structure of

2.1 Band structure in solids

A great variety of semiconductors properties are fundamentally explained

Fig. 2.1: Split of energy of electronic states [35]

2.1.1 Electrons in semiconductors

To understand how the band structure appears in semiconductors we start

Fig. 2.3: Wave-functions of electrons in a nuclear potential well.

Fig. 2.4: Periodic potential of a lattice of atomic nuclei.

cases of what happens to electrons in semiconductors, however, the inter-

reduced E /k diagram of figure 2.5 c). The energy discontinuity at the

Fig. 2.7: Band scheme for metals, semiconductors and insulators.

2.2 Electronic conduction in semiconductors

At this point, it is important to mention two special energy bands often

Fig. 2.8: Charge carriers under the influence of an electric field E.

2.3 Optical emission

The optical properties of a semiconductor are dominated by the inter-band

energy and crystalline momentum: