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Final Thesis
Spin Dependent recombination in GaNAs
Yuttapoom Puttisong
LITH-IFM-A-EX--09/2187—SE
Examiner: Irina Buyanova, Linköping University
Division of Functional Electronic Materials
Department of Physics, Chemistry and Biology
Linköping University, Sweden
Linköping 2009
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Upphovsrätt
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© Yuttapoom Puttisong
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Abstract
Spin filtering properties of novel GaNAs alloys are reported in this thesis. Spin-
dependent recombination (SDR) in GaNAs via a deep paramagnetic defect center is intensively
studied. By using the optical orientation photoluminescence (PL) technique, GaNAs is shown to
be able to spin filter electrons injected from GaAs, which is a useful functional property for
integratition with future electronic devices. The spin filtering ability is found to degrade in
narrow GaNAs quantum well (QW) structures which is attributed to (i) acceleration of band-to-
band recombination competing with the SDR process and to (ii) faster electron spin relaxation in
the narrow QWs. Ga interstitial-related defect centers have been found to be responsible for the
SDR process by using the optically detected magnetic resonance (ODMR) technique. The
defects are found to be the dominant grown-in defects in GaNAs, commonly formed during both
MBE and MOCVD growths. Methods to control the concentration of the Ga interstitials by
varying doping, growth parameters and post-growth treatments are also examined.
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“Thanks to the world with uncertainty principle”
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Acknowledgement
I grateful to my supervisor, Prof. Irina Buyanova and Prof. Weimin Chen for letting me be a part
of this interesting project, for always opening the door to have fruitful discussions and for their
support and encouragement.
I would like to thank Xingjun Wang for all valuable time we spend in labs, for sharing
the knowledge in semiconductor spintronics as well as for teaching me experimental techniques
during my work on the thesis.
I also would like to thank my opponent, Huan-Hung Yu for intensively discussing my
thesis.
I am also grateful to Shula Chen, Shun-Kyun Lee, Daniel Dagnelund, Jan Beyer and
Deyong Wang for family-like research atmosphere, I am kind of working in a very lovely family.
I further thank Arne Eklund for technical assistance and Lejla Vrazalica for her help with
administrative matters.
Finally, I am grateful to my mother for always supporting me during all her life. I cannot stand
in this place without you.
Yuttapoom Puttisong
.
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Tables of contents
Introduction 8
Chapter One: Fundamental electronic structure of GaNAs 9
The empirical band anti-crossing (BAC) model..................................................................9
Pseudopotential LDA calculation......................................................................................10
Band alignment in GaNAs/GaAs hetero-structures...........................................................11
Strain-induced splitting of the valence band......................................................................11
Confinement effect-induced lh-hh splitting in a QW system............................................12
Radiative recombination process in GaNAs......................................................................13
Non-radiative (NR) recombination....................................................................................14
Chapter Two: Spin dynamics 15
Optical orientation and spin polarization...........................................................................15
Spin relaxation...................................................................................................................17
Chapter Three: Spin Dependent Recombination (SDR) 20
General principles of SDR.................................................................................................20
Optical orientation in the presence of a deep paramagnetic center...................................21
SDR ratio...........................................................................................................................22
Two spin pools picture.......................................................................................................23
Physical realization of an efficient spin dependent-recombination process......................24
Chapter Four: Experimental Approach 27
Optical orientation PL spectroscopy..................................................................................27
Magnetic resonance technique...........................................................................................30
Chapter Five: Experimental Results
Defect Engineering for Spin Filtering Effect in GaNAs 37
Defect engineered spin filter from a low dimensional semiconductor structure; spin
filtering effect in QW structures........................................................................................37 Effect of growth temperature and post-growth treatment on the SDR process.................41
7
Effects of doping on the formation of the Gai-interstitial paramagnetic centers...............46 Effects of growth techniques on the defect formation.......................................................50
Summary 53
Bibliography 54
8
Introduction
Diluted-nitrides (i.e. N containing III-V ternary and quaternary alloys) have emerged as a
subject of considerable theoretical and experimental research efforts because of their unique and
fascinating electronic properties. Unlike conventional ternary III-V alloys, such as AlGaAs,
GaInAs, etc, where the band gap energy of the alloy can be approximated as a weighted linear
average of the parental compounds, the dilute nitrides exhibit a huge bowing in the band gap
energy. Consequently, GaInNAs has been considered as a key material for long wavelength
lasers emitting at the optical-fiber communication wavelength window (1300-1550 nm) [1].
Unfortunately, from numerous optical studies it has been concluded that the radiative efficiency
of dilute nitrides rapidly degrades with incorporation of nitrogen as a result of N-induced
formation of efficient non radiative (NR) defect centers. This efficient NR recombination
currently prevents efficient utilization of dilute nitrides in light emitting devices. On the other
hand, the recent study by X.J. Wang et al. [2] provides different perspectives on the role of
defect-mediated recombination in GaNAs. It shows a possibility to utilize this material as an
efficient semiconductor spin-filter which operates at room temperature and does not require
using a ferromagnetic metal (or diluted magnetic semiconductors) or applying a magnetic field.
It has been shown that the spin filtering effect in GaNAs relies on existence of a paramagnetic
defect and selective recombination under Pauli exclusion principle. Therefore, the NR defects
decremented in terms of optical properties were found to have an important role in spintronics
application.
The work presented in this thesis focuses on detailed characterization of the SDR process
in GaNAs alloys. The thesis is organized as follows. In the first chapter we attempt to give a
brief review on the present knowledge of electronic properties of GaNAs, mainly from
experimental perspectives. The second chapter is devoted to physical mechanisms which govern
spin relaxation in semiconductors and to optical methods of generating spin polarization. Basic
principles of the spin-dependent recombination (SDR) are introduced in chapter three. Chapter
four describes characterization techniques utilized in this work. Finally, experimental results and
summary are presented in chapter five and in the final part of the thesis, respectively.
9
Chapter One: Fundamental electronic structure of GaNAs
Early absorption measurements [3] [4] [5] [6] have unambiguously demonstrated that
GaN𝑥As1−𝑥 is a direct band gap semiconductor, similar to parental GaAs and GaN. However,
instead of the expected blue shift from the GaAs band gap with N incorporation, the GaNAs
alloy has shown a considerable red shift in the fundamental absorption edge (see figure 1.1.) This
was accompanied by the splitting of the conduction band (CB) of GaNAs into two subbands, as
demonstrated by the electro- [7] and photo [8] -reflectance measurements. The lower one is
usually denoted as E− and represents the CB edge of the alloys, whereas the upper subband is
denoted by E+. The E− and E+energies depend on the concentration of nitrogen [N]. With
increasing the nitrogen composition, the E− subband shifts towards lower energies while the E+
position increases with [N]. Photo-reflectance measurements have also shown that a spin-orbit
splitting energy (∆0) remains independent of the nitrogen concentration.
Two theoretical approaches, i.e. the so-called band-anti-crossing (BAC) model [9] and
local-density approximation (LDA) calculations [10], [11], [12] are usually considered to
describe the formation of the E+ and E− states under the presence of nitrogen.
The empirical band anti-crossing (BAC) model
According to this model, the formation of the E− and E+ states is induced by an
interaction between the delocalized CB states of the Γ character and the localized nitrogen-
related state EN (EN = 1.65 eV in GaAs.) A magnitude of the splitting is mainly determined by
an inter-band matrix element VMN. The E− sub-band is delocalized, conduction band-like while
the E+ state is derived from the localized EN state. The dispersion relation is then given by:
Figure 1.1: Compositional dependence of
the band gap energy of III-V-N alloys at
room temperature. Lines show result from
model calculation. Local density
approximation and dielectric model is
used.
10
E± = E𝑔 ± [( E𝑔 − E𝑁 2
+ 4𝑉𝑀𝑁2 )1/2 − |E𝑔 − E𝑁|]/2,
where E𝑔 is the bandgap of the parental III-V compound before alloying it with N. VMN is the
interaction term which depends on nitrogen composition:
𝑉𝑀𝑁 = 𝐶𝑀𝑁𝑥1/2,
Here x refers to nitrogen composition and 𝐶𝑀𝑁 is a constant equal to 𝐶𝑀𝑁 = 2.7eV for GaNAs.
This model is empirical since it only considers the interaction of the CB states with the N
level related to an isolated substitutional N atom. It neglects mixing of the CB states introduced
by nitrogen and also a complexity of formed nitrogen centers. However, the BAC model
provides a simple, analytical expression to describe the GaNAs electronic properties, including
the position of E±, a temperature induced shift of the band-gap, an electron effective mass, etc.
The position of E± as a function of nitrogen concentration is shown in figure 1.2.
Pseudopotential LDA calculation
The more complicated theory based on pseudopotential provides more general physical
explanation of the existence of the sub-bands. It shows that the formation of the E−and E+ states
is induced by a strong perturbation by nitrogen of host states resulting in symmetry breaking.
The degenerate L and X CB minima are now split into a1 and t1 states. Mixing between the
a1(Γ) and a1(L) conduction band states leads to the formation of E−. On the other hand, the
E+ state originates from a weighted average of a1(L) and a1(N) states. According to this model,
the interaction between the CB and EN is small and E+ exhibits the L-like characterer. However
pseudopotential LDA calculations require a substantial effort and the numerical results are
difficult to use.
Figure 1.2; positions of E+ and E− in
GaNAs alloy according to the empirical
band-anti-crossing model. E𝐿 refers to
the position of the L CB minimum relative
to the top of the VB in GaAs.
11
Band alignment in GaNAs/GaAs hetero-structures
Band alignment in GaNAs/GaAs heterostructures is of importance for optoelectronic and
spintronic applications. Both type-I and type-II band alignment in GaNAs/GaAs quantum wells
(QWs) has been concluded as schematically illustrated in figure 1.3. However, the type-I band
alignment seems to be more probable based on several experimental observations [13]. Firstly,
according to the time-resolve photoluminescence measurements, recombination lifetime of
electron-hole pairs in the GaNAs QWs is of the same order of magnitude as in bulk GaAs. Since
in the type-II structures the recombination lifetime is expected to be longer due to spatial
separation of electron-hole pairs, the GaNAs/GaAs structures have the type-I alignment.
Secondly, it has been found that the lowest energy photoluminescence (PL) originates from the
CB-light hole (lh) transitions, based on the PL polarization measurements in GaNAs/GaAs QWs.
This means that holes participating in the recombination should be located in the GaNAs QW as
the uppermost VB states in GaAs barriers are heavy hole (hh) states.
Strain-induced splitting of the valence band
At the Γ point (k =0) the top VB states has a total angular momentum 𝐽 = 3/2, due to
spin orbit interaction. At this point, the Jz=±3/2 and Jz=±1/2 states are degenerate. But if the
bulk material is subjected to compressive or tensile stain, this degeneracy will be lifted. Indeed,
let us consider the in-plane biaxial strain. In this case the in-plane deformation energy (say in a
xy plane) will be different from that a z-direction. Hence, symmetry of the system is reduced
and the degeneracy is lifted [14]. The result is a splitting between the hh (Jz=±3/2) and the lh
(Jz=±1/2) states. Therefore, if a lattice constant of an epilayer material is smaller than that of a
Figure 1.3; schematics of type I and type
II band alignment in GaNAs/GaAs QW
system. The arrows show dominant
recombination transitions, i.e. direct in
space of the type I transitions (the solid
line) and indirect in space for the type II
transitions (the dashed line).
Recombination rate is higher in the type I
QW which is preferred for optoelectronic
applications in terms of high radiative
efficiency.
12
substrate, i. e. when the epilayer is under tensile strain, the VB lh states will lie above the hh
states. On the other hand, if the system is under compression, the lh states lie below the hh states
(see figure 1.4.)
GaAs is a common substrate for GaNAs. The lattice constant of GaNAs is smaller than
that of GaAs and biaxial tensile stain dominates. Thus, in the strained GaNAs the lh VB states
usually lie above the hh states.
Figure 1.4; fundamental semiconductor band structure under tensile and compressive strain.The degeneracy of the
VB states is lifte and the, lh and hh states are spit.
Confinement effect-induced lh-hh splitting in a QW system
Due to the confinement effect, energy levels in quantum wells are separated into discrete
levels. The separation between adjacent levels is determined by a size of the quantum well and
by values of effective masses of carriers. By solving the Schrödinger equation for the QW
structure it can be shown that the energy positions of levels in the QW are inversely proportional
to the QW size and also to effective masses of the carriers [14]. Thus, for a fixed size and a
fixed quantum number, the lh VB states, which have the smaller effective mass, will be pulled
further down in energy as compared with the heavy hole states. If the system is unstrained, the
degeneracy between the lh and hh states is lifted and the lh states have higher energy than the hh
states (see figure 1.5.)
lh
hh
so
E(p)
tension
Eg
lh
hh
so
E(p)
∆
unstrained
Eg
lh
hh
so
E(p)
compression
p
Eg
13
Radiative recombination process in GaNAs
As mentioned above, one of the promising applications of the III-V-N alloys is for the
near-infrared light emitters. Therefore, understanding origin of radiative recombination
processes in these materials is of importance. Previous optical measurements have shown that
introduction of nitrogen induces strong localization effects. As a result, low temperature PL in
these materials is due to localized exciton (LE) recombination [13]. This assignment was based
on several experimental observations. (i) A strong red shift of the PL maximum is observed with
increasing temperature and exhibits the so-called S-shape behavior (see figure 1.6). The physical
explanation of this behavior is as follows. When temperature is increased, carriers in the
localized excitonic states can be excited into the delocalized states in CB. The S-shape point is
the transition from the localized states to the delocalized states. (ii) A blue shift of the PL
maximum is observed when excitation power is increased as a result of filling of higher energy
states within the localized states.
700 750 800 850 900 950 1000 1050 1100 1150
6 K
60 K
120 K
180 K
240 K
300 K
PL
In
ten
sit
y (
No
rmali
zed
)
wavelength (nm)
GaNAs, N = 0.54%
Figure 1.6; PL spectra from GaNAs as a
function of temperature.
Eg
n = 1 n = 2
hh, n = l lh, n = 1
Figure 1.5; quantum size effect. Due to
quantum confinement the lh states have
higher energy than the hh states. Optical
transitions in the well follow selection
rules, ∆n=0, ∆m=±1.
14
Non-radiative (NR) recombination
The radiative efficiency of III-V-N compounds rapidly degrades when nitrogen
composition is increased. The observed degradation is commonly attributed to poor structural
quality of the N-containing alloys and also to increasing concentrations of non-radiative (NR)
defects [15]. For optoelectronic applications, radiative luminescence has to be utilized.
Fortunately, according to previous studies the radiative efficiency can be improved by post-
growth treatments [13]. Rapid thermal annealing has also been employed to narrow a spectral
width of the PL spectrum and to increase the PL intensity.
Spin-dependent recombination
GaNAs shows fascinating spin dynamics of carriers. Specifically, an apparent spin
relaxation time has been shown to dramatically increase with increasing temperature and is
longer than several ns at room temperature. Long spin polarization life-time in diluted nitrides
can be explained by the spin-dependent recombination (SDR) model initially developed by
Weisbush and Lampel in AlGaAs [16]. As will be discussed later, this unusual spin dynamics is
due to a large concentration of the NR paramagnetic centers induced by the presence of nitrogen.
15
Chapter Two: Spin dynamics
The success of spintronics relies on the ability to create, control, maintain and manipulate spin
orientation over practical time and length scales. Below we will discuss how spin orientation can
be created and detected in semiconductors by optical means and also physical mechanisms which
govern losses of this orientation.
Optical orientation and spin polarization
During all physical processes a total momentum must be conserved. Therefore, optical
excitation with circularly polarized light can provide spin orientation of carriers in a
semiconductor. The total spin of electron and hole must be equal to the angular momentum of an
absorbed photon. Photons of right or left polarized light have a projection of the angular
momentum on the direction of their propagation (helicity) equal to +1 or −1, respectively.
Linearly polarized photons are in a superposition of these two states. When a circularly polarized
photon is absorbed its angular momentum must be distributed between the photoexcited electron
in the conduction band and hole in the valence band. Probability of optical transitions within the
dipole approximation is described by a transition matrix element [17]:
𝐷𝑖𝑓 = 𝑓 𝐷 𝑖 ,
where 𝐷 is the dipole moment operator and | 𝑖, 𝑓 refer to an initial and final states, respectively.
Wavefunction of the VB holes is p-like whereas the CB electrons have the s-like wavefunction.
Due to these symmetry properties the only matrix elements not equal to zero are:
𝑆 𝐷 𝑥 𝑋 = 𝑆 𝐷 𝑦 𝑌 = 𝑆 𝐷 𝑧 𝑍 ,
where | 𝑆 refers to the conduction band state (S symmetry) and | 𝑋, 𝑌, 𝑍 refers to the p-type
coordinate parts of the Bloch amplitudes, which transforms as the coordinates x, y, z. Matrix
elements for different interband transitions are summarized in table 2.1. Two dipoles rotating
clockwise and counter-clockwise in a plane perpendicular to wave vector k (which is usually
defined as the direction of the wave vector of light propagating perpendicularly to the
semiconductor layer and normally defined to be z-axis) corresponds to hh-c transitions. The lh-c
transitions and SO-c transitions correspond to two dipoles oscillating along k and two dipoles
rotating in the plane perpendicular to k.
16
Band
Initial (VB)
Final (CB)
½
-1/2
hh
lh
SO
+3/2
−3/2
+1/2
−1/2
+1/2
−1/2
− 1/2(𝑥 + 𝑖𝑦)
0
− 2/3 𝑧
1/6(𝑥 − 𝑖𝑦)
− 1/3 𝑧
− 1/3(𝑥 − 𝑖𝑦)
0
1/2(𝑥 − 𝑖𝑦)
− 1/6(𝑥 + 𝑖𝑦)
− 2/3 𝑧
− 1/3(𝑥 + 𝑖𝑦)
1/3 𝑧
Table 2.1; matrix elements of dipole moment for different interband transitions, x and y are unit vector along a
plane perpendicular to the momentum k, z is a unit vector along k.
Figure 2.1; selection rules and relative intensities of transitions. I+ and I - are the intensities of right-and left
polarized emission, respectively.
Since matrix elements of dipole transitions are not equal for the transitions involving lh
and hh, relative intensities of these transitions are also different. Therefore, optical absorption of
the 100% circularly polarized light in the strain-free material will generate 50% of electron spin
polarization in CB, if only the hh and lh VB states are involved – see Figure 2.1. For example, if
the pumping light is σ+ –polarized the photogenerated electrons in the conduction band will be
preferentially generated in the -1/2 spin state (see figure 2.1) (Note, the two spin states in the
conduction band will be populated equally if the photon energy sufficiently exceeds Eg+Δ,
where Δ is the spin-orbit splitting). If both photo-excited electrons and holes retain their spin
orientations without spin relaxation, the reverse PL process should lead to 100 % σ+polarization
+1/2 -1/2
-3/2 +3/2
-1/2 +1/2
I+
Emission
I - I
+ I -
VB
lh
hh
+1/2 -1/2
-3/2 +3/2
-1/2 +1/2
σ+ σ+
Absorption: σ+ light ∆mj = +𝟏
lh
VB
hh
17
in optical detection. If complete spin relaxation occurs between the hole states, e.g. due to strong
hh-lh mixing, the polarization degree of optical detection should decrease down to 25 %. The
latter is defined as in equation 2.1
𝑃𝑐= I+ − I –
(I+ + I -)
,
where I+ and I - are the intensities of +- and
--polarized emission, respectively. The absolute
value of the polarization degree will be twice higher in the strained structures where the
degeneracy of the VB states is lifted and only one of the VB states is populated. A sign of the PL
polarization will depend on whether the hh or lh states are involved. For example, the PL will be
+- polarized for the hh transitions, whereas it will be
--polarized if the lh states are involved.
Spin relaxation of the CB electrons will cause a reduction of the PL polarization degree. Since
circular polarization of emission is directly linked to the spin orientation of electrons in the
conduction band created via optical orientation, circular polarization can give the information
about how much electrons are polarized. We would like to point out that no PL polarization is
expected under linear excitation (σx) as equal populations of spin-up and spin down electrons
will be generated.
Spin relaxation
Central issue for developing spintronic devices is how to preserve spin orientation of
carriers. Understanding of spin relaxation mechanisms is, therefore, required. Spin relaxation, i.e.,
disappearance of initial non-equilibrium spin polarization, can be generally understood as a
result of the action of fluctuating in time magnetic fields. In most cases, these are not real
magnetic fields, but rather “effective” magnetic fields originating from the spin–orbit, or,
sometimes, exchange interactions. The magnetic field causes spin precession around the field
direction. However, as the latter randomly changes in time, the initial spin information will be
completely lost after several changes.
Two main parameters describing spin relaxation are spin precession frequency in random
magnetic field, ω, and its correlation time 𝜏𝑐 , i.e., the time during which the field may be roughly
considered as constant. These two parameters are the most commonly used to explain any
mechanism of spin relaxation.
Elliot-Yafet Mechanism [17, 18]
The electrical field, accompanying lattice vibrations or the electric field of charged
impurities is transformed to an effective magnetic field via the spin–orbit interaction. Thus
momentum relaxation is usually accompanied by spin relaxation. For phonons, the correlation
Eq. 2.1
18
time is on the order of the inverse frequency of a typical thermal phonon. Spin relaxation by
phonons is normally rather weak, especially at low temperatures.
In the case of charge impurities, scattering by an impurity center causes a change of
effective magnetic field and, thus, a change of mean spin direction. As a result, spin relaxation
time can be expressed as the function of scattering time and scattering angle. Thus, spin
relaxation rate is proportional to impurity concentration.
Dyakonov-Perel Mechanism [20]
The Dyakonov-Perel mechanism is due to spin orbit splitting of the conduction band due
to bulk inversion asymmetry (BIA) in non-centro-symetric semiconductors. In this case the
precision frequency is dependent on momentum of electron, ω=Ω(p). An electron with a certain
momentum will experience an effective magnetic field caused by spin-orbit splitting and hence
starts its precession motion around an effective magnetic field axis. If the electron takes long
time before relaxing to a lower momentum state, electron will precess long enough to forget an
initial spin state. So, the spin relaxation time is mostly controlled by momentum relaxation time
at a certain momentum,
1
𝜏s
~Ω 2 𝑝 𝜏p,
where Ω(p) has three components along crystals axis,
Ωx(p)~px(py2 − pz
2), Ωy (p)~py(pz2 − px
2), Ωz(p)~pz(px2 − py
2).
In contrast to the Elliott–Yafet mechanism, now the spin rotates not during, but between the
collisions. Accordingly, the relaxation rate increases when the impurity concentration decreases.
Bir-Aronov-Pikus Mechanism [21]
Bir-Aronov-Pikus mechanism is mainly caused by the exchange interaction between
electrons in the conduction band and holes in the valence band. According to this mechanism,
spin relaxation rate is proportional to a number of holes. In other words, spin relaxation of an
electron in the CB is contributed by exchange interaction with all electrons in the VB.
Spin relaxation of holes in the valance band
In the VB, spin relaxation time is mainly controlled by the spitting between the lh- and hh
states. One can say that the hole “spin” J is rigidly fixed with respect to its momentum p, and
19
because of this, momentum relaxation leads automatically to spin relaxation. For this reason,
normally it is virtually impossible to maintain an appreciable non-equilibrium polarization of
bulk holes and their spin direction is absolutely random.
20
Chapter Three: Spin Dependent Recombination (SDR)
General principles of SDR
As was mentioned in chapter one, GaNAs shows fascinating spin dynamics of carriers at room
temperature. Long spin polarization life-time in diluted nitrides can be explained within the
framework of the SDR model initially developed by Weisbush and Lampel in AlGaAs [16]. The
SDR mechanism is due to the well known Pauli principle which states that two electrons cannot
have the same spin orientation in the same orbital state. The key point in SDR is the existence of
a deep paramagnetic center which possesses an unpaired electron before trapping a CB electron.
As a consequence, if the photogenerated electron in the CB and the resident electron on the deep
center have the same spin, the photo-generated electron cannot be captured by the center. The
SDR effect can be explained as the following:
1. In the absence of photoexcitation, an electron at a deep defect level is not spin polarized.
The center can only capture a photogenerated electron from the CB with a spin
antiparallel to the spin of the electron present at the center (figure 3.1 a)).
2. Once the deep paramagnetic center is occupied by two electrons, no more electrons can
be captured by this center until one of electrons (of either spin) recombine with a VB hole
(figure 3.1 b)).
3. Even though the capture process of the CB electron by the center is spin-selective,
recombination of electrons trapped by the center with the VB holes is not. Thus, after a
few circles electrons left on the center become dynamically spin-polarized.
4. When the center is polarized, it acts as a spin-selective filter. The photogenerated CB
electron with a spin direction opposite to that of the center is immediately captured and
recombines with the VB holes. As a result, only the electrons with spins parallel to that
of the center are left in the CB. (Figure 3.1 c)).
5. The same spin orientation of conduction and defect electrons prevents the former from
being captured by the defect, resulting in higher concentrations of free carriers. The only
remaining recombination channel under these conditions is band-to-band recombination-
see figure 3.1 d).
21
Figure 3.1 a); photo-generated electrons are created by circular polarization excitation; populations of the spin up
and spin down states are not equal due to optical selection rules. Electrons with a spin direction opposite to that of
a paramagnetic center are immediately captured. Due to the Pauli exclusion principle, capture of the electrons with
opposite spin is blocked. b) Once the center forms a singlet state, the capture process is stopped. One of the
captured electrons with either spin recombines with a VB hole. The paramagnetic center is again ready to capture
electrons. c) After some circles the electron trapped by the paramagnetic center is dynamically polarized. Any
electron with the spin direction opposite to that of the trapped electron is extracted from the CB which results in
complete spin polarization of the CB electrons. d) The same spin orientation of conduction and defect electrons
blocks the defect-related recombination channel. Carrier recombination is only possible as a result of band-to-band
transitions.
Optical orientation in the presence of a deep paramagnetic center
Figure 3.2 demonstrates effects of the SDR process on the band-to-band recombination.
If the excitation light is linearly polarized, photogenerated electrons are not polarized. Thus, the
capture process by the center is efficient. Under these conditions the recombination via the center
efficiently competes with the band-to-band recombination and hence the corresponding PL
intensity is low. On the other hand, when the excitation light is circularly polarized, the electrons
are photo-generated with preferential spin orientation. Therefore, the electron trapped by the
centers can be dynamically polarized and, hence, the capturing process is blocked. Therefore, the
band-to-band recombination is more efficient, resulting in the higher intensity of the PL signal.
VB
CB
3.1 d) VB
CB
3.1 c)
Forbidden
VB
CB
3.1 b)
STOP
P
𝜎+
VB
CB
3.1 a)
22
Figure 3.2; optical excitation and recombination transitions observed under linear (the left part of the Figure) and
circular (the right part of the Figure) excitation, respectively.
SDR ratio
An SDR ratio is used as an indicator of the SDR process since in this case a total PL
intensity under linear excitation always lower than that under circular excitation. The SDR ratio
is defined as in equation 3.1:
𝑆𝐷𝑅 𝑟𝑎𝑡𝑖𝑜 =𝐼𝜎+𝑜𝑟 𝜎−
𝐼𝜎𝑥,
where, 𝐼𝜎+𝑜𝑟 𝜎− and 𝐼𝜎𝑥 are total PL intensities detected under the circular and linear excitations
respectively. When the SDR process dominates, the SDR ratio will be higher than one. This ratio
indicates to what degree the capture of the photogenerated electrons by the center can be blocked
when the centers are dynamically polarized and, hence, the SDR ratio is proportional to the spin
polarization of the CB electrons.
Several processes affect the dynamic behavior of the photogenerated carriers. Firstly, the
depletion rate of free carriers is determined by their capture by the centers. This process is spin-
dependent. Secondly, the recombination between the trapped electrons and the VB holes is also
essential. Since the VB holes rapidly loose their spin orientation, this process is spin independent.
The band to band recombination also contributes to carrier dynamics. All these processes can be
described by the following coupled nonlinear rate equations 3.2 [2]:
𝑑𝑛±
𝑑𝑡= −𝛾𝑒𝑛±𝑁∓ −
𝑛± − 𝑛∓
2𝜏𝑠+ 𝐺± −
𝑛±
𝜏𝑑,
𝑑𝑁±
𝑑𝑡= −𝛾𝑒𝑛∓𝑁± −
𝑁± − 𝑁∓
2𝜏𝑠𝑐+
1
2𝛾𝑝𝑁↑↓,
𝜎+
VB
CB
𝜎+ 𝜎𝑥
VB
CB
𝜎− 𝜎+
Eq. 3.1
23
𝑑𝑝
𝑑𝑡= −𝛾𝑝𝑁↑↓ + 𝐺+ + 𝐺− −
𝑛+ − 𝑛−
𝜏𝑑,
𝑁𝑐 = 𝑁↑↓ + 𝑁+ + 𝑁−, 𝑝 = 𝑛+ + 𝑛− + 𝑁↑↓,
where 𝑛± denotes the number of photogenerated electrons with spin up and down respectively.
𝑁± is the number of the paramagnetic centers with a single spin up/down electron, 𝑁↑↓ is the
number of the centers that already form a singlet state and 𝑁𝑐 is the total number of the defect
centers contributing to the spin filtering process. 𝛾𝑒 (𝛾 ) is a capture coefficient for electrons
(holes), which is characteristic for the defect. 𝜏𝑠 (𝜏𝑠𝑐 ) is spin relaxation time of the free (trapped)
electrons. The density of free holes is denoted by p. 𝐺± is the photo-generation rate of the spin
up and spin down electrons. τd denotes the free carrier decay time, including all radiative and
spin-independent non-radiative recombination channels except that via the paramagnetic center.
The SDR process is power dependent. Before the defects start to spin filter the free
electrons they need to be dynamically polarized. This is only possible if the number of the
photogenerated electrons is higher than the number of the defect centers.
Two spin pools picture
Let us simplify description of the SDR process by considering two spin pools as
schematically shown in Figures 3.4 a) and b). Suppose that the CB electrons can be subdivided
into two sub groups, spin up and spin down pools. In the SDR process, once the center is
polarized, the pool with the spin orientation opposite to the center will be depleted. The capture
process is very fast initially, however, when all the centers are occupied, the capture process will
stop. Therefore, this decay process of the CB electrons is controlled by how fast the trapped
electrons recombine with the holes.
After one pool is depleted, another decay process will start. This decay process is
controlled by spin relaxation. As shown in figure 3.4 c) if the electron flips its spin, it will be
transferred to another pool and quickly depleted by the center (see figure 3.4 d)). Thus, the PL
decay contain two components related to the hole capture and electron spin relaxation.
Eqs. 3.2
24
Figure 3.4 a) and b); the idea of two spin pools, the deep paramagnetic center acts as a spin filter depleting
electrons in the spin up pool, decay time of this process is mainly controlled by hole recombination life time. c) and
d). After spin up pool is empty the PL decay time is controlled by spin relaxation which causes spin flips to the
other pool.
Physical realization of an efficient spin dependent-recombination process
Since the proposal of SDR, slightly enhanced electron polarization Pe in e.g. AlGaAs and
GaAs by optical orientation has been demonstrated at low temperatures and was attributed to an
SDR process via deep-level defects. However, it is only until very recently that a giant Pe was
achieved at RT in Ga(In)NAs [22, 23]. From cw- and time-resolved PL, it was shown that very
high degree of circular PL polarization can be achieved in optical orientation experiments in
these alloys, in sharp contrast with the parental GaAs. Moreover, according to the time resolved
PL measurements [22], this circular polarization in GaInNAs remained practically constant
within the measurement window of 2 ns in GaNAs QW whereas it rapidly decreased with a
UP DOWN
Capture by center
Capture by hole
HOLE
Spin flip due to spin relaxation
UP DOWN
HOLE
100% spin polarization 3.4 c)
UP DOWN
Capture by hole
HOLE
SLOW
3.4 b)
UP DOWN
Capture by center
HOLE
FAST
3.4 a)
3.4 d)
25
characteristic time of 50 ps in the N-free QW (see figure 3.5). This indicated that nitrogen
incorporation caused an apparent increase of the spin relaxation time.
The physical mechnism behind this finding as being due to the SDR process was
suggested by V.K. Kalevich et. al. [23] who found that the strong PL polarization is
accompanied by the strong SDR ratio and that both of them can be suppressed in transvered
magnetic fileds.
Figure 3.5 a); PL and PL polarization of the N-free and N-containing QW sample with N=0.6%. b) Decays of the
circular polarization detected from the same samples as in a) [22].
Figure 3.6 a); calculated energy levels associated with the electronic and nuclear spin states of the Gai2+
defect. The
allowed ESR transitions (mS=±1 and mI=0) occur when the electron spin splitting matches the microwave photon
energy, and are marked by the vertical lines. b) Typical ODMR spectra by monitoring the total intensity of the BB
PL from an RTA-treated GaN0.021As0.979 epilayer, obtained at 3K under x and +
excitation at 850 nm. The
microwave frequency used is 9.2823 GHz. A simulated ODMR spectrum of the identified Gai defect (denoted by Gai-
C) is also shown. From Ref.[2]
3.6 a) 3.6 b)
26
In order to identify the SDR-active defects and thus to provide the first unambiguous
proof that the strong Pe can indeed be generated by SDR, a combination of optical orientation
with the optically detected magnetic resonance (ODMR) technique was employed [2]. ODMR is
known to be sensitive to SDR, especially if SDR acts as a dominant carrier recombination
channel, and also to be able to identify chemical nature of defects in semiconductors. A Gai2+
self-interstitial was unambiguously identified as the common core of the defects responsible for
the monitored SDR, based on a hyperfine structure – see Figure 3.6 This study has shown a
promising way to construct a spin filter by introducing a suitable defect center to a
semiconductor material.
27
Chapter Four: Experimental Approach
Optical orientation PL spectroscopy
PL spectroscopy is a contactless and non-destructive method of probing the electronic
structure of a semiconductor. The principle of the PL measurements is simple: when a
semiconductor sample is optically excited with a photon having energy above the band gap of
the semiconductor, electrons and holes are created, usually in the near surface region by
absorption of the excitation light. These photogenerated electrons and holes diffuse into the bulk
and at the same time, they relax and recombine via various channels. Some of the most important
applications of the PL spectroscopy are listed below:
Bandgap determination: Radiative transitions in semiconductors can occur between
states in the conduction and valence bands, with the energy difference equal to the
bandgap energy. This can be used to determine the bandgap energy of the semiconductor
provided that the origin of the PL transitions is proven to be the band-to-band
recombination.
Impurity levels and defect detection: Radiative transitions in semiconductors often
involve localized defect levels. The PL energy associated with these levels can be used to
identify specific defects, and the PL intensity, if calibrated, can be used to determine their
concentration.
Recombination mechanisms: The return to equilibrium, known as recombination, can
involve a radiative recombination process. Properties of the corresponding PL such as its
line shape, dependences of the PL intensity on photo-excitation power and temperature
can be used to understand the origin of the radiative recombination.
Material quality: In general, competing NR processes are associated with localized
defect levels, whose presence is harmful to material quality and subsequent device
performance. As the NR processes compete with PL, material quality can be evaluated by
quantifying an amount of radiative recombination.
A typical PL set-up can be divided into three parts; an excitation side, a cryostat, and a detection
side.
Excitation side: An excitation source is used to create photogenerated electron-hole pairs. In our
experiments, a tunable Ti-sapphire laser was used for these purposes. Resonance cavity
conditions in a Ti-sapphire rod can be adjusted to tune the laser wavelength within the range of
750-1100 nm. Long Wavelength Past (LWP) and Short Wavelength Past (SWP) filters were used
to avoid any leakage of stray laser light.
28
A focusing lens was placed close to a cryostat window. Since the SDR process is
sensitive to the excitation power, the laser beam was focused. For this purpose, a fine adjustable
lens holder was used.
Cryostat: PL measurements are often performed at low measurement temperatures, i.e around T
= 3 - 6 K. This can be achieved by using liquid He which flows into a cryostat where a sample is
placed. The cryostat usually consists of four chambers. A vacuum chamber with vacuum in the
range of 10−6 mbar is used to thermally isolate other chambers from the environment. The 2nd
chamber contains liquid nitrogen to pre-cool the sample chamber down to the temperature of
around 160 K. The 3rd
chamber will be filled with liquid He. The helium chamber and the sample
chamber are linked via a needle valve. The He flow between these chambers can be controlled
by using a mechanical pump. The temperature can be adjusted in the range of 2-9 K by changing
the flow rate. To achieve temperatures from 10 to 300 K, a heater is used.
Detection side: The PL signal from a sample can be collected and focused by two lenses on an
entrance slit of a monochromator. A photodetector will then register the PL emission. Two types
of detector were used in this work, i.e. a Si charge-coupled device (CCD) and a Ge detector. The
former is sensitive in the spectral range of 300 – 1050nm, whereas the later can be used to detect
emissions with longer wavelengths up to 1600 nm. By scanning the monochromator through the
desired energy range, and registering the intensity, a PL spectrum is obtained.
Lock-in technique
The PL signals were detected using the lock-in technique. By modulating the intensity of
the excitation light beam at a certain frequency and using a lock-in amplifier, stray light, that is
not connected to the PL emission, will be discriminated – see Figure 4.1.
Figure 4.1; lock-in amplifier technique; only a signal in-phase with reference is amplified and noise can be
subtracted.
29
The PL set up can be easily modified for optical orientation measurements by placing
appropriate polarizers in detection and excitation optical paths. At the excitation side, the
excitation beam is circularly polarized by installing a linear polarizer followed by a quarter wave
plate. If optical axis of the quarter wave plate is rotated ±45 degree from the optical axis of
incoming linearly polarized light, right-handed (σ+) and left-hand (σ -) polarized light (see figure
4.2) will be produced. On the detection side, a quarter wave plate combined with a linear
polarizer are again used to monitor a polarization state of the PL emission. The experimental
set-up used for optical orientation measurements is shown schematically in figure 4.3.
Figure 4.3; photoluminescence set up for optical orientation PL measurements, the set up is a typical PL set up
with retarders installed to produce/ detect circularly polarized light.
Ar+ laser Ti: sapphire
Linear polarizer
𝜆/4 retarder
Focusing lens
Lock-in amplifier
Chopper
sample
Cryostat Collection lens Focusing lens
Linear
retarder
Monochrometer
Detector
Computer
Figure 4.2; the principle of a retarder. The
principle of retarder; the figure represents
quarter wave plate retarder, in case that linearly
polarized input is deviated 45 degree from optical
axis, the output will be circularly polarization
according from the chance in phase delay speed
when light passes though the retarder.
30
Magnetic resonance technique
Electron Paramagnetic Resonance (EPR)
EPR is a spectroscopic method1 which can be used to study paramagnetic systems, i.e. systems
containing one or several unpaired electron. An unpaired electron has an intrinsic spin angular
momentum S with an associated magnetic moment 𝒎 = −𝜇𝐵𝒈𝒆𝑺 where 𝑔𝑒 is the electron g-
factor and 𝜇𝐵 is the Bohr magneton. If the unpaired electron is placed in a static magnetic field B,
the so-called Zeeman interaction energy between the applied field and the magnetic moment is
given by the classical expression E = -m·B. This expression can be represented by the spin
Hamiltonian
𝑯 = 𝜇𝐵𝒈𝒆 ∙ 𝑺 ∙ 𝑩.
There are two allowed directions of the electron spin S=1/2, parallel or antiparallel to the
direction of the static magnetic field B, which is applied along the z-axis. These can be
represented by the two spin states |1
2,
1
2 and, |
1
2, − 1
2 respectively, having the corresponding
spin quantum number 𝑚𝑠 = ±1/2. The degeneracy of the energy level of the electron will thus be
removed in the presence of the external field as shown in Figure 4.4, in which the level is split
into two sublevels. In order to induce a transition between two sublevels, an electromagnetic
field with energy quanta hν with the time-dependent component perpendicular to the static
magnetic field is applied. In thermal equilibrium the population difference between the two spin
states is given by the Boltzmann distribution
𝑁−
𝑁+= exp(−𝑔𝑒𝜇𝐵𝐵𝑧/𝑘𝐵𝑇),
𝑁− and 𝑁+ are the populations of the different spin states. At normal temperature (T< 300 K), a
slight difference in the relative population between the two states is anticipated, and hence it is
possible to induce a transition. If an energy quantum hν is absorbed the following condition must
be satisfied according to Planck’s law
𝜈 = 𝜇𝐵𝒈𝒆 ∙ 𝑺 ∙ 𝑩.
This relation defines the basic resonance condition in the EPR experiment. The energy separation
between the two sublevels depends on the magnitude of the applied magnetic field. Note that the
1 It is also reffered as Electron Spin Resonance (ESR).
Eq. 4.1
Eq. 4.2
Eq. 4.3
31
value of the g-factor in a semiconductor deviates from the free electron value ge = 2.0023. This is
due to the effect of the orbital angular momentum L of the unpaired electron. The g-value is
usually anisotropic, i.e. the magnitude depends on the direction of the static magnetic field
relative to the orientation of the paramagnetic centre.
Figure 4.4; microwave induced transition and corresponding EPR signal of two cases: a) S=1/2, I=0 and b) S=1/2,
I=1/2.
In practice, an EPR setup basically consists of several essential parts such as a cavity
where the sample is placed, a magnet to produce the static magnetic field and an electromagnetic
source, usually with a fixed frequency in the range of 9-95 GHz. The resonance occurs when the
energy separation between two states caused by an applied magnetic field is identical to the
microwave energy – Equation 4.3. In order to increase the sensitivity of the spectrometer, a small
AC component is added to a DC magnetic field. This results in an AC modulated EPR signal,
which can be detected using a lock-in amplifier. Consequently, the EPR spectrum is recorded as
the first derivative of microwave intensity dI/dB reflected from the cavity versus the magnetic
field B (see Figure 4.4.)
The EPR technique has been successfully applied to study the electronic structure and
identification of defects in semiconductors. In a more general form, Equation 4.1 can be
rewritten as
𝑯 = 𝜇𝐵𝒈𝒆 ∙ 𝑺 ∙ 𝑩 + 𝑺 ∙ 𝑫 ∙ 𝑺 + 𝑺 ∙ 𝑨𝒊
𝒊
∙ 𝑰𝒊.
Here 𝑺 and 𝑰𝒊 represent an effective electronic spin and a nuclear spin of a defect or
ligand atom i. the anisotropy of the g-tensor and D-tensor reflects the symmetry of the crystal
E E
+1/2
-1/2
-1/2
+1/2
b)
dB
dI
B
B
mS=+1/2
mS=-1/2
B
dB
dI
S=1/2 S=1/2
B
mS = -1/2
mI I=1/2
a)
mS=+1/2
Eq. 4.4
32
lattice and the defect. The first term describes the usual linear term of electron Zeeman
interaction. The second term introduces a fine structure, i.e. zero-field splitting, important only
for S > 1/2. The most important information in EPR experiments is usually obtained from the
hyperfine coupling, which is due to the interaction between the magnetic moments of the
effective electronic spin S and the nuclear spin Ii, which is described by the third term in
Equation 4.4. The nuclear Zeeman term and the other higher order terms have not been included
in Equation 4.4 due to their negligible effects in most cases of EPR and ODMR investigations.
Let us consider a simple case (S=1/2) with an isotropic g-factor and an isotropic central
hf interaction which is small compared to the electron Zeeman interaction. Equation 4.4 can be
solved by a perturbation theory in the first order and for energies one obtains
𝐸 = 𝑔𝜇𝐵𝐵𝑚𝑆 + 𝐴𝑚𝐼𝑚𝑆 ,
with eigenfunctions Ψ = | 𝑚𝐼 , 𝑚𝑆 . For S=1/2, I=1/2 there are now four energy levels instead of
two without the hf interaction because of the mS = ±1/2 and mI = ±1/2 quantum numbers.
Application of a microwave field induces the EPR transitions with the selection rule
∆𝑚𝑠 = ±1, ∆𝑚𝐼 = 0.
Instead of one transition observed in the case of I=0, there are now two lines with the separation
between them ∆B=A/(gμB).
In general, there are 2I+1 lines due to hf splitting. By analyzing the hf pattern obtained
from EPR spectra we are able to identify the chemical and electronic properties of the defect and
its surroundings. One excellent example of this can be found in ref. [15] where two Ga
interstitials were ambiguously identified based on the analysis of the hf interaction. Gallium
consists of two isotopes, 69
Ga with 60.4% abundance and 71
Ga with 39.6% abundance. Both
isotopes have a nuclear spin I=3/2. The hf interaction of each isotope with an unpaired electron
gives rise to four transitions with the contribution to the relative intensity following the ratio of
natural abundances. Due to the difference in their nuclear magnetic moment, the two Ga isotopes
give rise to slightly different hf splittings leading to a characteristic hf structure shown in Figure
4.5. This is the signature of the hf interaction involving a Ga atom.
Though EPR shows a great potential in defect indentification, it still has some limitations.
First of all, a paramagnetic ground state is required. Some defects have zero-spin ground state
and thus cannot be detected in EPR. Secondly, no information on carrier recombination related to
defects can be obtained by EPR. And thirdly, the sensivity is low due to microwave detection.
Fortunately, the first limitation can be overcome if another charge state of the same defect can be
reached by changing the Fermi level position, e.g by doping with shallow impurities or by
Eq. 4.5
Eq. 4.6
33
illuminating samples. The last two limitations could only be resolved if another methods or
extended techniques are used. A combination of EPR with optical detection methods such as PL
is a solution to the problems.
Optically Detected Magnetic Resonance
Optically detected magnetic resonance is a combination of EPR and PL. The technique is
based on the fact that the recombination processes are spin-dependent. When the microwave
field induces transitions between two Zeeman sublevels that have different recombination rates
or polarizations, the total PL intensity or its polarization can be changed. ODMR spectrum is
obtained by a measurement of this change versus magnetic field (Figure 4.6). Figure 4.7 shows a
schematic illustration of an ODMR setup.
ODMR measurements not only preserve all the potentials from conventional EPR and PL
but also add more advantages. It is more sensitive due to higher sensitive optical detection over
the microwave detection. This advantage makes ODMR suitable for studies of thin films, layered
and quantum structures. The radiative recombination spectrum from PL measurements of a deep
level defect often shows up as a broad featureless band, from that, very little information can be
obtained. By measuring the spectral dependence of the ODMR signal, the ODMR spectrum can
be assigned to the relevant PL spectrum of a specific defect, which is suitable for studies of
carrier recombination processes and for assigning them to corresponding defects.
Typical ODMR set up is shown in Figure 4.7. The sample is placed in a microwave
cavity inside a cryostat to obtain liquid He temperature. Liquid He is continually supplied by a
He transfer tube which is connected to a liquid He reservoir. A static magnetic field is provided
by a magnetic coil. A microwave field with a frequency of about 9.5 MHz (X-band) is generated
3200 3400 3600
(a)
(b)
(c)
95GHz
OD
MR
Inte
nsi
ty (
a.u.)
Magnetic field (mT)
Figure 4.5; (a) simulation at 95GHz of
the hf splitting arising from the
interaction between an unpaired
electron and the nuclear spin of a Ga
atom. The contribution from (b) 69
Ga
and (c) 71
Ga.
34
in the cavity by a microwave generator through a waveguide. The microwave frequency is
always kept constant and the static magnetic field can be swept from 100 to 10000 Guass by
applying a current to the magnetic coil. Optical detection is used. For these purposes, the PL
emission from the sample is excited by a laser (Ti-Sapphire for GaNAs) and is detected by a
detector without a monochromator. The PL signal is detected by selecting proper LWP and SWP
filters.
Figure 4.7; schematic illustration of an ODMR set-up.
Ar+ laser Ti: sapphire
Linear polarizer
𝜆/4 retarder
Focusing lens
Lock-in amplifier
Chopper
Collection lens Focusing lens
Detector
Computer
Microwave
generator
Chopper
Static magnetic field
E
B
B
S=1/2
𝑛1
1
𝑛2
2
k2
k1
∆I
Figure 4.6; principle of an ODMR experiment.
Microwave field induces a transition between two
sublevels. The ODMR signal is obtained as a
change of total light ∆I~∆k∆n.
n1, n2 populations of the spin at sublevels.
∆k= k1- k2 the difference in recombination rates of
two sublevels.
∆n number of carriers transferred between two
sublevels due to microwave field.
35
Chapter Five: Experimental Results
Defect Engineering for Spin Filtering Effect in GaNAs
According to previous findings, GaNAs is a very promising material for spin filtering
which can be accomplished at room temperature and without application of an external magnetic
field. However, the fundamental knowledge on how to control and optimize this ability is still
lacking. The purpose of this work is to understand effects of growth parameters and structural
design on the formation of deep centers responsible for SDR aiming at optimization of spin
filtering. First of all, the effect of quantum confinement on the spin filtering ability is examined.
This is performed under conditions of electron injection from GaAs barrier layers, i.e. under
conditions relevant to device applications. Secondly, optimization of the fabrication conditions
(i.e. growth temperature and post-growth annealing) for efficient formation of spin-filtering
defects is performed. Effects of doping on the formation of these defects are also analyzed. And
finally, defect formation during different epitaxial processes, such as molecular beam epitaxy
growth (MBE) and metal-organic chemical vapor deposition (MOCVD), is also studied.
5.1 Defect engineered spin filter from a low dimensional semiconductor structure; spin
filtering effect in QW structures
In this set of measurement, PL and ODMR measurements under optical orientation were
performed for a set of GaNAs multiple quantum well (MQW) structures. Parameters of the
samples are summarized in table 5.1.1. The measurements were performed at room temperature
(300 K) for optical PL orientation and at 6 K for ODMR. Excitation laser beam was aligned
parallel to a growth direction.
Sample
QW
width
GaAs
barrier
width
GaAs
buffer
layer
GaAs
capping
layer
Growth
method
Growth
Temperature
Substrate
Nitrogen
composition
(%)
GaAs
band-
(300 K)
GaNAs
peak
(300K)
2521
30 Å
7-
period
202 Å
2500 Å
500 Å
MBE
420 C
Semi-
insulating
GaAs
1.6
875.5
nm
956.5
Nm
2522
50 Å
7-
period
202 Å
2500 Å
500 Å
MBE
420 C
Semi-
insulating
GaAs
1.6
875.5
nm
987.0
Nm
2523
70 Å
7-
period
202 Å
2500 Å
500 Å
MBE
420 C
Semi-
insulating
GaAs
1.6
875.5
nm
997.0
Nm
36
Table 5.1.1; parameters of the structures, all samples contain 7-periods GaN0.016As0.984/GaAs QWs grown on a
semi-insulating GaAs substrate with a GaAs capping layer.
The excitation wavelength was 827 nm. Under these conditions most of the carriers
participating in the band-to-band recombination in the GaN0.016As0.984 QWs are injected from
GaAs, since a total thickness of the GaAs barriers is much larger than that of the GaNAs QWs.
For GaAs, such excitation can be used for optical orientation as the spin-orbit--split VB states do
not participate in the absorption process and a preferential spin orientation of the CB electrons is
created. Circular polarization and the SDR ratio are detected via the GaNAs- related band-to-
band PL emission, to determine the ability of this material to spin filter the injected electrons.
Figure 5.1.1; PL spectra of the GaNAs/GaAs QW samples. The low energy PL band originates from the band-to-
band emission in the GaNAs QWs.
PL spectra of the investigated samples are shown in figure 5.1.1. The strong band-to-band
emission was observed at room temperature for all samples, allowing the SDR measurements.
The results of these measurements are summarized in figure 5.1.2, taking as an example the 2521
sample. The SDR ratio of 1.23 at the PL peak position and a circular polarization degree of 12%
were observed for the excitation power W of 200 mW.
2524
90 Å
7-
period
202 Å
2500 Å
500 Å
MBE
420 C
Conducting
GaAs
1.6
875.5
nm
1003.5
nm
800 850 900 950 1000 1050 1100
2521 N = 1.6% 30 A
2522 N = 1.6% 50 A
2523 N = 1.6% 70 A
2524 N = 1.6% 90 A
PL
Int
ensi
ty (
Arb
itar
y un
it)
wavelength (nm)
Full spectrum 2521, 2522 and 2523 multi-QW(300 K)
exc. wavelength 827 nm
Exc. power = 200 mW
37
Figure 5.1.2; results of optical orientation measurements performed for the 2521 sample.
Fig. 5.1.3; power dependences of the SDR ratio (a) and the circular polarization degree (c-d) measured for the
investigated QW samples.
0 50 100 150 2000.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6a)
2521 L = 30 A
2522 L = 50 A
2523 L = 70 A
2523 L = 90 A
cir
cu
lar
po
lari
za
tio
n
cir
cu
lar
po
lari
za
tio
n
cir
cu
lar
po
lari
za
tio
n
excitation power (mW)excitation power (mW)
excitation power (mW)
SD
R r
ati
o
excitation power (mW)-50 0 50 100 150 200 250
-0.10
-0.05
0.00
0.05
0.10b)Exc:
0 50 100 150 2000
5
10
15
20
c)Exc:+
0 50 100 150 200 2500
-5
-10
-15
-20d)Exc:
900 960 1020 900 960 1020
900 960 1020 900 960 1020
1.0
1.2
1.4
1.6
-5
0
5
10
15
20
-20
-15
-10
-5
0
5
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
PL I
nten
sity
(A
rb.U
nits
)Exc:
x
2521
T: 300 K
Cir
cula
r po
lari
zatio
n C
ircu
lar
pola
riza
tion
Exc:
Det:
+
Exc:
Laser power: 200 mW
Excitation wavelength : 827 nm
Det:
+
C
ircu
lar
pola
riza
tion
Exc:+
Wavelength, (nm)S
DR
Rat
io (/
Det:
+
L = 30 A
38
Both SDR ratio and circular polarization degree decrease with decreasing excitation
power, as shown in figure 5.1.3. The same trend was observed for all investigated structures: the
SDR ratio and the PL polarization degree increase with W and saturate at high excitation powers.
This can be explained by dynamic polarization of paramagnetic defect centers. When W is low, a
number of photogenerated electrons is lower than a number of deep paramagnetic centers.
Therefore, the centers are not polarized and photogenerated electrons are rapidly depleted by the
centers. After increasing the excitation power the number of electrons becomes high enough to
polarize the centers and the SDR process dominates. Further slight increase of W will not affect
the center polarization and the SDR ratio and spin polarization saturate.
Also obvious from Figure 5.1.3, the saturation value of the SDR ratio increases with
increasing width of the QW. Possible explanations for this effect are as follows.
1. The effect of band-to-band recombination; quantum confinement- induced enhancement
of the band-to-band recombination rate in narrow QWs.
In narrow QW structures, strong confinement-induced overlap of electron and hole wave
functions promotes the efficient band-to-band recombination. This would suppress
importance of the defect-related recombination and the SDR process and would degrade
the spin filtering.
2. The effect of electron spin relaxation; acceleration of electron spin relaxation in narrow
QWs.
Spin relaxation usually accelerates in narrow QWs, promoted via the Dyakonov-Perel
mechanism [20]. This would diminish the ability of the injected electrons to polarize the
defect centers which would, in turn, lead to a reduction of the SDR ratio.
To identify chemical nature of the deep paramagnetic defects responsible for the SDR
process in the investigate samples and to determine the origin of the observed degradation of the
spin filtering efficiency in the narrow QWs, ODMR measurements were performed. A typical
ODMR spectrum is shown in Figure 5.1.4 a). Similar spectra were also detected from other
structures. The ODMR spectrum shows the following two distinct features originated from
different defects. The first one is a single strong line situated in the middle of the ODMR
spectrum, with a g-value close to 2. Due to a lack of hyperfine (HF) structure, unfortunately, the
chemical nature of the corresponding defect cannot be identified. Below we shall simply refer to
it as the “unknown 1” defect. The second feature of the ODMR spectra consists of a complicated
pattern of lines spreading over a wide field range. Such multiple ODMR lines arise from a high
39
electron spin state exhibiting a zero-field splitting caused by a defect crystal field or from HF
interaction involving a high nuclear spin, or from several overlapping ODMR signals due to
different defects. To resolve this issue, the obtained ODMR spectrum was compared with the
results of Ref.[2]. It was found that the ODMR spectrum in fact consists of three groups of lines
from three different defects (denoted as Gai-A, Gai-B and Gai-C).
Figure 5.1.4 a); ODMR spectrum of sample 2523, simulation fitting indicated the mixing of three kinds Gai defect
denoted A, B and C. ODMR spectrum was measured under both linear and circular excitation but nothing
significantly change was observed. b) Simulation curve of all defects participating to ODMR spectra. c) Simulation
cruves o f each Ga-interstitial defect with two natural isotopes abundance.
Indeed, the spectrum can be simulated using a spin-Hamiltonian
𝑯 = 𝜇𝐵𝒈𝒆 ∙ 𝑺 ∙ 𝑩 + 𝐴𝑺 ∙ 𝑰
Here, 𝜇𝐵 is the Bohr magneton, g the electronic g-factor, and A the hyperfine parameter.
Hyperfine parameter is set to be a scalar due to the fact that the ODMR spectrum is isotropic
with a rotation of magnetic field B with respect to the crystallographic axes. Spin Hamiltonian
parameters of the Gai- related defects were taken from ref. [15] and ref. [2] and are summarized
in Table 5.1.3. It is apparent that the agreement between the simulations and the experimental
results is excellent, which justifies the assignment. The experimental results again confirm that
-100 0 100 200 300 400 500 600 700
x
Sim
Magnetic field (mT)
2523 L = 70 A
-100 0 100 200 300 400 500 600 700
unknown "I"
Gai-C
Gai-B
Gai-A
OD
MR
(A
rb
. U
nit
s)
total
Gai-A 71
Gai-A 69
Gai-A
total
Gai-B 71
Gai-B 69
Gai-B
total
Gai-C 71
Gai-C 69
Gai-C
a)
b)
c)
40
Gai acts as the core of the spin-dependent recombination center. This conclusion is based on the
following experimental facts. Firstly, the observed multiple ODMR lines arise from a hyperfine
structure derived from a strong interaction between an unpaired localized electron spin (S=1/2)
and a nuclear spin of an atom that has two isotopes with a nuclear spin I=3/2 and a 60/40 ratio of
natural abundance. This gives rise to four allowed ODMR transitions (mS=±1 and mI=0) for
each Ga isotope, see Fig.5.1.4 c). Ga is the only atom with such unique properties, i.e. Ga has
two naturally abundant isotopes, 69
Ga (60.4% abundant) and 71
Ga (39.6% abundant), and a
nuclear spin I=3/2 for both isotopes. Thus, the identification of a Ga atom in the defect core is
beyond doubt. Secondly, the ODMR spectra were shown to be isotropic with a rotation of
magnetic field with respect to the crystallographic axes. This finding revealed that the electron
wave-function at the defects should be s-like. This is consistent with the observed strong
hyperfine interaction, as the s-like electron wavefunction results in a strong Fermi contact term.
The Ga atom involved in the defect should then be a Gai2+
self-interstitial in which the unpaired
electron has an A1 electronic state, as a GaAs antisite was predicted to possess a non-A1 state that
should lead to a strongly anisotropic ODMR spectrum.
Type Isotope g- factor Hyperfine constant (A)
(𝟏𝟎−𝟒 𝒄𝒎−𝟏)
Gai-A
69 2.005 770
71 2.005 1000
Gai-B
69 1.960 1250
71 1.960 1590
Gai-C
69 2.000 620
71 2.000 806
Unknown “I” - 2.003 -
Table 5.1.3; spin Hamiltonian parameters of Gai A, B and C. All types of Gai interstitial defects contains two
natural Ga isotopes, i.e. 𝐺𝑎69i (60.4% abundance) and 𝐺𝑎71
i (39.6% abundance).
The intensity of the ODMR spectra was found to strongly depend on the quantum well
width as illustrated in figure 5.1.5. The observed dependence is consistent with both mechanisms
(i.e. the effect of band-to-band recombination and the effect of electron spin relaxation),
suggested to be responsible for the decreasing filtering efficiency in the narrow QW. Indeed:
1. The enhancement of the band-to-band recombination will suppress the role of the defect-
related recombination and, therefore, the ODMR intensity.
2. A reduction of the spin relaxation time for the CB electrons will lead to a weak
dynamical polarization of the paramagnetic center. This will decrease a population
41
difference between the sublevels at the defect center resulting in the weaker ODMR
intensity.
In summary, the GaNAs/GaAs multiple quantum well structures can be employed for
spin filtering of the injected electrons at room temperature. However, the quantum confinement
is found to degrade the spin filtering ability of GaNAs.
5.2 Effect of growth temperature and post-growth treatment on the SDR process
Since both growth temperature and post-growth annealing will likely influence the
formation of the NR centers, it is important to understand how they will affect the spin-filtering
process. Parameters of the samples selected for these studies are listed in table 5.2.1 a) and b).
Table 5.2.1 a); parameters of the samples used to investigate effects of RTA on the spin-filtering process.
.
Sample
Epilayer
Growth
method
Growth
Temperatu
re
Post
growth
treatment
Substrate
Nitrogen
compositi
on (%)
GaAs
band-
gap
(300 K)
GaNAs
band-gap
estimate
(300 K)
GaNAs peak
(300K)
2468
1000 Ǻ
Gas
source
MBE
420 C
-
Semi-
insulating
GaAs
1.3
875.5 nm
1026.5 nm
1018.5 nm
2468
RTA
1000 Ǻ
Gas
source
MBE
420 C RTA
Semi-
insulating
GaAs
1.3 875.5 nm
1026.5 nm
1018.5 nm
Figure 5.1.5; ODMR intensity as a
function of the QW width. The ODMR
signal increases when the QW width is
increased.
20 30 40 50 60 70 80-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
OD
MR
(a
rb.u
nit)
Well width (Å)
42
Table 5.2.1 b); parameters of the samples used to investigate effects of growth temperature on the spin-filtering
process.
Post-growth RTA
Results of optical orientation measurements performed for the samples 2468 and
2468RTA are shown in figure 5.2.1 a) and b), respectively. Both samples demonstrate the spin
filtering effect at room temperature.
Figure 5.2.1 a) and b); results of optical orientation and SDR measurements performed for the 2468 and 2468RTA
samples under the excitation power of 200 mW.
In order to quantify changes in defect concentrations after RTA, excitation power dependences
of the PL polarization degree were measured and simulated using the set of rate equations:
Sample
QW
width
GaAs
barrier
width
GaAs
buffer
layer
GaAs
capping
layer
Growth
method
Growth
Temperature
Substrate
Nitrogen
composition
(%)
GaAs
peak
(300 K)
GaNAs
peak
(300K)
2458
30 Ǻ
7-
period
202 Ǻ
2500 Ǻ
500 Ǻ
MBE
420 C
Semi-
insulating
GaAs
1.2
875.5
nm
1005.1
Nm
2513
50 Ǻ
7-
period
202 Ǻ
2500 Ǻ
500 Ǻ
MBE
580 C
Semi-
insulating
GaAs
1.1
875.5
nm
1000.8
Nm
a) b) Before RTA After RTA
43
𝑑𝑛±
𝑑𝑡= −𝛾𝑒𝑛±𝑁∓ −
𝑛± − 𝑛∓
2𝜏𝑠+ 𝐺± −
𝑛±
𝜏𝑑,
𝑑𝑁±
𝑑𝑡= −𝛾𝑒𝑛∓𝑁± −
𝑁± − 𝑁∓
2𝜏𝑠𝑐+
1
2𝛾𝑝𝑁↑↓,
𝑑𝑝
𝑑𝑡= −𝛾𝑝𝑁↑↓ + 𝐺+ + 𝐺− −
𝑛+ − 𝑛−
𝜏𝑑,
𝑁𝑐 = 𝑁↑↓ + 𝑁+ + 𝑁−, 𝑝 = 𝑛+ + 𝑛− + 𝑁↑↓,
Under the steady-state conditions:
𝑑𝑛±
𝑑𝑡=
𝑑𝑁±
𝑑𝑡=
𝑑𝑝
𝑑𝑡= 0.
For numerical fit, we have used the time constants that were reported in the literature [2], i.e. τr =
10 ns16
and τs=150 ps. τsc is insensitive in the analysis, as long as it is >1.5 ns. These parameters
were set identical for both 2468 and 2468RTA samples. This only leaves γe/γh and γeN as fitting
parameters, where N is the total defect concentration. (As the absolute values of γe and defect
concentration N cannot be determined independently in our experiments, we used a combined
fitting parameter γeN that represents a capture rate of free electrons by the defect and can also be
employed to compare relative defect concentrations in different samples.) The obtained fitting
curves are displayed by the dashed lines in Figure 5.2.2, with γe/γh =4 and γeN values given for
each sample, showing a reasonably good agreement with the experimental results.
0 50 100 150 200
4
6
8
10
12
cir
cu
lar
(sp
in)
po
lari
za
tio
n (
%)
excitation power (mW)
Before RTA: 𝛾𝑒𝑁 = 0.088 ps-1
After RTA: 𝛾𝑒𝑁 = 0.042 ps-1
2468 and 2468 RTA
Figure 5.2.2; circular (spin) PL
polarization as a function of an excitation
power. The dots denote the experimental
data. The dashed lines are the simulated
curves. After RTA, the number of defects
contributing to the SDR is reduced.
44
As shown in figure 5.2.2, after the post-growth RTA the relative defect concentration is
reduced by half. Physical nature of the SDR process can be clearly seen from this analysis. In
the 2468 sample, the number of defect centers exceeds the number of the photogenerated
electrons. Therefore, the saturation of the PL polarization can not be reached even at the highest
photoexcitation power of 200 mW as it is insufficient to polarize all defects. However, after the
RTA treatment the defect concentration is reduced and the defects can be polarized under a
lower density of the photogenerated electrons (i.e. when W=40 mW). With further increase of
W, on the other hand, the capture process becomes relatively less important, as it is limited by
the defect concentration. This degrades the spin filtering effect.
Similar conclusions are also reached from the ODMR measurements which show that the
ODMR intensity is reduced after RTA – see figure 5.2.3.
Growth temperature
Growth temperature typically influences the defect formation in a semiconductor material. To
understand its effects on the SDR process all measurements were repeated for the samples with
similar structure but grown at different temperatures, i.e. 𝑇𝑔 = 420o C for the #2458 and 𝑇𝑔 =
5800 C for the #2513. Spectral dependences of the SDR ratio and the circular PL polarization are
presented in figure 5.2.4 a) and b). Both samples unambiguously demonstrate the SDR process.
The corresponding ODMR spectra are shown in figure 5.2.5. The ODMR intensity is apparently
higher for the structure grown at lower temperature. The same conclusion was reached after
fitting the excitation power dependences of the PL polarization using the coupled rate equations -
figure 5.2.6.
Figure 5.2.3; ODMR spectra
measured from the 2468 sample
before and after RTA. The
simulation curve was obtained
assuming that the ODMR spectrum
in the as-grown sample contains
contribution from Gai-A, Gai-B and
Gai-C defects, as well as from the
“unknown 1” signal. The ODMR
intensity is dramatically reduced
after RTA indicating a reduction of
the defect concentration. -100 0 100 200 300 400 500 600 700
OD
MR
(A
rb.
Un
its)
x
Magnetic field (mT)
Simulation Gai-A+B+C+ unknown "I"
Before RTA
After RTA
45
Figure 5.2.4 a) and b); results of optical orientation and SDR measurements performed for the 2458 and 2513
samples under the excitation power of 200 mW excitation.
Figure 5.2.5; ODMR spectra
recorder from the samples grown at
𝑇𝑔 as indicated in the Figure.
a) b) 𝑻𝒈 = 420 C 𝑻𝒈 =580 C
0 100 200 300 400 500 600 700
OD
MR
(A
rb.
Un
it)
Magnetic field (mT)
Tg = 580 C
x
Tg = 420 C
46
0 50 100 150 2000
2
4
6
8
10
12C
irc
ula
r (s
pin
) p
ola
riza
tio
n (
%)
excitation power (mW)
The observed reduction of the defect concentration during the high temperature growth is
probably not surprising as at higher Tg a Ga atom arrived to a substrate will have kinetic energy
high enough to move to a suitable substitutional position to form the perfect alloy.
The results presented in this section clearly demonstrate that the concentration of Gai-
related centers responsible for SDR can be controlled by varying the growth temperature and via
the post growth annealing.
5.3 Effects of doping on the formation of the Gai-interstitial paramagnetic centers.
It is well known that the defect formation is largely affected by the Fermi level position
during the growth determined by doping. To clarify importance of this effect for the formation of
the Ga-interstitials, samples with different doping were studied.
5.3.1 P-type doping
GaNAs:C epilayer with nitrogen composition of 0.54% was studied. According to the
Hall measurements, the hole concentration in the sample was 2.3e17
cm-3
. In order to identify the
band-to-band emission from the alloy, temperature dependent PL measurements were employed
-see Figure 5.3.1.1. It was found this PL dominates at all measurement temperatures. Indeed, the
PL maximum position exhibits the characteristic S-shape temperature behavior as discussed in
the first chapter. From the ODMR measurements, the employed doping favors the formation of
the Ga𝑖- C defect as demonstrated in figure 5.3.1.2.
𝑇𝑔 = 420 𝐶 : 𝛾𝑒𝑁 = 0.087 ps-1
𝑇𝑔 = 580 𝐶 : 𝛾𝑒𝑁 = 0.065 ps-1
Figure 5.2.6; circular (spin) PL
polarization as a function of excitation
power. The dots denote the
experimental data. The dashed lines are
the simulated curves. After RTA, the
number of defects contributing to the
SDR is reduced.
47
5.3.2 N-type doping
Figure 5.3.2.1 a) and b) shows PL spectra measured from two investigated n-type GaNAs
epilayers with similar N compositions of 0.21% (EB129) and 0.23% (EB128). Electron
concentrations in the samples were −3.3 × 1014 cm-3(EB129) and−4.8 × 1015 cm-3 (EB128),
as determined from the Hall effect measurements. The GaNAs PL emission clearly dominates in
both structures. The corresponding ODMR spectra measured when monitoring these emissions
are shown in figure 5.3.2.2 a) and b). The intensity of the ODMR signals increases for the
EA719 N = 0.54% n = 2.3e17 cm-3
-100 0 100 200 300 400 500 600 700
-2.2
-2.0
-1.8
-1.6
-1.4
-1.2
-1.0
-0.8
-0.6
x
OD
MR
(n
orm
ali
zed
)
Magnetic field (mT)
Sim Gai-C
Figure 5.3.1.2; ODMR spectrum of
GaNAs:C epilayer detected via the near-
band-edge emission. The spectrum is
related to the Ga𝑖-C defect center.
700 750 800 850 900 950 1000 1050 1100 1150
6 K
60 K
120 K
180 K
240 K
300 K
PL
In
ten
sity
(N
orm
ali
zed
)
wavelength (nm)
EA719 N = 0.54% n = 2.3e17 cm-3
Figure 5.3.1.1; temperature dependence
measured from the GaNAs:C epilayer.
48
sample with the higher carrier density which indicates that the formation of the involved centers
is promoted by the n-type doping. From the performed angular dependent measurements it can
be concluded that at least two components contribute to the ODMR spectra, as relative intensities
of different lines within the spectra vary with B. This is especially pronounced for the EB129
sample – see Figure 5.3.2.3 a).
700 750 800 850 900 950 1000 1050 1100 1150
6 K
60 K
120 K
180 K
240 K
300 K
PL
In
ten
sity
(N
orm
ali
zed
)
wavelength (nm)
EB128 N = 0.23% n = -1.8e15 cm-3
700 750 800 850 900 950 1000 1050 1100 1150
6 K
60 K
120 K
180 K
240 K
300 K
PL
In
ten
sity
(N
orm
ali
zed
)
wavelength (nm)
EB129 N = 0.21% n = -3.3e13 cm-3
Figure 5.3.2.1 a); temperature
dependent PL spectra measured from
the EB129 sample (n = −3.3 ×
1014 cm-3).
Figure 5.3.2.1 b); temperature
dependent PL spectra measured from
the EB128 (n = −1.8 × 1015 cm-3 ).
This sample shows relatively higher
intensity of the GaNAs emission as
compared with EB129.
49
Figure 5.3.2.2 a) and b); ODMR spectra detected via the near band edge emission from the samples as specified in
the figure.
Figure 5.3.2.3 a) and b.; angular dependences of the ODMR spectra. Note that a relative intensity of the 480 mT
line changes with the angle.
The existence of two ODMR components was further confirmed by varying experimental
conditions, such a microwave power and measurement temperature. The results of these
measurements are summarized in figure 5.3.2.4.
a) b) EB128 N = 0.23, n =-1.8e15 cm-3 EB129 N = 0.21, n =-3.3e13 cm-3
-100 0 100 200 300 400 500 600 700 800 900
WINDOW:
LWP 1250
OD
MR
(A
rb.
Un
it)
Magnetic field (mT)
Sim
x
b)
EB129 EB128
-100 0 100 200 300 400 500 600 700 800
WINDOW:
LWP+SWP 1000OD
MR
(A
rb.
un
it)
Magnetic field (mT)
x
Sim
a)
0 100200300400500600700800
0 degree
40 degree
60 degree
80 degree
Magnetic field (mT)
OD
MR
(nor
mal
ized
)
0 100 200 300 400 500 600 700
0 degree
20 degree
40 degree
60 degree
80 degree
Magnetic field (mT)
OD
MR
(nor
mal
ized
)
50
Figure 5.3.2.4 a); microwave power dependence of the ODMR spectra measured from the EB129 sample, the
relative intensities of the peak at 48o mT (g = 1.357) and the others lines depend on the microwave power. b) the
same trend was observed when the temperature was changed. These results show that at least two components
contribute to the ODMR signal.
As the ODMR spectra are isotropic and contain more than four lines it is probable that at
least one component is related to the Ga𝑖-interstitial defect. Thus simulations using the spin-
Hamiltonian were performed. Best fit of the experimental data was obtained when using the
following parameters: g = 1.960, A ( 𝐺𝑎69i) = 1000 and A ( 𝐺𝑎71
i)= 1270. The simulation curve
using these parameters is shown in the upper part of Figure 5.3.3.2 and can reasonably account
for the majority of the detected ODMR lines. It is interesting to note that the obtained parameters
differ significantly from those of the previously studied Ga interstitial defects. This likely
indicates a different local configuration of the Ga interstitials in n-type GaNAs, e.g. due to
perturbations by Si.
5.4 Effects of growth techniques on the defect formation
The very important question is how the Gai defects are formed. The defects have never
been found in GaAs, which implies that their formation is related to introduction of nitrogen
atoms. Recently it has been reported that the formation of Gai is induced by N bombardment
during the MBE growth process [24]. In principle, this can explain the defect formation in all
previously discussed structures as they were all grown by MBE. Alternatively, the defect
formation can also be induced by the presence of nitrogen as it may minimize a total energy of
the system. To check whether or not this is indeed the reason for the defect formation we have
studied ODMR properties of GaNAs epliyaer grown by MOCVD. Here, the defect formation
should be mainly determined by thermodynamics during the growth process, as N bombardment
is no longer present. Parameters of the investigated samples which were all grown on semi-
insulating GaAs substrates are listed in table 5.4.1.
0 100 200 300 400 500 600 700
Microwave power
200 mW
100 mW
50 mW
OD
MR
(n
orm
aliz
ed)
Magnetic field (mT)
a) b)
0 100 200 300 400 500 600 700
N = 0.21%
n-doped (Si) -3.3e14 cm-3
WINDOW:
LWP+SWP 1000
Temperature
5 K
13 K
OD
MR
(n
orm
aliz
ed)
Magnetic field (mT)
EB128 N = 0.23, n =-1.8e15 cm-3 EB129 N = 0.21, n =-3.3e13 cm-3
51
Table 5.4.1; parameters of the investigated MOCVD-grown GaNAs epilayers. GaNAs bandgap energies were
estimated from the BAC model.
PL spectra measured at 6K from the investigated samples are shown in figure 5.4.1. As is
seen from the figure, the intense band-to-band emission is observed from the MD232 (N =
0.36%) and MD 207 (N = 0.94%) samples, whereas it is rather week for all other structures.
Figure 5.4.1; PL spectra detected from the MOCVD samples.
Sample
Type
Nitrogen
composition (%)
Doping
Carrier
concentration
(cm−𝟑)
Estimated 𝑬𝒈
(6 K)
GaNAs
𝑬𝒈 estimate
(300 K)
MD234
epilayer <0.1% - 5× 1016
<839.63 nm <889.55 nm
MD204
epilayer 0.29% - 6.8× 1016
870.18 nm 917.44 nm
MD232
epilayer 0.36% - 7.4× 1016
879.60 nm 926.58 nm
MD230
epilayer 0.67% - 1.0× 1017
839.63 nm 889.55 nm
MD207
epilayer 0.94% - 2.0× 1016
949.95 nm 998.40 nm
800 900 1000 1100
MD 234 (N < 0.10%)
MD 204 (N = 0.29%)
MD 232 (N = 0.36%)
MD230 (N = 0.67%)
MD207 (N = 0.97%)
PL I
nten
sity
(A
rbita
ry u
nit)
Wavelength (nm)
Full spectrum (MOCVD) at T = 6 K
945 nm
882.18 nm915.8 nm
870 nm840nm
52
Defect properties of the samples were studied by using the ODMR technique.
Representative ODMR spectra recorded via the near-band-edge PL are shown in Fig. 5.4.2. In
all samples the dominant ODMR signal (denoted as Gai-C*) originates from the Ga interstitials
with parameters which are very close to that for the Gai-C center detected in the MBE-grown
GaNAs. The simulated ODMR spectrum using the spin-Hamiltonian is shown in the lower part
of the figure and reasonably agrees with the experimental one, which justify the choice of the
used parameters. As expected, the signal is negative which means that the involved defects
participate in the competing NR recombination. In addition, a positive ODMR signal is found in
the sample with N=0.67%. This signal becomes more intense when detecting via the defect-
related emission at longer wavelength. As the involved recombination center does not compete
with the band-to-band transitions, it is unlikely important for SDR and therefore, will not be
discussed in this work.
-0.0004
0.0000
0.0004
N < 0.1 %
-0.006
-0.004
-0.002
0.000N = 0.29 %
-0.0015
-0.0010
-0.0005
0.0000 N = 0.36 %
0.0000
0.0005N = 0.67 %
0 100 200 300 400 500 600 700
-1.8
-1.2
-0.6
0.0
0.6 Simulation
Gai-C*
Magnetic field (mT)
Near band edge window
Figure 5.4.2; ODMR spectra of MOCVD – grown GaNAs. The spectra were detected at the near band edge spectral
window.
In summary, formation of Ga interstitials was for the first time observed in GaNAs grown
by MOCVD. These results prove that these defects are common grown-in defects in GaNAs
formed in these alloys upon N incorporation independent of the growth procedure. The defects
act as an important recombination center and, therefore, will likely affect performance of all
electronic devices based on dilute nitrides.
53
Summary
Spin filtering properties of novel GaNAs alloys were extensively studied in this thesis by
using optical orientation and spin resonance techniques. It has been proven that a GaNAs layer
can be utilized as a spin filter for the injected carriers from other materials. It was shown that the
main physical mechanism behind spin filtering is spin-dependent recombination via Ga
interstitial-related defects revealed from the ODMR measurements. These defects were found to
be the dominant grown-in defects in GaNAs, commonly formed during both MBE and MOCVD
growths. Several parameters were found to affect the efficiency of SDR and, therefore, of spin-
filtering, such as growth temperature, post-growth annealing, doping and quantum confinement
in the corresponding low-dimensional structures. Our results clarify approaches to be utilized to
achieve the efficient spin filter and also demonstrate the capability to integrate the GaNAs spin
filter with others functional semiconductor devices. We hope that a relievable, functional spin
filter with reasonable prize will be available to global market in the nearest future.
“I see spin in your future”
Yuttapoom Puttisong
54
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