3.

Materiales semiconductores
compuestos III-V
Dr. Karim Monfil Leyva

E-mail: karim.monfil@correo.buap.mx
 2
CONTENIDO
A. Aspectos básicos (covalente-iónico, zincblenda,
modulación del ancho de banda prohibido)
B. Defectos nativos
C. Heteroestructuras
D. Propiedades optoelectrónicas
E. Impurezas
 3

Aspectos básicos
(covalente-iónico,
zincblenda, modulación
del ancho de banda
prohibido)
 INTRODUCTION 4
Next in importance to the elemental semiconductor Si, we have the III-V
compound semiconductors obtained by combining group III elements
(essentially Al, Ga, In) with group V elements (essentially N, P , As, Sb). This
gives us 12 possible combinations; the most important ones are probably
GaAs, InP, GaP and GaN.
All of these III-V combinations crystallize either in the diamond lattice
like Si or Ge, often called "Zinc blende" or ZnS structure (the term
"sphalerite structure" is used, too), or in an hexagonal lattice known as
"wurtzite". For your edification both structures are shown and explained in
the link.
What can III-V's do that Si cannot do? This is an absolutely essential
question for an engineer.
In your engineer mode (as opposed to your scientist mode) you think
exclusively in terms of applications and products.
 INTRODUCTION 5
In a good first approximation, using a new material for an
existing product is only sensible if it makes the product better or
cheaper (or both). Looking at just "raw" Si single crystals, no other
semiconductor comes even remotely close with respect to prize /
performance. There are simply no large practically defect-free
cheap wafers of other semiconductors!
So there must be a very compelling reason to use III-V's for
application that Si just can't hack. Obviously, this is optoelectronics
for starters.
Obviously, because by now you know that Si has an indirect
band gap and that means it will not emit light. If we want to
produce light emitting diodes (LED's'), we simply cannot use Si.
This brings us right to the most important set of III-V properties:
Size and nature of the band gap
6
7
 III-V COMPOUNDS

•Light emitters, including lasers and LEDs

•Detectors
•Amplifiers
•Waveguides and switches
•Absorbers and filters
•Nonlinear crystals
 Interband transistion

h  Eg h  Eg

  nanoseconds in GaAs
Intraband transitions

  < ps in GaAs

n-type
 UV

Optical fiber
communication
GaAs ZnSe InP
Bandgap rules

The bandgap increases with decreasing lattice

constant.

The bandgap decreases with increasing

temperature.
Interband vs Intraband

Interband: C

Most semiconductor devices

operated based on the interband
transitions, namely between the
conduction and valence bands.
The devices are usually bipolar
involving a p-n junction. V

Intraband:
A new class of devices, such as the
quantum cascade lasers, are based on
the transitions between the sub-bands in
the conduction or valence bands.
C
The intraband devices are unipolar.
Faster than the intraband devices
Generation and Forms of 16
Nanodefects in Crystals
 Nanodefects in Crystals 17
• It is a general tendency in nature that a combination of two
or more defects is energetically more favorable than a
configuration from the contributing isolated defects. This
means that two (or more) vacancies (interstitials complexes)
have the tendency to form a double vacancy, triple vacancy
etc., since the potential energy of a double vacancy is smaller
than that of two single vacancies. A larger number of
vacancies can form a cavity in the crystal which can again be
filled with foreign atoms so that filled bubbles are formed.
• Defects in a crystal can result from natural growth or from
external manipulation. The production of defects takes place
intentionally (in order to dope) or unintentionally during certain
process steps such as diffusion, ion implantation, lithography,
plasma treatment, irradiation, oxidation, etc. Annealing is
often applied in order to reduce the number of (produced)
defects.
 18
Characterization of Nanodefects in Crystals
• A rather large number of procedures was developed in order to determine the
nature of defects and their densities. Other important parameters are charge
state, magnetic moment, capture cross sections for electrons and holes,
position in the energy bands, optical transitions, to name but a few.
When Cu, which is a fast diffuser, is
driven into Si (immersing the silicon into
a CuSO4 containing solution), it will be
trapped by available defects. Cu is
accessible by infrared measurements,
while the available defects are invisible.
The Fig. shows 2 closed dislocation
loops and a third one inside shortly
before completion. A dislocation can
be explained by assuming a cut in a
crystal so that n crystal planes end in
the cut plane. n + 1 crystal planes may
end on the other side of the cut. Then
an internal level remains without
continuation. Roughly speaking, the
end line of this plane forms the
dislocation, which can take the form of
a loop.

Characterization of Nanodefects in Crystals
Formation of a (100) platelet in Si by
hydrogen plasma at 385 °C (image
from TEM).
19
Now, we consider the case where Si is
exposed to a hydrogen plasma and
then annealed. A platelet is a two-
dimensional case of a bubble, i.e.,
atoms from one or two lattice
positions are removed and filled with
hydrogen, so that a disk-like structure
is formed.
The proof of H2 molecules and Si-H
bonds shown in Fig. can be done by
means of Raman spectroscopy. With
this technique, the sample is
irradiated with laser light. The energy
of the laser quantum is increased or
decreased by the interaction of
quasi-free molecules with the
incoming light.
The modified reflected light is
analyzed in terms of molecular
energies which act as finger print of
the material and its specific defects.
Characterization of Nanodefects in Crystals 20

p-type Czochralski (Cz) Si is

plasma-treated for 120 min
at 250 °C and annealed in
air for 10 min at temperatures
between 250 °C and 600 °C.
The Raman shift is measured
in two spectral regions. At
energies around 4150 cm–1
the response due to H2
molecules is observed (Fig.
a), and around 2100 cm–1
that due to Si-H bonds.

Raman shift of H2 bonds (a) and of Si-H

bonds (b)
 21
Characterization of Nanodefects in
Crystals
• It should be noted that after
plasma exposure the surface is
nanostructured & SiOx
complexes are formed there.
The p-type sample has been
exposed to a hydrogen plasma
for 120 min at 250 °C and
annealed in air 10 min at 600
°C. The SiOx complexes are
detected with
photoluminescence.
 IR Absorption 22

If oxygen-rich (e.g., Czochralski, Cz)

material is exposed to a hydrogen
plasma at approximately 450 °C, the
so-called thermal donors are formed
(most likely oxygen vacancy
complexes). They can be measured
with infrared (IR) absorption. The
signal of the two types of thermal
donors is shown in next Fig.

IR absorption spectra for neutral thermal

donors (a) and single-ionized thermal
donors (b)
 23
Some defects possess magnetic moments (or spins) which are
accessible by electron spin resonance measurements.
The MOS capacitance is an efficient tool for detecting defects in the
oxide, in the neighboring silicon and at the Si/SiO2 interface. We are
limited to the discussion of defects in silicon, approximately in the
neighborhood of 1 to 10 μm from the interface. If the (high
frequency) capacitance is switched from inversion into deep
depletion, it follows first the so-called pulse curve and then returns to
the initial inversion capacitance at a fixed voltage.
MOS capacitance after switching
from inversion in deep depletion (a)
and during the relaxation (b)
 Deep level transient spectroscopy (DLTS) 24
DLTS is another helpful electrical procedure.
It measures the trap densities, activation
cross sections, and energy positions in the
forbidden band. It is applied to Schottky
and MOS diodes.
In the Fig., the Schottky diode is switched
from the forward to the reverse direction.
Similarly, the MOS diode is switched from
accumulation to depletion. After pulsing
and retention of a fixed voltage it turns out
that the capacitance runs back to a higher
value. The summation of all pulse and
relaxation capacitances produce the
capacitance curves CP and C=. All
information is obtained from the
DLTS on a Schottky diode (top)
capacitance-transient C(t), an exponential-
and on an MOS diode (bottom)
like function.
 25

The reason for the capacitance

relaxation is the presence of traps (only
bulk traps for the Schottky diode and
surface states for the MOS
capacitance). The figure demonstrates
the behavior of the traps after pulsing.
The emission time constant te is reflected
in the capacitance relaxation of
previous figure.
Technically, it is difficult to measure the
full transient. In the worst case this would
be called a speedy measurement of a
maximum of a few femtofarad within
a time span of less than one micro second. The measurement is done in such
a way that two time marks are set for instance, at 1 and 2 ms.
 26
Then the transient is repeatedly measured within this window at
different temperatures. It should be noted that in reality the
capacitance C(t→∞) is defined as zero and the negative deviation
from C(∞) represents the signal. On the right of the figure, the
capacitance difference│C(t1) –C(t2)│ is plotted against the
temperature.
The emission time constant
(e.g., for electron emission) is

cn is the capture constant of the emitting traps,

σn the capture cross section, ni the intrinsic density,
ET the position of the traps in the band gap, Ei the
intrinsic Fermi level, and vth the thermal velocity.
 27
At very low temperatures the emission time is high compared to the time
window t1 – t2. At very high temperatures the reverse applies, so that the
transient is finished long before t1 is reached. In between, there is a maximum
δCmax, at the temperature Tmax. For a given window t1, t2, the emission time at
this maximum is calculated as

Now a data pair (T2max e, Tmax) is available. The same procedure is repeated
for other time windows, so that a curve T2max e vs Tmax and thus, the energy EC
– ET, i.e., the position of the trap energy in the forbidden band can be
determined. From the same equation, the unknown quantity σn can be
determined. In order to describe the determination of the trap density, we
will use the example of the Schottky diode. It is shown that NT is given by
 28
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
When two crystals of semiconductors with different energy gaps are
combined, a heterojunction is formed. The conductivity type of the
smaller energy gap crystal is denoted by a lower case n or p and that of
the larger energy gap crystal is denoted by an upper case N or P.
Semiconductor p-N Heterojunction
Consider first a p-type narrow-gap semiconductor, such as GaAs, in
contact with an N-type wide-band-gap semiconductor, such as
AlxGa1-xAs. Let χ be the electron affinity, which is the energy required to
take an electron from the conduction band edge to the vacuum level,
and let Φ be the work function (the difference between the vacuum
level and the Fermi level).
Depletion Approximation for an Unbiased p-N Junction. Since the
charge density is
 29
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
and the free carriers p and n are depleted in the space charge
region near the junction, we have

From Gauss's law, we know that , which gives

the electric field is given by two linear functions

 30
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
 31
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
Illustrations of (a) a p-N junction
geometry, (b) the charge
distribution, (c) the electric field,
and (d) the electrostatic potential
based on the depletion
approximation.
 32
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
Energy band diagrams for a p-N
heterojunction under (a) forward bias,
and (b) reverse bias based on the
depletion approximation
 33
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
a) The carrier concentration and b)
the current densities as functions of
position x in a forward biased p-N
heterojunction diode using the
depletion approximation
 34
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
a) The carrier concentration and b)
the current densities as functions of x
for a reversed biased p-N
heterojunction diode using the
depletion approximation
 35
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
Example. A p-GaAs/N-AlxGa1-xAs (x=0.3) heterojunction is formed at
thermal equilibrium without an external bias at room temperature. The
doping concentration is Na = 1 x 10 18 cm-3 in the p side ND = 2 x 1017 in
the N side. Assume that the density of states hole effective mass for
AlxGa1-xAs is
which accounts for both the heavy-hole and light-hole density of states.
Other parameters are

where x is the mole fraction of aluminum.

 36
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
 37
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
b) We calculate the quasi Fermi levels Fp and FN for the bulk
semiconductors for the given Na and ND separately.
P-GaAs region

𝐸𝑣𝑝 − 𝐹𝑝 𝐸𝑣𝑝 − 𝐹𝑝
𝑝 = 𝑁𝑎 = 𝑁𝑣 𝐹1 2 ≈ 𝑁𝑣 𝑒𝑥𝑝
𝑘𝐵 𝑇 𝑘𝐵 𝑇
𝑁𝑎
𝐹𝑝 − 𝐸𝑣𝑝 = −𝑘𝐵 𝑇𝐿𝑛 = 56.4 𝑚𝑒𝑉
𝑁𝑣
 38
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
 39
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
 40
SEMICONDUCTOR p-N AND n-P
HETEROJUNCTIONS
 Lasers y Leds basados en InGaN y GaN
Hoy en día se presta especial atención al desarrollo científico y tecnológico de los
diodos emisores de luz y los diodos láser basados en la tecnología del nitruro de
galio.
Hace algunos años que “los nitruros” eran los peores materiales desde el punto de
vista estructural y los mejores desde el punto de vista óptico y optoelectrónico. La
referencia a “los nitruros”, lo hacía específicamente al nitruro de galio (GaN) y una
de sus aleaciones, el nitruro de galio-indio (InxGa1-xN). Y esas malas y buenas
propiedades, muy influyentes tecnológicamente, se extienden desde sus tamaños
volumétricos hasta cualquiera de sus variantes nanométricas, como pueden ser los
pozos cuánticos y multicapas cuánticas, los hilos cuánticos y los puntos cuánticos
 Lasers y LEDs de InGaN
El nitruro de galio-indio (InGaN o InxGa1-xN) es una aleación
semiconductora de nitruro de galio (GaN) y de nitruro de indio (InN). Este
sistema se trata de un semiconductor cuyo gap se puede ajustar, variando la
cantidad de indio en la aleación. La proporción de In/Ga está normalmente
entre 0,02/0,98 y 0,3/0,7. La longitud de onda emitida por esta aleación va
desde el ultravioleta, pasando por el violeta-azul, hasta el azul. Para
proporciones mayores de In/Ga pueden alcanzarse emisiones en el rojo. Esta
aleación tiene una alta capacidad calorífica y su sensibilidad a la radiación
ionizante es baja, por lo cual es también potencialmente un material adecuado
para componentes en satélites. Al igual que el GaN y el AlGaN puede ser
depositado en forma de capas sobre sustratos de zafiro y carburo de silicio. Y,
del mismo modo que en la aleación AlGaN, en el InGaN se presenta también
la llamada luminiscencia amarilla aunque en menor grado, lo que la hace algo
más eficiente.
 Lasers y LEDs de InGaN
Sin embargo, el InGaN tiene una desventaja “ventajosa”. Se ha comprobado
que, cuando la proporción de indio de encuentra entre un 15% y un 85%, se
presenta un efecto llamado descomposición espinoidal (spinoidal
decomposition) en esta aleación. Este efecto es un mecanismo por el cual dos
o más componentes de un sistema pueden separarse en distintas regiones o
fases con distinto porcentaje de composición química, las cuales tienen
diferentes propiedades físicas.
 Lasers y LEDs de InGaN

Emisiones de dispositivos optoelectrónicos en base a InGaN.

White LEDs
Su desarrollo es un intento muy bien
fundamentado para sustituir las
bombillas actuales por dispositivos
mucho más ventajosos caracterizados
por:
• Un consumo de un 92% menos que
las bombillas incandescentes de uso
doméstico común;
• Un consumo de un 30% menos que
la mayoría de los sistemas de
iluminación
fluorescentes;
• Una duración de hasta 20 años.
 LASERS Y LEDs de GaN
La buena calidad cristalina de
las capas de GaN, así como la
uniformidad de espesores
fueron confirmadas con
caracterizaciones ópticas,
eléctricas y mecánicas. Con
mucho esfuerzo experimental,
lográndose capas de GaN tipo p
con buena calidad y
disminuyendo la región activa
del diodo a espesores
nanométricos, se aseguraba un
LED azul de buen rendimiento
Esquema simplificado de un diodo emisor de luz de GaN, óptico (Hiroshi Amano et al.,
según patente US 6, 787, 435 B2 de septiembre 7 de 2004
1989)
 LASERS Y LEDs de GaN
Esquema del LED azul de Shuji Nakamura. Takeda Award (2002).

Diseño y construcción del LED azul.

Su diseño de diodo láser tenía la particularidad de ser una extensión del diseño del diodo
con región activa con base en una estructura de pozos cuánticos múltiples de InGaN. Este
resultado fue publicado en Nakamura, S. et al. (1996). En 1999 la compañía Nichia
Chemical Industries, Ltd., lanzó al mercado su primer LED azul con una eficiencia de más
de 9% y un tiempo de vida estimado en más de 10 mil horas. La complicación del diseño y
construcción tecnológica de estos dispositivos ha ido creciendo con los desarrollos y las
innovaciones tecnológicas en universidades, centros de investigación y empresas.
 LASERS Y LEDs de GaN
APLICACIONES
El InGaN se ha convertido en el compuesto clave para la producción de emisores
de luz ultravioleta, azul, verde y amarilla, con tan solo cambiar la composición del
indio en la capa activa intermedia de los diodos. El desarrollo del LED azul
permitió que en 2002 saliera al mercado la nueva generación de CDs y DVDs
conocidos como los “Blu-ray Disc”. Cada vez más se usan los LED azules para
remplazar bombillas incandescentes domésticas y públicas, así como en
señalizaciones de tránsito. Debido a las excelentes propiedades de estos
dispositivos emisores de luz, su uso o remplazo de otras fuentes de luz permiten un
millonario ahorro de energía eléctrica y una reducción de emisión de CO2 de más
de 110 mil toneladas anuales. Desde la primera comercialización de los LEDs de
GaN de Shuji Nakamura, la comercialización ha aumentado en 400 mil millones
de dólares en los EUA. Por otro lado, la industria de TV ha logrado éxitos
inalcanzados anteriormente con el uso de las combinaciones de LEDs azules, rojos
y verdes para lograr las pantallas planas de “full-color”que desde hace años ya se
están comercializando.
LASERS Y LEDs de GaN