03 - Semiconduttori Composti Ed Eterostrutture 2016-2017

Compound Semiconductors
Elemental Semiconductors
Elemental Semiconductors
Reticolo diamante e zincoblena
Struttura a bande del GaAs (sinistra) e del Si (destra)
GaAs: semiconduttore a gap diretto, minimo della banda di conduzione

in
Compound minimi Dispositivi
Γ; altriSemiconductors Optotelettronici
in L (a 0.3 eV) e in X 2005-2006
(a 0.48)
Struttura a bande di energia di Si e GaAs
Differenze tra GaAs e Si
la massa dell’elettrone nella valle Γ del

GaAs è molto piccola sia rispetto a quella delle altre
valli sia rispetto a quella del silicio
la distanza energetica tra la valle Γ e le altre è nel

GaAs molto minore rispetto a quella tra le valli del
silicio
la banda di valenza del GaAs presenta tre massimi di

cui uno ad elevata massa efficace
il GaAs è un semiconduttore a gap diretto, mentre il Si

è un semiconduttore a gap indiretto
Velocità di deriva vs campo elettrico: GaAs e Si
Distribuzione degli elettroni tra le varie valli vs E
Velocity overshoot in GaAs
Figure 3.24. One possible velocity-field characteristic of a two-valley

semiconductor.
III-V Semiconductors
II-VI Semiconductors
Compound Semiconductors: Group IV Materials
A Chemical Trend – Material Bandgap as a function of
Near-Neighbor Distance for Diamond Structure Solids
Decreasing Bandgap Eg correlates with
Increasing Nearest-Neighbor Bond Length d
Atom Eg (eV) d (Å)
C 6.0 2.07
Si 1.1 2.35
Ge 0.7 2.44
Sn (a semimetal) 0.0 2.80
Pb (a metal) 0.0 1.63
Not the diamond
structure!
Compound Semiconductors: III-V Compound
Column III Column V

B N
Al P
Ga As
In Sb
Tl ← not used → Bi
Some possible compounds which
are semiconductors are:
BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN
GaP, GaAs, GaSb, InP, InAs, InSb,….
Compound Semiconductors - GaAs
• Blende Zinc structure : 2 fcc sublattices : III and V

• [110] and [-110] axes : cleave directions
– Equivalent in bulk, not at the surface or in 2D
– [-110] refers to As surface dangling bond
– Rotate by 90º between top and bottom surfaces !
[-110]
As
Ga
[-110]
Compound Semiconductors: III-V Compound
Some Applications of III-V Materials
IR detectors, LED’s, solid state lasers, switches, ….
BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN
GaP, GaAs, GaSb; InP, InAs, InSb,….
A Chemical Trend
The bandgap decreases & the interatomic distance
increases going down the periodic table. There is
tetrahedral coordination of the atoms. Many III-V
compounds have the zincblende crystal structure.
Some (B compounds & N compounds) have the wurtzite
crystal structure. Interatomic Bonding: The bonds
are not purely covalent! The charge separation due to
the valence differences leads to Partially Ionic bonds.
Semiconduttori composti
Compound Semiconductors: II-VI Compound
Column II Column VI
Zn O
Cd S
Hg Se
Mn ⇐ sometimes Te
not used ⇒ Po
Some possible compounds which are
semiconductors or semimetals are:
ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS
HgSe, HgTe,… + some compounds with Mn….
Compound Semiconductors: II-VI Compound
Some Applications of II-VI Materials
IR detectors, LED’s, switches, solar cells, …
ZnO, ZnS, ZnSe, ZnTe; CdS, CdSe, CdTe, HgS
HgSe, HgTe (semimetals) + some compounds with Mn
A Chemical Trend
The bandgap decreases & the interatomic distance increases
going down the periodic table. There is tetrahedral coordination of
the atoms. Except for the Hg compounds, which are semimetals with
zero gaps, the II-VI materials have large bandgaps compared to the
Column IV and the III-V materials. Some of these materials have a
zincblende crystal stucture & some have wurtzite crystal
structures. Interatomic Bonding: The charge separation due to the
valence difference is large.
⇒ The bonds are more ionic than covalent!
Compound Semiconductors: IV-IV
Column IV
Binary combinations of
C, Si, Ge, Sn ⇒ SiC
Other compounds: GeC, SnC, SiGe, SiSn, GeSn,..
Cannot be made or cannot be made without species
segregation or are not semiconductors. Two common
crystalline phases for SiC are zincblende (a semiconductor),
& hexagonal close packed (a large gap insulator).
There are also MANY other crystal
structures for SiC!
Compound Semiconductors: Others ….
• “Alloy” mixtures of elemental materials (binary alloys):
SixGe1-x ,... (0 ≤ x ≤ 1)
• “Alloy” mixtures of binary compounds (ternary alloys):
Ga1-xAlxAs, GaAs1-xPx,… (0 ≤ x ≤ 1)
• “Alloy” mixtures of binary compounds with mixtures
on both sublattices (quaternary alloys):
Ga1-xAlxAs1-yPy, .., (0 ≤ x ≤ 1, 0 ≤ y ≤ 1)
• In the growth process, x & y can be varied, which
varies the material bandgap & other properties.
“BANDGAP ENGINEERING!”
Semiconduttori III-V : composti ternari
The bandgap energy Eg for this
material varies between 1.42 e V for
GaAs and 2.16 e V for AlAs, as x
varies between 0 and 1 along the
line connecting GaAs and AlAs.
Because this line is essentially
vertical, AlxGal-xAs is lattice
matched
to GaAs;
(InxGal-x)As is widely used for photon

sources and detectors in the near-
infrared region of the spectrum.
(AlxGal-x)N and (InxGal-x)N are
important ternary semiconductors
for photonic devices that operate in
the ultraviolet, violet, blue, and green
regions of the spectrum
(InxGal-x)As/InP heterojunction
bipolar transistors can be switched
at speeds approaching 1 THz
Compound Semiconductors: InxGa1-xAs
AlAs
InxGa1-xAs
Da GaAs passando a InAs attraverso InGaAs

hanno parametro reticolare sempre più diverso.
Ma InAs ha µn = 33000 cm2/(Vs)
Semiconduttori III-V : composti quaternari
For Inl-xGaxAsl-yPy, the bandgap
energy varies between 0.36 eV
(InAs) and 2.26 eV (GaP) as the
compositional mixing ratios x and y
vary between 0 and 1.
The stippled area indicates the

range of bandgap energies and
lattice constants spanned by this
compound. For mixing ratios x
and y that satisfy y = 2.16(1 - x),
Inl-xGaxAsl-yPy can be lattice
matched to InP.
This quaternary compound is used

for fabricating light-emitting diodes,
laser diodes, and photodetectors,
particularly in the vicinity of the
1550-nm optical fiber
communications wavelength
The III-nitride compound

(AlxInyGal-x-y)N, serves
the green, blue, violet, and
ultraviolet spectral regions.
Convenient templates for the
Ill-nitrides are sapphire and
SiC.
Compound Semiconductors: AlxGa1-xN, InxGa1-xN, ….
Binary II-VI materials, i.e.,
compounds formed from
elements in column II (e.g.,
Zn, Cd, Hg) and column VI (e.g.,
S, Se, Te) of the periodic table
are also useful semiconductors.
This family includes ZnS, ZnSe,
ZnTe, CdS, CdSe, CdTe, HgS,
HgSe, and HgTe. All of these
materials have a zincblende
structure and all are direct-
bandgap semiconductors; the
exceptions are HgSe and HgTe,
which are semimetals with small
negative bandgaps. A particular
merit of ZnSe, is that it can
be deposited on a GaAs
substrate with a relatively low
defect density since the lattice
constants of the two materials are
similar.
Moreover, HgTe and CdTe are
nearly lattice matched, so the
ternary semiconductor
HgxCd 1 - xTe can be grown
without strain on a CdTe
substrate. This material system is
widely used for fabricating photon
detectors, as are other II-VI
compounds. Unlike the III-V
alloys, photon sources fabricated
from II-VI materials currently
suffer from limited lifetimes.
Nevertheless, binary II-VI

semiconductor materials are
readily fashioned into quantum
dots with tunable
photoluminescence emission
wavelength.
Ternary IV-VI semiconductor

compounds, such as PbxSnl- x Te
and PbxSnl-xSe, have also been
used as infrared photodetectors
and laser diodes.
However, these alloys have

slower response times because
of their large dielectric constants.
They also have high thermal

coefficients of expansion, so
cycling between room and
cryogenic temperatures can be
problematic.
Eterostrutture
Crescita Epitassiale
• From the greek : Επι = on Ταξει = order

• The science to preserve crystal order from the substrate to the
grown material
Tecniche di crescita epitassiale
Epitassia = Tecnica di crescita di un film monocristallino (privo di difetti)
su di un substrato monocristallino (=mantenendo la stessa struttura e
la stessa perfezione cristallografica)
επι (epi) = sopra

ταξις (taxis) = ordine
Tecniche di crescita epitassiale
Crescita epitassiale:
lattice-matched (“ad accordo reticolare”)
pseudomorfica (“con piccole differenze di parametro reticolare”)
metamorfica (su substrato con parametro reticolare nettamente

diverso, attraverso la crescita di uno strato intermedio “buffer”
entro il quale termina la zona difettosa)
Strain in heteroepitaxial layers
Strain in heteroepitaxial layers
Detrimental effects of dislocations
Strained heteroepitaxial layers: critical thickness
Defects in Epitaxial Growth
Dislocations
Semiconduttori Ternari e Quaternari
Es. GaAs, AlAs AlxGa1-xAs, 0<x<1
Legge di Vegard Dati due semiconduttori binari AC e BC, con

Energy Gap EG(AC) e EG(BC), l’Energy Gap del
semiconduttore ternarioAxB1-xC è dato da:
EG(AxB1-xC)=x∙EG(AC)+(1-x) ∙EG(BC)
Lo stesso vale per altri parametri del semiconduttore: costanti
reticolari, costante dielettrica, e inverso della
massa efficace
In generale:
P(AxB1-xC)=x∙P(AC)+(1-x)∙P(BC)
Talvolta la relazione lineare non è sufficientemente precisa, e si introduce un
ulteriore termine, con un parametro b detto, in inglese, bowing parameter:
Legge di Vegard Semiconduttori Quaternari
P(A1-xBxCyD1-y)=(1-x)∙y∙P(AC)+
(1-x)∙(1-y)∙P(AD) +
x∙(1-y) ∙P(BD)+
x∙y∙P(BC)
P = energy gap, costante reticolare, …..
http://www.ioffe.rssi.ru/SVA/NSM/Semicond/
Semiconduttori Ternari
AlxGa(1-x)As
AlAs GaAs x=0.1 x=0.2 x=0.3 x=0.4

Eg (eV) 2.671 1.424 1.549 1.673 1.798 1.923
εr 10.9 13.1 12.880 12.660 12.440 12.220
χ 2.97 4.07 3.960 3.850 3.740 3.630
Nc (cm-3) 1.50E+19 4.00E+17 1.86E+18 3.32E+18 4.78E+18 6.24E+18

Nv (cm-3) 1.70E+19 9.00E+18 9.8E+18 1.06E+19 1.14E+19 1.22E+19
a (Å) 5.611 5.6533 5.64907 5.64484 5.64061 5.63638
InxGa(1-x)As
InAs GaAs x=0.2 x=0.4 x=0.5 x=0.53

Eg (eV) 0.36 1.424 1.211 0.998 1.105 0.860
εr 15.1 13.1 13.500 13.900 13.700 14.160
χ 4.9 4.07 4.236 4.402 4.319 4.510
Nc (cm-3) 2.10E+17 4.00E+17 3.62E+17 3.24E+17 3.43E+17 2.993E+17

Nv (cm-3) 7.70E+18 9.00E+18 8.74E+18 8.48E+18 8.61E+18 8.311E+18
a (Å) 6.0583 5.6533 5.7343 5.8153 5.7748 5.86795
InP 5.8687
N.B. servirebbero le relazioni quadratiche, ma semplifichiamo con le lineari
Inl-xGaxAsyP1-y
InAs InP GaP GaAs x=0.2; x=0.47
y=0.2 Y=0.24
Eg (eV) 0.36 1.344 2.26 1.424 1.34 1.56
εr 15.1 12.5 11.1 13.1 12.72 12.40
χ 4.9 4.38 3.8 4.07 4.36 4.20
Nc 2,1x1017 5,7x1017 1,8x1019 4x1017 3,3x1018 6,7x1018
(cm-3)
Nv 7,7x1018 1,1x1019 1,9x1019 9x1018 1,2x1019 1,3x1019
(cm-3)
a (Å) 6.0583 5.8687 5.4505 5.6533 5.82 5.72
P(A1-xBxCyD1-y)=(1-x)∙y∙P(AC)+(1-x)∙(1-y)∙P(AD) + x∙(1-y) ∙P(BD)+ x∙y∙P(BC)
AlxGa(1-x)N
AlN GaN x=0.1 x=0.2 x=0.28 x=0.3
Eg (eV) 6.2 3.2 3.5 3.8 4.04 4.1
εr 9.14 8.9 8.924 8.948 8.9672 8.972
χ 2.1 4.1 3.9 3.7 3.54 3.5
Nc (cm-3) 1.20E+15 1.20E+18 1.08E+18 9.6E+17 8.64E+17 8.40E+17
Nv (cm-3) 9.40E+16 4.10E+19 3.69E+19 3.28E+19 2.95E+19 2.87E+19
a (Å) 3.11 3.16 3.155 3.15 3.146 3.145
InxGa(1-x)N
InN GaN x=0.1 x=0.2 x=0.25 x=0.3

Eg (eV) 2.05 3.2 3.085 2.97 2.9125 2.855
εr 15.3 8.9 9.54 10.18 10.5 10.82
χ 4.55 4.1 4.145 4.19 4.2125 4.235
1.168E+1
Nc (cm-3) 8.80E+17 1.20E+18 1.14E+18 1.12E+18 1.104E+18
8
Nv (cm-3) 5.20E+19 4.10E+19 4.21E+19 4.32E+19 4.375E+19 4.43E+19
a (Å) 3.5446 3.16 3.19846 3.23692 3.25615 3.27538
AlAs
InxGa1-xAs

Il caso dell’Arseniuro di Gallio
Il caso dell’Arseniuro di Gallio
2.8
Direct Gap
2.6
Indirect Gap
Energy Gap (eV)
2.4
2.2
2.0
1.8
1.6
1.4
0.0 0.2 0.4 0.6 0.8 1.0

x
III-V Energy Gap diretto
Semiconduttori Quaternari
AlAs
InxGa1-xAs

L'evoluzione dei sistemi per telecomunicazione su
fibra ottica segue l’evoluzione dei materiali per
l’optoelettronica:
fine anni '70: fibre multimodo in silica,

emettitori a 850 nm, sistema AlGaAs/GaAs
anni '80: sfruttamento del minimo di dispersione

cromatica a 1300 nm e del minimo di assorbimento
a 1550 nm delle fibre in silica monomodo; si usa
il sistema quaternario InGaAsP
oggi la maggior parte dei sistemi opera a 1550 nm con

amplificatori ottici a fibre drogate Er (erbio)
Dispositivi Optoelettronici
2005-2006
Tecniche di crescita dei substrati
• Czochralski Method
• Bridgman Method
Non tutti i substrati sono disponibili ad ugual costo e
qualità
Tecniche di crescita: Czochralski e Bridgman

Substrati cirstallini generalmente disponibili (in ordine
CRESCENTE di costo e DECRESCENTE in qualità e
diametro):
Si (fino a 300 (400) mm di diametro), GaAs (8”), InP,

SiC (3", 4"), GaN
Substrate growth techniques
• Czochralski Method
Nel metodo Czocharlski, un seme monocristallino viene inserito in un crogiolo

contenente il semiconduttore fuso, dal quale si estrae lentamente un monocristallo
Velocità di crescita 2-3 mm/minuto; O, C contaminanti del Si

Il GaAs spesso contiene B come contaminante
Substrate growth techniques
• Bridgman Method
Nel metodo Bridgman, parte del materiale policristallino viene riscaldato e

poi fatto raffreddare in contatto con un "seme" monocristallino
Epitaxial growth techniques
Epitaxial growth methods

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Compound Semiconductors

GaAs: semiconduttore a gap diretto, minimo della banda di conduzione

la massa dell’elettrone nella valle Γ del

la distanza energetica tra la valle Γ e le altre è nel

la banda di valenza del GaAs presenta tre massimi di

il GaAs è un semiconduttore a gap diretto, mentre il Si

Figure 3.24. One possible velocity-field characteristic of a two-valley

Column III Column V

• Blende Zinc structure : 2 fcc sublattices : III and V

(InxGal-x)As is widely used for photon

Da GaAs passando a InAs attraverso InGaAs

The stippled area indicates the

This quaternary compound is used

The III-nitride compound

Nevertheless, binary II-VI

Ternary IV-VI semiconductor

However, these alloys have

They also have high thermal

• From the greek : Επι = on Ταξει = order

επι (epi) = sopra

lattice-matched (“ad accordo reticolare”)

pseudomorfica (“con piccole differenze di parametro reticolare”)

metamorfica (su substrato con parametro reticolare nettamente

Es. GaAs, AlAs AlxGa1-xAs, 0<x<1

Legge di Vegard Dati due semiconduttori binari AC e BC, con

Legge di Vegard Semiconduttori Quaternari

P = energy gap, costante reticolare, …..

AlAs GaAs x=0.1 x=0.2 x=0.3 x=0.4

Nc (cm-3) 1.50E+19 4.00E+17 1.86E+18 3.32E+18 4.78E+18 6.24E+18

InAs GaAs x=0.2 x=0.4 x=0.5 x=0.53

Nc (cm-3) 2.10E+17 4.00E+17 3.62E+17 3.24E+17 3.43E+17 2.993E+17

Nc (cm-3) 1.20E+15 1.20E+18 1.08E+18 9.6E+17 8.64E+17 8.40E+17

Nv (cm-3) 9.40E+16 4.10E+19 3.69E+19 3.28E+19 2.95E+19 2.87E+19

a (Å) 3.11 3.16 3.155 3.15 3.146 3.145

InN GaN x=0.1 x=0.2 x=0.25 x=0.3

Da GaAs passando a InAs attraverso InGaAs

0.0 0.2 0.4 0.6 0.8 1.0

Da GaAs passando a InAs attraverso InGaAs

fine anni '70: fibre multimodo in silica,

anni '80: sfruttamento del minimo di dispersione

oggi la maggior parte dei sistemi opera a 1550 nm con

Tecniche di crescita: Czochralski e Bridgman

Si (fino a 300 (400) mm di diametro), GaAs (8”), InP,

Nel metodo Czocharlski, un seme monocristallino viene inserito in un crogiolo

Velocità di crescita 2-3 mm/minuto; O, C contaminanti del Si

Nel metodo Bridgman, parte del materiale policristallino viene riscaldato e

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