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Compound Semiconductors

Compound Semiconductors
Compound Semiconductors

Compound Semiconductors
Elemental Semiconductors

Compound Semiconductors
Elemental Semiconductors

Compound Semiconductors
Compound Semiconductors

Compound Semiconductors
Compound Semiconductors

Compound Semiconductors
Reticolo diamante e zincoblena

Compound Semiconductors
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

Compound Semiconductors
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

Compound Semiconductors
Velocità di deriva vs campo elettrico: GaAs e Si

Compound Semiconductors
Distribuzione degli elettroni tra le varie valli vs E

Compound Semiconductors
Velocity overshoot in GaAs

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


semiconductor.
Compound Semiconductors
Compound Semiconductors
III-V Semiconductors

II-VI Semiconductors

Compound 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
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
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
Compound Semiconductors

Compound Semiconductors
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.
Compound Semiconductors
Semiconduttori composti

Compound Semiconductors
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
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
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
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!”
Compound Semiconductors
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
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)
Compound Semiconductors
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

Compound Semiconductors
Semiconduttori composti

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
Compound Semiconductors: AlxGa1-xN, InxGa1-xN, ….

Compound Semiconductors
Semiconduttori composti
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.
Compound Semiconductors
Semiconduttori composti
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.

Compound Semiconductors
Semiconduttori composti

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.

Compound Semiconductors
Eterostrutture

Compound Semiconductors
Crescita Epitassiale

• From the greek : Επι = on Ταξει = order


• The science to preserve crystal order from the substrate to the
grown material

Compound Semiconductors
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

Compound Semiconductors
Crescita Epitassiale

Compound Semiconductors
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)

Compound Semiconductors
Crescita Epitassiale

Compound Semiconductors
Strain in heteroepitaxial layers

Compound Semiconductors
Strain in heteroepitaxial layers

Compound Semiconductors
Detrimental effects of dislocations

Compound Semiconductors
Strained heteroepitaxial layers: critical thickness

Compound Semiconductors
Defects in Epitaxial Growth

Compound Semiconductors
Dislocations

Compound Semiconductors
Semiconduttori Ternari e Quaternari

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

Compound Semiconductors
Semiconduttori Ternari e Quaternari

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:

Compound Semiconductors
Semiconduttori Ternari e Quaternari

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/

Compound Semiconductors
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

P(AxB1-xC)=x∙P(AC)+(1-x)∙P(BC)
Compound Semiconductors
Semiconduttori Ternari
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

P(AxB1-xC)=x∙P(AC)+(1-x)∙P(BC)
N.B. servirebbero le relazioni quadratiche, ma semplifichiamo con le lineari
Compound Semiconductors
Semiconduttori Ternari
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)
Compound Semiconductors
Semiconduttori Ternari
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

P(AxB1-xC)=x∙P(AC)+(1-x)∙P(BC)
N.B. servirebbero le relazioni quadratiche, ma semplifichiamo con le lineari
Compound Semiconductors
Semiconduttori Ternari
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

P(AxB1-xC)=x∙P(AC)+(1-x)∙P(BC)
N.B. servirebbero le relazioni quadratiche, ma semplifichiamo con le lineari
Compound Semiconductors
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)
Compound Semiconductors
Il caso dell’Arseniuro di Gallio

Compound Semiconductors
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
Compound Semiconductors
III-V  Energy Gap diretto

Compound Semiconductors
Semiconduttori Quaternari

Compound Semiconductors
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)
Compound Semiconductors
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

Compound Semiconductors
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

Compound Semiconductors
Substrate growth techniques
• Bridgman Method

Nel metodo Bridgman, parte del materiale policristallino viene riscaldato e


poi fatto raffreddare in contatto con un "seme" monocristallino

Compound Semiconductors
Epitaxial growth techniques

Compound Semiconductors
Epitaxial growth methods

Compound Semiconductors