Growth and Characterization of

IV-VI Semiconductor Multiple

Quantum Well Structures
Patrick J. McCann, Huizhen Wu, and Ning Dai*
School of Electrical and Computer Engineering
*Department of Physics and Astronomy
University of Oklahoma
Norman, OK 73019




Electronic Materials Conference
Santa Barbara, CA
June 27, 2002

Outline
IV-VI Semiconductors
Biomedical Applications
MBE Growth and Characterization
Square and Parabolic MQWs
Summary

IV-VI Semiconductors
(Pb-Salts)
Unique Features
High Dielectric Constants Defect Screening
Can be Grown on Silicon Low Cost, Integration Possibilities
Symmetric Band Structure High Electron and Hole Mobilities
Applications
Thermoelectric Coolers (Low Lattice Thermal Conductivity)
Infrared Detectors (Silicon Integration Possible)
Spintronics (Quantum Dots with Magnetic Impurities)
Tunable Mid-IR Lasers (Medical Diagnostics, etc.)
Tin Concentration in Growth Solution, x (%)
0 2 4 6 8 10
Tin Concentration in layer, x
S
(%)
E
n
e
r
g
y

(
m
e
V
)
60
80
100
120
140
160
180
200
220
240
260
280
W
a
v
e
l
e
n
g
t
h

(
m
i
c
r
o
n
s
)
5
6
7
8
9
10
12
15
20
W
a
v
e
n
u
m
b
e
r

(
c
m
-
1
)
2200
2000
1800
1600
1400
1200
1000
800
600
0 2 3 4 5 6 7 8 9
Room
Temperature
109 - 125 K
Pb
1-x
Sn
x
Se
Lattice Parameter (Angstroms)
6.0 6.1 6.2 6.3 6.4 6.5
7
7

K

W
a
v
e
l
e
n
g
t
h

(

m
)
3.3
5.0
8.0
12.0
18.0
7
7

K

B
a
n
d
g
a
p

E
n
e
r
g
y

(
m
e
V
)
60
80
200
400
600
100
7
7

K

W
a
v
e
n
u
m
b
e
r
s

(
c
m
-
1
)
3000
2000
1300
800
500
PbTe
PbSe
Pb
1-x
Sr
x
Se
Pb
1-x
Sn
x
Se
Pb
1-x
Sn
x
Te
PbSe
1-x
Te
x
Pb
1-x
Sr
x
Te
W
a
v
e
l
e
n
g
t
h

(
m
i
c
r
o
n
s
)
14.0
11.0
9.0
8.0
7.0
6.0
5.5
5.0
4.5
E
n
e
r
g
y

(
m
e
V
)
50
75
100
125
150
175
200
225
250
275
Temperature (K)
0 50 100 150 200 250 300 350
W
a
v
e
n
u
m
b
e
r
s


600
800
1000
1200
1400
1600
1800
2000
2200
2400
PbSe
0.78
Te
0.22
Photoluminescence
PbSe
0.78
Te
0.22
Absorption Edge
Pb
0.95
Sn
0.05
Se
0.80
Te
0.20
Photoluminescence
Pb
0.95
Sn
0.05
Se
0.80
Te
0.20
Absorption Edge
IV-VI Laser Materials
PbSrSe p-type
PbSe Substrate
~
~
~
~
~
~
PbSe n-type
PbSrSe n-type
Double Heterostructure Laser
Breath Analysis with IV-VI Lasers
Heat Sink
Heat Sink
IV-VI Laser
Wavenumber (cm
-1
)
1912.6 1912.7 1912.8 1912.9 1913.0
V
o
l
t
a
g
e

(
V
)
-5.0
0.0
5.0
V
o
l
t
a
g
e

(
V
)
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
Wavenumber (cm
-1
)
1912.68 1912.74 1912.80 1912.86 1912.92 1913.00
I
n
t
e
n
s
i
t
y
(
c
m
-
1
/
m
o
l
e
c
u
l
e

x

c
m
-
2
)
1e-27
1e-26
1e-25
1e-24
1e-23
1e-22
1e-21
1e-20
1e-19
CO
2
(A)
CO
2
(B)
NO
CO
2
+ H
2
O
H
2
O - Spectral Reference
HITRAN '96
eNO
eCO
2
Upper Airway or
Nasal NO (nNO)
Lower Airway
NO (eNO)
40
20
0
e
N
O

C
o
n
c
e
n
t
r
a
t
i
o
n

(
p
p
b
)
0
2
4
6
0 5 25 45
Time (seconds)
Start Exhalation End Exhalation
e
C
O
2
C
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
End Tidal
CO
2
eNO
eCO
2
eNO eNO
eCO
2
eCO
2
Upper Airway or
Nasal NO (nNO)
Lower Airway
NO (eNO)
40
20
0
e
N
O

C
o
n
c
e
n
t
r
a
t
i
o
n

(
p
p
b
)
0
2
4
6
0 5 25 45
Time (seconds)
0 5 25 45
Time (seconds)
Start Exhalation End Exhalation
e
C
O
2
C
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
End Tidal
CO
2
Asthma Diagnosis
Time (seconds)
0 5 10 15 20 25 30 35 40 45 50
C
o
n
c
e
n
t
r
a
t
i
o
n

(
a
r
b
.

u
n
i
t
s
)
Non-Asthmatic
Asthmatic
Exhaled NO
Exhaled CO
2

High exhaled NO indicates airway inflammation.
People with asthma suffer from chronic airway inflammation.
Quantum cascade mid-IR lasers have not been able to do such
measurements even though several attempts have been made.
Laser Focus World,
June 2002, P. 22

Roller et al., Optics
Letters 27, 107 (2002).
IV-VI Epitaxial Layers
High quality layers can be grown on silicon
McCann et al., Journal of Crystal Growth 175/176, 1057 (1997).
Strecker et al., Journal of Electronic Materials 26, 444 (1997).
Room temperature cw photoluminescence
McCann et al., Applied Physics Letters 75, 3608 (1999).
McAlister et al., Journal of Applied Physics 89, 3514 (2001).
Optical devices on silicon
Through-the-substrate inter-chip optical interconnects (PC Magazine, January 21, 2002).
Modulators for free-space optical communication.
Infrared imaging arrays.
MBE Growth on Silicon and BaF
2
SiO
2
desorption at 700C allows epitaxial
growth of nearly lattice-matched CaF
2
on Si
CaF
2
growth on Si is layer-by-layer
BaF
2
growth on CaF
2
is layer-by-layer
PbSrSe growth on low surface energy BaF
2

is initially 3D (island)
PbSrSe layer eventually becomes 2D after
growth of more than 1 m
IV-VI MBE Chamber at OU
Sources: PbSe, Sr, Se, PbTe, BaF
2
, CaF
2
, Ag, Bi
2
Se
3
In Situ RHEED
Si(111) (77) after
oxide desorption
After growth of
2 nm CaF
2
After growth of
600 nm BaF
2

Lattice Parameter (Angstroms)
5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8
W
a
v
e
l
e
n
g
t
h

(
m
i
c
r
o
n
s
)

0.1
0.2
0.3
0.5
0.8
1.3
2.0
3.3
5.0
8.0
12.0
18.0
26.0
40.0
B
a
n
d
g
a
p

E
n
e
r
g
y

a
t

7
7

K

(
e
V
)
0.01
0.1
1
10
W
a
v
e
n
u
m
b
e
r
s

(
c
m
-
1
)
50000
30000
20000
12500
8000
5000
3100
2000
1300
800
500
300
200
PbTe
PbSe
Silicon
CaF
2

BaF
2

Pb
1-x
Sn
x
Se
1-y
Te
y

Pb
1-x
Eu
x
Se
1-y
Te
y

EuTe
Pb
1-x
Sn
x
Se
Pb
1-x
Sn
x
Te
EuSe
BaF
2
(111) substrate
(11) at 500 C
After growth of 6
of PbSrSe on BaF
2
After growth of 3 m
of PbSrSe on BaF
2
PbSe/PbSrSe MQWs

PbSe
PbSrSe
PbSe
PbSrSe
PbSrSe
PbSe
PbSrSe
Buffer layer
Substrate
20
4 nm to 100 nm
e/2u (degree)
25.2 25.4 25.6 25.8 26.0 26.2 26.4 26.6
L
o
g

D
i
f
f
r
a
c
t
i
o
n

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
1e+0
1e+1
1e+2
1e+3
1e+4
1e+5
0
+1
+2
+3
+4
+5
+6
-1
-2
BaF
2
(222)
-3
-4
1e+0
1e+1
1e+2
1e+3
1e+4
1e+5
(a)
(b)
0
+1
+2
+3
+4
+5
-2
-1
-3
Si Substrate
BaF
2

Substrate
HRXRD
MQWs on Si have high crystalline quality
MQWs on BaF
2
substrates have higher crystalline
quality due to better thermal expansion match
Photoluminescence

Energy (meV)
280 300 320 340 360 380 400 420 440
P
L

I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
0.0
0.5
1.0
1.5
2.0
2.5
Wavenumbers (cm
-1
)
2200 2400 2600 2800 3000 3200 3400 3600
4 nm (x5)
20 nm
12 nm
10 nm
5
o
C
Measured Spectra
Gaussian Fits
BaF
2
Substrates
Near-IR (~980 nm) cw diode laser pumping (low intensity, ~250 mW)
Strong Quantum Size Effect
Strong CW Emission at 55C
Interference Fringes Dominate Spectra
Spacings depend on index of refraction and epilayer thickness
Strong optical resonance indicates stimulated emission processes
Energy (meV)
280 300 320 340 360 380
P
L

I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
0.0
0.2
0.4
0.6
0.8
1.0
Wavenumber (cm
-1
)
2100 2200 2300 2400 2500 2600 2700 2800 2900 3000 3100
20 nm
5
o
C
25
o
C
35
o
C
45
o
C
55
o
C
15
o
C
Measured Spectra
Gaussian Fits
CO
2
Absorption
Mid-IR Emitter on Silicon
Wavenumber (cm
-1
)
2000 2500 3000 3500
P
L

I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
0.0
0.2
0.4
0.6
0.8
Energy (meV)
220 260 300 340 380 420 460
W331: 800 mA
15
o
C
25
o
C
35
o
C
Temperature (
o
C)
0 50
E
n
e
r
g
y

(
m
e
V
)
330
350
dE/dT=0.381 meV/K
CO
2
Absorption
Measured Spectra
Gaussian Fits
Si Substrate
Near-IR (~980 nm) cw
diode laser (~250 mW)
Emission through Silicon Substrate
Promising optical interconnect architecture

IV-VI MQW
Si Substrate
P
L

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
T = 2 5
o
C
2 8 0 0 m A
2 6 0 0 m A
2 4 0 0 m A
2 2 0 0 m A
2 0 0 0 m A
1 8 0 0 m A
1 6 0 0 m A
M Q W / B a F
2
/ C a F
2
/ S i ( 1 1 1 )
P h o t o n E n e r g y ( m e V )
2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0
T = 2 5
o
C
1 7 0 0 m A
1 8 0 0 m A
1 9 0 0 m A
2 0 0 0 m A
2 1 0 0 m A
2 2 0 0 m A
2 3 0 0 m A
M Q W / B a F
2
( 1 1 1 )
InGaAs (972 nm) diode
laser pump current
Pumping laser injection current (mA)
1400 1600 1800 2000 2200 2400 2600 2800 3000
E
p
i
l
a
y
e
r

t
e
m
p
e
r
a
t
u
r
e

(
o
C
)
25
50
75
100
125
MQW/BaF
2
(111)
MQW/BaF
2
/CaF
2
/Si(111)
MQW bonded on Si
BaF
2
Substrate
Silicon
Substrates
35
Pumping laser injection current (mA)
1400 1600 1800 2000 2200 2400 2600 2800 3000
E
p
i
l
a
y
e
r

t
e
m
p
e
r
a
t
u
r
e

(
o
C
)
25
50
75
100
125
MQW/BaF
2
(111)
MQW/BaF
2
/CaF
2
/Si(111)
MQW bonded on Si
BaF
2
Substrate
Silicon
Substrates
35
BaF
2
Substrate
Silicon
Substrates
Less epilayer heating
with higher thermal
conductivity silicon
substrates
Optical Heating of Epilayers
H. Z. Wu et al., J. Vac. Sci. and Technol. B 19, 1447 (2001).
hv (meV)
150 175 200 225 250
A
T
/
T
0.0
0.1
4K
70K
(2-2)
O
(2-2)
N
(1-1)
O
(1-1)
N
(2-2)
N
(1-1)
N
(1-1)
O
20.6 nm
IR Transmission
Differential Transmission Fourier
Transform Infrared Spectroscopy

Subtract transmission spectra collected at two
different temperatures

Peaks yield interband transition energies


H. Z. Wu et al., Applied Physics Letters 78, 2199 (2001).

20 or more pairs of
PbSe/PbSrSe
PbSrSe
Band
Gap
PbSe
Band
Gap
[111]
20 or more pairs of
PbSe/PbSrSe
PbSrSe
Band
Gap
PbSe
Band
Gap
PbSrSe
Band
Gap
PbSe
Band
Gap
[111] [111]
4 nm to 100 nm
hv (meV)
150 200 250 300 350 400 450 500 550
A
T
/
T
0.0
0.1
0.2
0.3
0.4
4K
70K
150K
210K
295K
(1-1)
N
(2-2)
N
(3-3)
N
x 2
x 3
x 5
(1-1)
o
(2-2)
o
(3-3)
o
Barrier
(1-1)
o
(2-2)
o
(3-3)
o
Barrier
(1-1)
N
(2-2)
N
(3-3)
N
(1-1)
o
(2-2)
o
(3-3)
o
Barrier
(1-1)
o
(1-1)
o
(2-2)
o
(2-2)
o
(3-3)
o
(3-3)
o
(2-2)
N
L
QW
=20.6 nm
hv (meV)
120 160 200 240 280 320 360 400
A
T
/
T
0.00
0.02
0.04
0.06
0.08
29.7 nm
20.6 nm
9.7 nm
(1-1)
o
(1-1)
N
(2-2)
N
(2-2)
o
(1-1)
N
(1-1)
o
(2-2)
N
(2-2)
o
(3-3)
N
(3-3)
o
(2-2)
o
(2-2)
N
(3-3)
o
(4-4)
o
(1-1)
N
(1-1)
o
Quantum Size Effects
Removal of L-Valley Degeneracy
Direct gap is at the L-point in k-space
Four Equivalent L-valleys
Symmetric conduction and valence bands
Potential variation in [111] direction
One L-valley is normal to the (111) plane in k-space
Three L-valleys are at oblique angles
Two different effective masses for
electrons (and holes) in the PbSe MQWs





Normal
Oblique
Oblique
Oblique
l
m
normal
m =
111
) 8 ( 9
111 t l t l
oblique
m m m m m + =
m
N
e
= 0.0788

m
O
e
= 0.0475

m
N
h
= 0.0764

m
O
h
= 0.0408

Normal Oblique
(3-Fold Degenerate)
Interband Transitions
QW Thickness (nm)
8 10 12 14 16 18 20 22 24 26 28 30
T
r
a
n
s
i
t
i
o
n

E
n
e
r
g
y

(
m
e
V
)
160
170
180
190
200
210
220
230
Normal Valley
Oblique Valleys
4 K
(1-1)
N
(1-1)
O
(1-1)
O
Eg (PbSe) = 150 meV (4K)
(1-1)
O
Energy Levels
QW Thickness (nm)
10 15 20 25 30
E
n
e
r
g
y

L
e
v
e
l
s

(
m
e
V
)
-50
0
50
100
150
200
E
g
(PbSe) = 150 meV at 4 K
QW Thickness (nm)
10 15 20 25 30
C
o
n
d
u
c
t
i
o
n

B
a
n
d

E
n
e
r
g
y

L
e
v
e
l
s

(
m
e
V
)
150
155
160
165
170
175
180
185
190
195
PbSe (Bulk) Conduction Band Edge
LO Phonon Energy
(16.7 meV)
TO Phonon Energy
(5.9 meV)
Normal Valley
Oblique Valleys
4 K
Normal
Oblique
PL Emission
Oblique Valleys
Lowest energy level has a low density of states
Lower threshold for population inversion
Stimulated emission at low excitation rates
Four-level laser design
Density of States
=
Lasing Thresholds
IV-VI Mid-IR VCSELs
Bulk Active Region
Optical pumping threshold: 69 kW/cm
2

Z. Shi et al., Appl. Phys. Lett., 76, 3688 (2000)
MQW Active Region
Optical pumping threshold: 10.5 kW/cm
2

C. L. Felix et al., Appl. Phys. Lett. 78, 3770 (2001)
Photon Energy (meV)
150 200 250 300 350
A
T
/
T
77 K
110 K
150 K
200 K
293 K
x2
(3-3)
N
(3-3)
O
(1-1)
N
(1-1)
O
(2-2)
N
(2-2)
O
(2-2)
O
(2-2)
O
(2-2)
O
(3-3)
O
(3-3)
O
(3-3)
O
(1-1)
O
(1-1)
O
(1-1)
O
(1-1)
O
(2-2)
O
CO
2
(2-2)
N
H
2
O Absorption
(1-1)
N
(2-2)
N
CO
2
Absorption
E
g
(77K) = 180 meV E
g
(77K) = 605 meV
L
QW
= 40 100 nm L
B
= 30 nm
Pb
1-x
Sr
x
Se
x = 14%
x = 0%
E
c
E
v
E
g
(77K) = 180 meV E
g
(77K) = 605 meV
L
QW
= 40 100 nm L
B
= 30 nm
Pb
1-x
Sr
x
Se
x = 14%
x = 0%
E
c
E
v
Parabolic MQWs
m
n E
e
g c
QW
E Q
L
nj
i
*
2
2
1
) ( 2
A
=

Expect Evenly-Spaced Harmonic
Oscillator Eigenvalues
hv (meV)
150 200 250 300 350
A
T
/
T
100 nm
80 nm
60 nm
T=77 K
40 nm
(1-1)
N
(1-1)
O
(2-2)
N
(2-2)
O
(3-3)
O
(3-3)
O
(2-2)
N
(2-2)
O
(3-3)
N
(3-3)
O
(4-4)
O
(5-5)
O
(6-6)
O
(2-2)
O
(2-2)
O
(2-2)
N
(2-2)
N
(1-1)
O
(1-1)
N
(1-1)
N
(4-4)
O
(4-4)
O
(5-5)
O
(3-3)
N
(1-1)
O
(1-1)
O
Parabolic MQW Analysis
Measured bandgaps in strained PbSe
(caused by lattice mismatch with PbSrSe)
compared to 77 K bandgap for bulk PbSe
allows determination of deformation
potentials: D
d
= 6.1 eV and D
u
= -1.3 eV.
Energies for the higher confined states in
100 nm sample allows determination of
band non-parabolicity parameters:

c
=
v
= 1.910
-15
cm
2

k (t/a)
-0.3 -0.2 -0.1 0.1 0.2 0.3
Energy (meV)
-750
-500
-250
250
500
750
Nonparabolic
Parabolic
Nonparabolic
Parabolic
Equally Spaced Energy Levels
(Harmonic Oscillator)
E
(2-2)
AE
HO
= [E
(2-2)
- E
(1-1)
]
n=1
n=2
n=5
n=4
n=3
n=6
E
(1-1)
AE
HO
E
g
= E
(1-1)
- AE
HO
E
(2-2)
AE
HO
= [E
(2-2)
- E
(1-1)
]
n=1
n=2
n=5
n=4
n=3
n=6
E
(1-1)
AE
HO
E
g
= E
(1-1)
- AE
HO
) 1 (
2
2
2 2
k
m
k
E
c
c
c
=

) 1 (
2
2
v
v
2 2
v
k
m
k
E =

Summary
IV-VI semiconductors are versatile materials for a
variety of applications.
A mid-IR laser spectroscopy application for asthma diagnosis
has been developed.
PbSe-based MQW structures have attractive properties
for improved mid-IR laser technology.
L-valley degeneracy removal.
Energy level structure in MQWs on (111)-oriented substrates
enables low population inversion thresholds.