609

Optical Properties of Wide Bandgap 111-V Nitride Semiconductors

(Invited)

k.M. Kolbas, I. K. Shmagin, J. F. Muth

Department of Electrical and Computer Engineering
NC State University, Raleigh N C 27695-791 1
9 19-5 15-7350; 919-5 15-5523(f); kolbas@eos.ncsu.edu

Abstract edge is at 369 nm and has a 10 nm width, which is

Applications of 111-V nitride materials, such as
GaN. AIN. InN and their allow include blue-ereen
light'emitting devices, solar -blind photodetectors,
and high power/frequency electronics. A number
of unique and potentially useful optical
phenomena have been observed in high quality
thin f i l m and heterostructures of AIGaN, GaN,
and InGaN. These include: 1) persistent optical
effects such as optical metastability in bulk GaN
single crystals; 2) tunable emission from InGaN
multiple quantum wells, (MQW) and; 3)
reconfigurable optical properties in InGaN/GaN
heterostructures.
comparable to 60 pm thick high quality epitaxial
films grown on sapphire substrates. The small
absorption coefficient and narrow width of the
absorption band edge imply that the bulk GaN
single crystals have a very high optical quality and
a low optical defect density. SIMS analysis
indicated that the sample had I-, 2-, 5x10'' cm
concentrations of [Si],[C], [HI, and 3x10'' cm' of
[O], respectively.
1.g

Photoinduced Metastable Defects

Persistent optical effects have been studied in wide
band-gap semiconductors by several research
groups. [l] Deep levels are responsible for
persistent photoconductivity in n- and p- type
GaN. In this case an impurity associated lattice
relaxation mechanism has been suggested to be
causing the persistent photoconductivity in the p-
and n-type GaN. Optical memory effects have
been seen and associated with oxygen impurities
in epitaxially grown GaN and A1N epitaxial thin
films that have distinct morphological features. In 600 550 500 450 400 350
general persistence lasts much longer than in other
semiconductors due to the large binding energies WAVELENGTH (nm)
in these wide band gap materials.
Fig. I Room temperature transmission spectrum through
Optical Metastability in a bulk GaN single crystal (=0.25 mm). The absorption
Bulk GaN Single Crystals coefficient was calculated to be 50 cm-' at 500 nm.
Optical metastability in high quality bulk GaN
single crystals (grown by sublimation of cold Photoluminescence from a bulk GaN crystal at
pressed GaN pellets in flowing ammonia) has been 77K is shown in Figure 2. The band edge
observed at both room and cryogenic emission peak is centered at 359.0 nm and has a
temperatures. Details of the growth by Professors full width at half maximum (FWHM) of 5 nm (48
Sitar and Davis can be found elsewhere. [ 2 ] The meV). The edge is.red-shifted approximately 10
crystals are well faceted hexagonally shaped rods nm relative to thin epitaxial GaN films grown on
(0.2-0.3 mm wide and 0.7-1.0 mm long) with the sapphire (due to selective absorption or lack of
e-axis along the length of the crystal. The crystals strain relative to thin films). The initial emission
are colorless and transparent to the naked eye and spectrum (Figure 2a) was centered on the band
have excellent room temperature transmission edge and appeared colorless to the naked eye (no
curves as shown in Figure 1. The absorption band yellow or blue).

0-7803-4306-9/98/$10.001998 IEEE
610
After 10 minutes the spectrum exhibits another
peak at 378.0 nm and the color gradually changes
to bright blue. After 27 minutes of excitation the
blue emission band is centered at 388.0 nm and
consists of at least one LO-phonon (90 meV)
assisted replica of the zero-phonon (378.0 nm)
line. The large FWHM of the blue emission (249
meV) implies a strong lattice interaction. No
decrease in the total output emission intensity was
detected at 77 K, while the ratio of blue (388.0
nrn) to UV (359.0 nm) output intensities increased
by a factor of 10 during 27 minutes of exposure.
Similar new peaks were observed at room
temperature but the integrated intensity of the
peaks decreased by a factor of 20. [3]
I ' . . .meV
B u l k G a N . ' . . ' 85 '.. ' beam from 0.11 mm (6.32 KW/cm3) to 1.6 mm
T= 77 K
480 440 400 360
WAVELENGTH (nm)
Fig. 2 77K photoluminescence spectra from a bulk GaN
single crystal. The ratio of blue to UV emission increased
by a factor of 10 during the 27 minutes exposure.
No physical damage was done to the surface of the
sample as observed under an optical microscope.
To verify that the changes in the optical properties
were indeed metastable, the room temperature
emission spectrum was taken from the sample two
weeks after the room temperature results were
obtained. The integrated output emission was
restored to its original intensity, but the blue
emission band was still clearly observed. Such a
long recovery time indicates that the photoinduced
levels have a large thermal activation energy or
that the process is not reversible.
Tunable Emission from
InGaN Multiple Quantum Wells
Tunable visible emission from InGaN/GaN
quantum wells from blue (470 nm) to yellow (560
nm) was achieved by varying the pump. power
density. The output emission was nearly constant
in intensity throughout the tuning range. The
sample used was grown by atmospheric pressure
MOCVD in the group of Prof. S . P. DenBaars,
University of California, Santa Barbara. The
sample consisted of 5 InGaN quantum wells
deposited on top of a 2.4 mm GaN layer (Si
doped). The InGaN quantum wells and
Inoo5Gq95Nbarriers were 2.5 and 7 nm thick,
respectively. The structure was completed with a
50 nm thick GaN capping layer. Details of the
growth process can be found elsewhere. [4]
The power density dependent room temperature
spectra representative of photoluminescence
measurements from the sample are shown in
Figure 3. The power density for the presented
data was changed by defocusing the excitation
(0.63 KW/cm3). As shown in Figure 3 (a), a single
short wavelength emission peak centered at 475
nm with a FWHM of 28 nm corresponded to the
highest input power density.
320
650 600 550 500 450 400 350;
WAVELENGTH (nm)
Fig. 3 Room temperature photoluminescence spectra
.from the 5-quantum well InGaN sample at various power
densities. The wavelength shifts more than 90 nm at
room temperature.
The peak wavelength and EWHM of 'the output
emission spectra from the InGaN/GaN MQWs at
77 K are plotted as a .function of input power
density in Figure 4 (a) and (b), respectively. Note
that the output emission spectra shift toward
shorter wavelengths and narrower FWHM at higher
pump densities. This is opposite to what would be
expected if the sample were heating. Even though
these results were obtained under pulsed excitation
similar power dependent results were observed
using CW excitation (Ar-ion laser, 305 nrn).
. .

The shift in emission wavelength with excitation
power density could be due to tunneling-assisted
donor to acceptor transitions, a change in binding
energies of impurities due to quantum size effects,
bandfilling effects, and piezoelectric field induced
energy shifts. However, none of these effects
alone appear to be sufficient to explain the large
observed shift. Additional work, including the
analysis of "V" shaped defects observed in TEM
cross sections, need to be considered.
470
65
60
55
50
45
40
35
-_
Rn
0 1 2 3 4 5 6 7
INPUT POWER DENSITY (KW cm' 2,
Fig. 4 Peak wavelength (a) and FWHM (b) of the output
emission from the Swell InGaN quantum well sample as
a function of pump power density at 77K.
Data Storage in InGaN Heterostructures
InGaN heterostructures may have potential
applications in optically encoded information
storage and other photonic devices such as spatial
light modulators. Specifically, it was found that
high density, high contrast patterns could be
written on InGaN/GaN heterostructures with
ultraviolet light at room and cryogenic (77K)
temperatures. After the written pattern is erased
new information can be written on the same spot
without degradation in efficiency or retention
time. These effects last more than 4 hours at room
temperature and have a much longer retention
time at 77 K.
The sample used in this study was grown in the
laboratory of Professor R. Dupuis at the University
of Texas at Austin by low pressure MOCVD. It
consisted of a 60 nm unintentionally doped
61 1
layer grown on 1.5 p m of GaN on a c-
In,, 14Ga,l.X6N
plane sapphire substrate. [5] The frequency
tripled pulsed output of a TiSapphire laser (250 fs
pulse at 280 nm) was used for both reading and
writing information.
The 300K CW photoluminescence peak was
centered at 403 nm (14% Indium composition)
with a (FWHM) of 19 nm. Pulsed
photoluminescence taken at 77 K with a frequency
tripled TiSapphire laser had a FWHM of 18 nm
(Fig. 5(a)) and narrowed under increased pump
levels to 3 nm as shown in Fig. 5(b) The line
narrowing and rapid increase in intensity is a
strong indicator of high quality of this sample and
is indicative of the onset of stimulated emission.
%
z
2~~~~
g
W
5 (a)
c
4
rl
a
Y
450 420 390 360 450 420 390 360
WAVELENGTH (nm) WAVELENGTH (nm)
Fig. 5 77 K pulsed photoluminescence spectra from the
InGaN/Gah' single heterostructure at power densities of
approximately 4 and 8 MW cnY2. The output emission
line width narrows from 18 nm to 3 nm with increased
power density, as shown in (a) and (b) respectively.
In "read" conditions the sample is broadly
illuminated at low power density (0.4 W cm.?
average power; peak power of 0.01 MW cm").
The grainy appearance in the photographs of
Figure 6 is the result of scattered light from the
unpolished side of the sapphire substrate and not
the epitaxial film which is smooth. To the naked
eye under these conditions the sample appeared
purple-violet.
Writing the vertical lines on the sample shown in
Figure 6 was accomplished by focusing the
frequency tripled output of the TiSapphire laser
(280 nm) to a spot size of approximately 200 pm.
The average power density in "write" condition was
approximately 160 W cnY2 (peak power of 4 MW
cm.'). To write a pattern the focused beam was
manually translated across the surface of the
sample using the X and Y micrometer screws on
the focusing lens mount. Translating the lens
612
slowly resulted in a bright high contrast line while
translating quickly resulted in a low contrast line.
The breaks in the line are due to the human
operator not moving the micrometer smoothly and
are not due to the material. These results suggest
that the writing process is fluence dependent.
The set of parallel vertical lines shown in Fig. 6
were written at room temperature. The sample was
left under room lights at room temperature and
photographs were taken under "read" conditions
after two, three, and four hours as shown in Figure
6 . Note that the visible contrast between the
written pattern and the unexposed area diminished
with time. The ability to repeat the writing and
reading process on the same location of the
sample without loss of contrast was confirmed
several times. [6]
InG."aU Single tletern\trurture. Kl
t=t,. It- Z hr
At= 3 hr. &=-I tir.
Fig. 6 An optical pattern consisting of a set of parallel
lines was written on the InGaNlGaN single heterostructure
by high-density W light at room temperature. The
photoinduced pattern is clearly observed in low intensity
UV light. Note the diminishing contrast between the
written pattern and the unexposed areas with time.
No damage or change in the surface of the sample
due to the writing process was observed. ' The area
on which information was written was examined
under an optical hefore and after
immersion in HC1 (20 min.). No Or
residual pattern was observed before or after the
HCI immersion. After the HCI immersion the
optical pattern w a still visible under "read"
conditions.
InGaN MQWs were also evaluated and found to
have longer retention times than the single
heterostructure. [7] The image is persistent for
more that five days for a 12 MQW sample and
more than several months for a 20 MQW sample.
The effect can be applied to optical data storage
technology and other photonic devices such as
spatial light modulators used in optical correlators
and optical interconnects.
Conclusions
The ability to write, store and read information
with ultra-violet light on an InGaN/GaN
heterostructure or quantum well heterostructure
have been demonstrated. The effect is quite
strong and persists at room temperature from a
few hours to several days. Understanding and
enhancing these effects could lead to a new high
density optical storage medium as well as other
photonic devices such as spatial light modulators
used in optical correlators and optical
interconnects. A more complete understanding of
these mechanisms should also help in the growth
and design of 111-V nitride-based optoelectronic
devices such as laser diodes, light-emitting diodes
and detectors.
References
1. See references 4 through 13 in reference 3 below
2. C. M. Balkas, Z. Sitar, T. Zheleva, L. Bergman, I. K.
Shmagin, J. F. Muth, R. M. Kolbas, R. Nemanich, and
R. F. Davis, Materials Research Society Symp. Proc.
Vol. 499,Ill-VNitrides, pp. 41-46(1997).
3. I. K. Shmagin, J. F. Muth, J. H. Lee, R. M. Kolbas,
C. M. Balkas, Z. Sitar and R. F. Davis, Applied Physics
Letters Vol. 71,No. 4,pp. 455-457(28July 1997).
4. S. Keller, B. P. Keller, D. Kapolnek, U. K. Mishra,
S . P. DenBaars, I. K. Shrnagin, R. M. Kolbas and S .
Krishnankutty, J. Crystal Growth Vol. 170, 349-352
(1997).
5. P. A. Grudowski, C. J. Eiting, J. Park, B. S . Shelton
and D. J. H. Lambert, and R. D. Dupuis, submitted to
Appl. Phys. Lett, Manuscript number L-1773.
6. I. K. Shmagin, J. F. Muth, R. M. Kolbas, R. D.
Dupuis, P. A. Grudowski, C. J. Eiting, J. Park, B. S .
Shelton and D. J. H. Lambert, Applied Physics Letters
Vol. 71,No. 18,pp. 2572-2574(3 November 1997).
7. I. K. Shmagin, J. F. Muth, R. M. Kolbas, M. P.
Mack, A. c. Abare, s. Keller, L. A. ColdEn, U. K.
Mishra and S. P. DenBaam, Applied Physics Letters Vol.
71,No. 11, pp. 1455-1457(15September 1997).