Journal o f Electronic Materials, Vol. 6 , N o .

3 , 1977

CHARACTERIZATION OF GaN EPITAXIAL LAYERS U S I N G

CATHODOLUMINESCENCE

*t *
S. S. Liu , T. R. Cass + and D. A. Stevenson

( R e c e i v e d J u l y 12, 1976)

Cathodoluminescence (CL) properties of GaN heteroepitaxial

layers, both undoped and Mg-doped, were studied by scanning
electron microscopy. The GaN samples examined were g r o w n
on single crystal sapphire substrates by v a p o r p h a s e epi-
taxy and contained different amounts of Mg. It was found
that the CL intensity of a GaN specimen depends on its Mg
concentration. As the amount of Mg in the GaN lattice in-
creases, the spectral maximum shifts to longer wavelengths;
as the full compensation level is approached, as indicated
by an abrupt increase in resistivity, the overall CL inten-
sity decreases to complete extinction. T h e s e effects are
presumably due to the increased density of recombination
centers, predominantly nonradiative, generated by the
incorporation of Mg deep level impurities.

Department of Materials Science and Engineering, Stanford

University, Stanford, Caiifornia 94305.
+
Hewlett-Packard Laboratories, Palo Alto, California 94304.

tCurrent address: Intel Corporation, 3065 Bowers Avenue,

S a n t a Clara, California 95051.

237

© 1977 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. No part
of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or
by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, with-
out written ~ermission of the publisher.
238 Liu, Cass, and Stevenson

T h e s e results established a basis for the qualitative

characterization of the Mg distribution in GaN layers.
This technique was applied to GaN metal-insulator (GaN:Mg~
n-type semiconductor (GaN) electroluminescent diodes in
order to determine the nonuniformity of Mg distribution
in the insulating layer. Relevant CL micrographs indicate
that, in some cases, isolated conducting grains are embed-
ded in an otherwise insulating matrix. This observation
was correlated with specific device characteristics to
provide a basis for rationalizing device performance.

Key words: gallium nitride, cathodoluminescence, vapor

p h a s e epit~xy, heteroepitaxy, electroluminescence.

Introduction

Gallium nitride (GaN), a member of the III-V compound

semiconductor family, has a wurtzite crystal structure with
direct band gap of about 3.4 eV at room temperature. It
may be synthesized by v a p o r phase heteroepitaxial growth on
single crystal sapphire substrates (i) yielding n-type
layers with carrier concentrations in the range of i018-i019
cm -3, resistivities of 10-2-10-~ohm-cm, and mobilities of
about I00 cm2/v-sec. The n-type conductivity can be com-
pensated by doping with group-II elements, e.g., Mg or Zn
during growth, forming an insulating layer. Fabrication
of metal-insulator-n-type semiconductor (MIN) electrolumi-
nescent GaN diodes that emit violet (I), blue (2), green
(3), and yellow (4) luminescence has been reported.

A mechanism for light emission in these MIN devices

has recently been proposed (5,6): upon application of a
voltage, electrons are injected by quantum-mechanical
tunneling at the cathode into the i-layer at a region of
high electric field, say 10SV/cm; these injected carriers
are accelerated and impact ionize impurity atoms or impurity
atom complexes. Recombination through the impurity centers
then produces luminescence. The epitaxial layers are
faceted and contain crystallites that are separated by
low-angle boundaries which are regions of high electric
field and thus preferred locations for tunneling (7). As
a consequence, the luminescence pattern consists of numer-
ous point light sources originating from these boundary
regions (8).
Characterization of GaN Epitaxial Layers 239

A good MIN diode is defined as a device that has a

sharp and uniform breakdown characteristic and w h i c h emits
visible light with an applied bias of 5 to 20 V. Two m a j o r
factors in controlling device performance are junction
geometry (i-n and m-i interfaces) and the impurity distri-
bution within the i-layer; both of these factors are influ-
enced by several independent growth parameters, as will be
reported elsewhere (7). The present p a p e r describes the
use of a scanning electron microscope with a dispersive
cathodoluminescence (CL) system to characterize heteroepi-
taxial GaN layers and correlates these CL observations with
device I-V properties.

Cathodoluminescence is the emission of light from a

substance as a result of electron irradiation and, when
dealing with semiconductors, it is analogous to photo-
luminescence (PL). Cathodoluminescence studies are parti-
cularly useful for large band gap semiconductors, such as
GaN, if intense UV excitation sources are not readily avail-
able. CL also offers other advantages over PL, the primary
one being that an electron beam can be focused to a much
smaller spot than can a laser beam, with correspondingly
higher excitation density. In addition, scanning CL images
may be obtained, with spatial resolution in the micron
range. Spectral information, similar to that obtained by
PL, may also be derived from electron beam excitation.

Experimental

The GaN samples used in this s t u d y were grown by v a p o r

p h a s e epitaxy on single crystal sapphire substrates, with
either (10"2) "R-plane", or (00-I) "Basal plane" orienta-
tion, using a procedure previously described (i). The
layers were generally single crystalline with the crystallo-
graphic orientation relationships of (II'0)GaNII(i0"2)AI20 3,
<ll'0>GaN] ]<12-0>A120s, or (00.1)G~] ] (00.1)AI205, <II.0>
GaNII<I2"0>AI203, respectively (9). Typically, either a
single layer (undoped or Mg-doped) was grown, or a doped
layer was subsequently grown on an undoped underlayer.
Doping was accomplished by addition of elemental Mg v a p o r
during growth. The partial pressure of Mg in the growth
chamber was controlled by the Mg source temperature and
the flow rate of the hydrogen carrier gas. To s t u d y the
effect of the Mg content in the GaN lattice on
240 Liu, Cass, and Stevenson

cathodoluminescence, several doped layers were grown with

differing Mg concentrations on R-plane substrates. For
most cases, both the undoped and d o p e d layers were grown
for 30 minutes each at about 950°C, with total flow rate
of 2050 ml/min, and NH 3 and GaCI partial pressures of
0.30 and 0 . 0 0 3 atm, respectively. It was found that the
growth rate decreases with increasing Mg partial pressure,
and the resulting doped layers generally have thicknesses
of a few microns (7).

The experimental arrangement of the SEM CL system is

shown in Figure i. The point of incidence of the electron
beam on the specimen is situated at one focus of an ellip-
soidal mirror and the monochromator input slit is at the
other. A 0.25 meter monochromator is used to select the
desired wavelength bandpass. A cooled GaAs photomultiplier
detects the CL transmitted by the monochromator. A shaft
encoder, fitted to the monochromator, drives a wavelength
display. The output of the photomultiplier is switched
by means of a coaxial relay to one of two signal paths.
If a CL image is desired, the photomultiplier output is
connected to a special v i d e o preamplifier and thence to
the existing SEM video system. The image can thus be
formed from any desired wavelength band, or, if required,
from the total spectrum, by setting the monochromator to
"zero" wavelength. Spectral information is obtained by
counting the current pulses leaving the photomultiplier
("photon counting") as the monochromator is scanned.
A f t e r amplification and discrimination, the resulting
p u l s e train is fed to a multichannel analyzer operating
in a multichannel scaling mode, w h e r e the data are accumu-
lated. Spectra reported in this p a p e r were produced with
20 keV electrons at a specimen current of 20 hA, while the
beam was rastered over an area of about 5 x i0-s cm2 and
the specimen was at room temperature. The spectra are un-
corrected for system response. Rastering was found to be
necessary because CL intensity usually varied across the
epi-surface. However, this variation was apparently re-
lated to surface morphology and/or layer structure and was
regular; it could thus be compensated for by averaging the
output over a sufficiently large area.

L a y e r resistivity was measured by the four-point probe

technique. For low-resistivity specimens, sufficiently
good contacts could be obtained by simply pressing an array
Characterization of GaN Epilaxial Layers 241

0¢J

0
CJ

0
¢J
~J
~J

O0

~ o~
o ~
~J

CJ

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0

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m
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242 Liu, Cass, and Stevenson

of four equidistant tungsten probes directly onto the sur-

face. For specimens of h i g h e r resistivity (>I0 ohm-cm),
four equidistant In p o i n t contacts were attached and sub-
sequently annealed in H 2 at ~,160°C to obtain o h m i c contacts.

Results and Discussion

Cathodoluminescence and Resistivity Measurements

Undoped layers gave the highest CL intensity with a

peak in the range of 3.3 to 3.4 eV h a v i n g a w i d t h at half-
maximum intensity of about 0.2 eV. These findings agree
with the results of Marasina et al. (i0) who interpreted
this peak as near band edge radiative recombination. In
general, the layers that produced the strongest UV CL also
had the most spatially uniform emission. The symmetry of
the UV peak as well as its intensity were found to vary
significantly amongst different growth runs. We speculate
that these variations may be due to unintentional doping,
differing growth rates and surface morphology, variable
built-in thermal strain (ii), or microstructural effects
(12). Liquid nitrogen CL spectra from the most efficient
undoped layers exhibited a donor-acceptor pair recombina-
tion band and phonon replicas in addition to the main
peak (i0).

Typical d o p e d CL spectra (TMg = 428 and 510°C) are

shown in Figure 2. The CL results are summarized in
Figures 3 and 4, which also include the dependence of
resistivity on Mg source temperature. Since the undoped
layers already have low mobility in the order of i00 cm2/
V-sec, largely due to the fine grain structure, the Mg-
doping should not appreciably alter the mobility, and the
observed resistivity change is probably due primarily to
the decrease in carrier concentration as a result of com-
pensation. Although there is scatter in the data, samples
prepared with lower Mg s o u r c e temperatures exhibit compa-
rable CL intensity compared to undoped samples, with the
emission peak shifting from near band gap transition to
2.95 eV and broadening continuously to a half-width of
about 0.6 eV. This shift occurs abruptly between 470 ° and
510°C. Note that the two spectra of Figure 2 straddle this
transition range, with the 4 2 8 ° C spectrum b e i n g essentially
indistinguishable from that of an undoped layer. The peak
Characterization of GaN Epitaxial Layers 243

o
4J
.e-I

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~ w go
L~
.. ~o
0 o

©
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~,~o
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AII~N31NI 3 A I I Y 3 3 N
244 Liu, Cass, and Stevenson

3,5" T O T A L FLOW R A T E = 2050 MJ~/MIN

PNH3 = 0 . 3 0 A T M ; PHCt = 0 . 0 0 3 A T M
i 0 . 1 2 ATM
PH2 FOR Mg
O TGROWTH m 9 5 0 ° C
T I M E OF GROWTH " 3 0 MIN.
0
lOS '0,80

:E .103 -0,60
w
X
:E 3,0"
...I o
0
& & -I01
o -0.40 a_
Z g, 3=
0
m -I
I" "l"
HALF
o m.
O.

&
-i0- i -0.20

;TIVITY

2.5 J I I I i 0 -3
300 400 500 600 700
TSOUROE ( ° C )

Fig. 3. Cathodoluminescence spectral peak energy, width at

half maximum intensity and layer resistivity as a function
of Mg Source Temperature.
Characterization of GaN Epitaxial Layers 245

; 107

TOTAL FLOW RATE= 2050M~IMIN 0

PNH 3 = 0 . 3 0 ATM: PHCl " 0 . 0 0 3
PH2 FOR Mg " 0 . 1 2 ATM:TGROWTH=950°C
TIME OF GROWTH,,30 MIN.
, =, , 105
O

-I

8 If!
i0 -I. .i03 o
A
0 A A z
#,- 0
m.
> >-

,<
,.I <¢=
~Lm I.-
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>-
w

z
111
I-
Z
RESISTIVIT'
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0
.I0-I
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NOISE LIMIT
OF
CL SYSTEM

i I 110-3
300 400 500 600 700
TSOURCE ( ° C )

Fig. 4. Cathodoluminescence relative intensity and layer

resistivity as a function of Mg Source Temperature.
246 Liu, Cass, and Stevenson

also becomes increasingly skewed toward lower energies as

the average Mg content increases. Ilegems and Dingle (13)
observed the same 2.95 eV level in GaN:Mg at 4.2°K by laser
excitation. The increases in resistivity and CL spectral
half-width follow the same trend with source temperature,
which implies that the peak-broadening is probably caused
by the incorporation of Mg into the GaN layer.

Figure 4 shows the complete resistivity data plus the

peak CL intensities as a function of source temperature.
For TMg > 680°C, full compensation is obtained. Although
there is significant scatter in the intensities of the
lightly doped layers, the CL intensity is totally extin-
guished in the higher resistivity layers. In the following
section we will exploit this correlation in order to quali-
tatively assess the uniformity and amount of dopant in Mg-
d o p e d i-layers in EL devices.

T h e r e are a n u m b e r of interesting and unusual trends in

the CL and resistivity that warrant further comment. The
abrupt increase in resistivity is typical of semiconductors
that have high native defect concentrations and which tend
to have one carrier type predominate (this is the case for
many of the larger band gap semiconductors). An abrupt
change in resistivity, from semiconducting state to an in-
sulator has been observed in such systems with changes in
component or doping concentration (14). The corresponding
abrupt extinction of the CL with increasing Mg content is
similar to the "poisoning" effect of luminescent materials
that occurs when excessive amounts of activator concentra-
t i o n s are present(15). This effect is not well understood
at the present time. The abrupt change in the CL maximum
from %3.3 eV to ~2.95 eV at a Mg source temperature of
%500°C, however, does not have any similarity to previous
observations or have an obvious logical explanation. The
broadening of the spectrum, upon increasing the Mg source
temperature, may also be explained partially by self-
absorption: the apparent narrowness of the undoped spec-
trum may be due to the absorption of its shorter wavelength
portion by the material itself before detection. Further-
more, it was observed that the morphology of the Mg doped
layer is distinctly different from the undoped layer and
is less perfect (7), w h i c h might broaden the acceptor level
in the band gap and thus cause a broadening of the peak.
Characterization of GaN Epitaxial Layers 247

Correlation Between CL and Device Properties

S i n c e the CL intensity from a small area of the sample

is controlled by the local Mg content in the GaN layer, the
Mg distribution in the lattice can be qualitatively charac-
terized by the appropriate CL micrographs and compared to
the resultant device properties. In general, a good MIN
structure device with large area contact (about 0.5 cmz)
will produce an I-V characteristic as Curve A in Figure 5.
Fairly sharp breakdown behavior can be expected in both the
forward and reverse directions, with the former typically
having a smaller threshold voltage(a few volts to more than
ten volts). However, nominally identical diodes prepared
from o t h e r growth runs exhibited a much shallower I-V
characteristic, Curve B in Figure 5, as m i g h t be expected
if a finite resistance shunted the diode. The CL and
secondary emission micrographs on such a diode are s h o w n
in Figures 6a and 6b, respectively. The dark regions are
the areas w h e r e the Mg content is sufficiently high enough
to extinguish the CL, whereas the light regions, w h i c h are

I (MA)

4
A

2
j
._,~1 n ~
~ v -- V ( V O L T S )
10 20 30

Fig. 5. Current-voltage characteristics for (A) a

good and (B) a poor MIN GaN diode.
248 Liu, Cass, and Stevenson

Figure 6a

Figure 6b

Fig. 6. Scanning Electron Micrograph of the

surface of the layer used to produce the diode
B of Figure 5. (a) Dispersive Cathodolumi-
nescence mode, ~ = 4100 A. (b) Emissive mode.
Characterization of GaN Epitaxial Layers 249

primarily facet faces, contained an inadequate amount of

dopant for total compensation. We conclude that Mg dis-
tributes nonuniformly in the GaN layer, and insufficient
Mg was present for uniform compensation.

It is proposed that Mg tends to concentrate at the

low-angle boundaries separating facets, leaving the facets
with lower Mg concentration. The fact that the d o p e d layer
actually consists of numerous conducting grains embedded
in an insulating matrix (16) explains the large leakage
current evident on the I-V characteristics. It should be
emphasized that large area contacts were used in these
devices. If point contacts had been used, the I-V behavior
of the leaky diode w o u l d have appeared much sharper, since
most conducting grains could have been avoided.

Since the CL intensity from the i-layer surface gen-

erally decreases to an undetectable level as the material
becomes sufficiently insulating to function as an electro-
luminescent device, as illustrated in Figure 4, a direct
comparison of CL and EL in the same specimen is difficult.
No efficient diode has yet been fabricated such that mea-
surable intensity could be observed in both i-layer CL and
forward-bias EL. This observation supports the contention
that EL originates near the n-i interface rather than in-
side the i-region (5), where nonradiative recombination
dominates. Moreover, the energy of the forward bias EL
peak (i) corresponds to that of the CL peak of a partially
compensated layer, suggesting that the initial stages of
i-layer growth may be crucial to device efficiency.

Cross sections of the devices w h o s e I-V curves were

s h o w n in Figure 5 were also examined. The UV CL in the
n-layer was structurally modulated; the intensity near the
sapphire interface diminished due either to interfac£al
strain or to diffusion of substrate atoms into the GaN.
The intensity in the i-layer was essentially zero in the
specimen that produced favorable I-V characteristics,
although the n-i interface position is somewhat uncertain.
A cross section of the poor diode is shown in Figure 7.
Several regions in the i-layer emit CL and thus appear
bright in this combined CL-secondary electron micrograph.
In this view, most of these areas do not extend to the n-i
interface; however, this observation does not preclude con-
tact between these regions and the conducting n-layer.
250 Liu, Cass, and Stevenson

Fig. 7. Scanning Electron Micrograph of a

polished cross section of the layer of
Figure 6. The image is the superposition
of the emissive and cathodoluminescence
modes (total spectrum).

Thus, we conclude that Mg concentration varies both parallel

to the growth direction and perpendicular to it.

The structural modulation for the UV CL in the n-region

is not well understood, but is presumably due to the influ-
ence of the layer structure upon the luminescence process.
The abruptness of the CL intensity variation near the n-i
interface indicates that this effect of structural modula-
tion was overwhelmed by that of Mg-doping in the i-region,
and is therefore not an important factor.

Summary

The influence of the Mg incorporation in GaN upon the

CL spectrum and the resistivity was studied and these re-
sults were correlated with the I-V characteristics of MIN
diodes. The m a j o r observations of this study include the
following:
Characterization of GaN Epitaxial Layers 251

i. Mg incorporation causes a s h i f t in the CL peak

from the near band v a l u e of about 3.3 eV to
2.95 eV, and the peak broadens as the Mg con-
centration is increased.

2. The CL peak intensity decreases with Mg incor-

poration, being extinguished as Mg fully com-
pensates the n a t i v e donors.

3. U s i n g the CL peak intensity as a qualitative

measure of the Mg concentration, the Mg distri-
b u t i o n in insulating GaN layers was sometimes
found to be nonuniform, with a higher concentra-
tion at sub-boundary regions.

4. MIN diodes with soft breakdown characteristics

show regions of low Mg concentration in the
i-layer, w h i c h introduces short circuits in
the device.

REFE RENCES

i. H. P. Marusaka, W. C. Pd~ines and D. A. Stevenson, Mat.

Res. Bull., 7, 777 (1972).

2. J. I. Pankove, E. A. ~4iller and J. E. Berkeyheiser, J.

Luminescence, 5, 84 (1972).

3. J. I. Pankove, E. A. M i l l e r and J. E. Berkeyheiser,

RCA Review, 32, 383 (1971).

4. J. I. Pankove, E. A. M i l l e r and J. E. Berkeyheiser, J.

Luminescence, 6, 54 (1973).

5. H. P. Maruska and D. A. Stevenson, S o l i d State Elec.,

I_Z_;, 1171 ( 1 9 7 4 ) .

6. J. I. Pankove and M. A. Lampert, Phys. Rev. Lett., 33,

361 (1974).

7. To be published.

8. H. P. Maruska, L. J. Anderson and D. A. Stevenson,

J. Electrochem. Soc., 121, 1202 (1974).
252 Liu, C a s s , and Stevenson

9. H. M. Hanasevit, F. H. Erdmann and W. E. Simpson, J.

Electrochem. Soc., 118, 1864 (1971).

i0. L. A. Marasina, A. K. Pikhtin, I. G. Pichugin and

A. V. Solomonov, Sov. Phys. Semicond., ~, 1162 (1975).

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12. J. J. Nickle, W. Just and R. Bertinger, Hat. Res.

Bull., 9, 1413 (1974).

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(1973).

14. D. A. Stevenson, Chapter 7 in Atomic Diffusion in

Semiconductors, Ed. D. Shaw, P'lenum Press (1973).

15. H. W. Leverenz, in An Introduction to Luminescence of

Solids, Dover, New York (1968), p. 336.

16. J. I. Pankove and E. R. Levin, J. Appl. Phys., 46,

1647 ( 1 9 7 5 ) ,