Effects of nitrogen on GaAsP light-emitting diodes

Tadashige Sato and Megumi Imai

Citation: Journal of Applied Physics 91, 6266 (2002); doi: 10.1063/1.1469664

View online: http://dx.doi.org/10.1063/1.1469664
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 JOURNAL OF APPLIED PHYSICS VOLUME 91, NUMBER 10 15 MAY 2002

Effects of nitrogen on GaAsP light-emitting diodes

Tadashige Sato and Megumi Imai
Mitsubishi Chemical Corporation, 1000 Higashimamiana, Ushiku, Ibaraki 300-1295, Japan
共Received 19 November 2001; accepted for publication 22 February 2002兲
The effects of nitrogen on GaAsP light-emitting diodes grown by hydride vapor phase epitaxy are
described. Nitrogen acts as an isoelectronic trap and this localized state makes GaAsP a widely used
material for from-yellow-to-red visible light-emitting diodes. The photoluminescence and
electroluminescence spectra, brightness, and reliability were investigated systematically in line with
the function of nitrogen concentration, from 0 共without nitrogen兲 to 2.3⫻1019 cm⫺3. When the
nitrogen concentration reached 2.3⫻1019 cm⫺3, the total emission in the photoluminescence
spectrum at 4.2 K showed a redshift. The study provides clarification of the effects of nitrogen on
the diodes and demonstrates that the characteristics of the diodes strongly depend on the nitrogen
concentration. © 2002 American Institute of Physics. 关DOI: 10.1063/1.1469664兴

I. INTRODUCTION of the nitrogen concentration, from 0 共without nitrogen兲 to

Nitrogen-doped GaAsP light-emitting diodes 共GaAsP:N
LEDs兲 have been the subject of numerous studies with re-
spect to epitaxial growth, optical properties, and LED appli-
cations, and commercial products have been successfully
produced by hydride vapor phase epitaxy 共VPE兲.1 Nitrogen
acts as an isoelectronic trap localized below the conduction
band minimum in GaAsP in a way similar to GaP, and this
helps to accomplish high light output LEDs. This localized
state makes GaAs1⫺x Px (0.5⬍x⬍1) a widely used material
for from-yellow-to-red visible LEDs even though GaAsP has
an indirect bandgap.1 As nitrogen produces large miscibility
gaps in both GaP and GaAs,2,3 incorporation of nitrogen in
GaAsP is limited to a nitrogen concentration of
⬃1018 cm⫺3. The bandgap energies of GaP and GaAs alloys
including nitrogen were predicted to be negative due to the
large electronegativity of the nitrogen atom.4 GaNx P1⫺x (x
⭐0.04) ternary alloy grown by metal-organic vapor phase
epitaxy 共MOVPE兲 showed a redshift of the total emission in
the photoluminescence 共PL兲 spectra with increase in x. The
broad band emission was taken as the band edge of the alloy,
and the bandgap was reduced by an increase in x.5 When
GaP:N LEDs were studied as a function of the nitrogen con-
centration, the electroluminescence 共EL兲 spectra were seen to
shift to longer wavelengths with increasing nitrogen concen-
tration, and the external quantum efficiency of the LEDs de-
pended strongly on the nitrogen concentration.6 Although the
characteristics of the GaAsP:N LEDs are sensitive markedly
affected by nitrogen concentration, studies so far have been
insufficient to clarify the effects of nitrogen on the LEDs.
To improve on this situation, the characteristics of
GaAsP:N were checked with an eye to the function of the
nitrogen concentration in the hope that this would prove use-
ful in improving the actual quality of the layers. GaAsP:N
layers with various nitrogen concentrations were grown by
hydride VPE. The PL spectra were used to evaluate the op-
tical property of the layers. The EL spectra, brightness, and
reliability of the LEDs, all important considerations for com-
mercial LEDs, were investigated systematically as a function
2.3⫻1019 cm⫺3. The EL emission decay times were used to
more fully understand the brightness of the LEDs. The ef-
fects of nitrogen on these characteristics is discussed.
II. EXPERIMENT
A. GaAsP preparation
GaAsP:N was grown by hydride VPE on S-doped 共100兲
GaP substrate with a 6° misorientation toward the 关011兴
direction.1 GaP substrates transparent to emitted light were
used to improve the light-extraction efficiency. Hydrogen
H2兲 was used as the carrier gas, while phosphine (PH3) and
arsine 共AsH3) were used as the P and As sources. Gallium
共Ga兲 metal was supplied as gallium chloride 共GaCl兲, a prod-
uct of the reaction with hydrogen chloride 共HCl兲. Epitaxial
growth was started by first growing a GaP layer through
supplying PH3 and GaCl on a GaP substrate which had been
heated to the growth temperature, typically 875 °C, in a
quartz reactor with flowing H2. The AsH3 flow rate was in-
creased gradually to achieve a graded composition GaAsP
layer, settling on a particular AsH3 flow rate to achieve a
constant composition GaAsP layer. Finally, nitrogen doping
was performed using ammonia 共NH3) as the doping gas, to
achieve a N-doped constant composition GaAsP:N layer as
the top layer. The GaAsP:N layers for the LEDs have to
employ thick graded composition layers to achieve a suitable
quality for the LEDs due to the large lattice-mismatch be-
tween GaAsP and GaP.1 The n-type dopant Te was incorpo-
rated in all the layers during epitaxial growth, using diethyl-
tellurium 关 共C2H5兲2Te兴 as the doping gas.
A schematic diagram of the GaAsP:N epitaxial layer is
shown in Fig. 1. The thickness of the graded composition,
constant composition, and top layers were typically 25, 15,
and 30 ␮m, respectively. The top layers were doped with
nitrogen concentrations ranging from 0 共without nitrogen兲 to
2.3⫻1019 cm⫺3 which were measured by secondary ion
mass spectroscopy. The carrier concentrations in the top lay-
ers were controlled ranging from 1.7⫻1015 to 1.3
⫻1016 cm⫺3, as measured by the capacitance-voltage

0021-8979/2002/91(10)/6266/7/$19.00 6266 © 2002 American Institute of Physics

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 J. Appl. Phys., Vol. 91, No. 10, 15 May 2002 T. Sato and M. Imai 6267

FIG. 1. Schematic diagram of the GaAsP:N epitaxial layer.

method, because they affect the characteristics of the LEDs.6

The layers, except for the top layers, were doped with a
carrier concentration of 2⫻1017 cm⫺3 to lower the resistiv-
ity. The compositions x in the GaAs1⫺x Px top layers were
0.866 to 0.902, as measured by electron microprobe an-
alysis. PL spectra were measured at 4.2 K using an Ar
laser. Etch pits in the top layers were observed using
HF:H2SO4 :H2O⫽1:2:1 at 80 °C for 2 min.7
GaAsP is hard to dope with nitrogen to a nitrogen con-
centration of above 5⫻1018 cm⫺3 due to the miscibility
gaps with both GaP and GaAs.2,3 When the NH3 flow rate
FIG. 3. PL spectra at 4.2 K for GaAsP:N with various nitrogen concentra-
was increased at a growth temperature of 875 °C, the nitro-
tions. E x are calculated by the compositions in the top layers using Eq. 共1兲
gen concentration was limited to about 3⫻1018 cm⫺3. The in Ref. 8 and are indicated by the arrows.
dependence of nitrogen concentration on the growth tem-
perature is shown in Fig. 2. When the top layers were grow-
ing, the PH3, AsH3, and NH3 flow rates were kept at 15, B. Chip fabrication and measurements
111, and 473 sccm, respectively, and the III/V mole ratio was
The p ⫹ layers at the surfaces of the top layers were
3.4. As the growth temperature was lowered from 900 to
produced by Zn diffusion without SiO2 coating. The thick-
790 °C, the nitrogen concentration increased from 7.0
ness of the p ⫹ layer was 3 ␮m. The LED was 500 ␮m by
⫻1017 to 2.3⫻1019 cm⫺3. Similar behavior was also ob-
500 ␮m and 180 ␮m in height. The p ⫹ side electrode was an
served in GaN1⫺x Px grown by MOVPE.5 This decreasing
AuZn alloy with a 200 ␮m diameter, while the n-side elec-
nitrogen incorporation with increasing growth temperature is
trode was an AuSn alloy cover on the back side. All the LED
supposed to be due to increasing nitrogen desorption from
chips were mounted on TO-5 headers without epoxy encap-
the surface of the epitaxial layer during growth and increas-
sulation. The light output and relative light output were mea-
ing PH3 decomposition,5 though the growth temperature in
sured at 30 mA at room temperature. The EL decay time was
hydride VPE is much higher than that in MOVPE.
measured at room temperature. Aging was achieved under a
stress current, dc 100 mA 共⫽40 A/cm2兲 at room temperature.

III. RESULTS AND DISCUSSION

A. Photoluminescence spectrum
Figure 3 shows the 4.2 K PL spectra for the top layers
with nitrogen concentrations ranging from 7.0⫻1017 to 2.3
⫻1019 cm⫺3. The X band edge minimum of GaAsP, E x ,
denoted with arrows in the PL spectra as calculated from
x using Eq. 共1兲 in Ref. 8, as the composition x in the
GaAs1-x Px top layers is influenced by the growth conditions.
The PL spectrum for the GaAsP:N with a nitrogen concen-
tration of 1.3⫻1018 cm⫺3 consisted of an A-line 共560 nm兲
band emission, with NN3-pair 共571 nm兲 and NN1-pair 共584
nm兲 band emission.9 This A-line band emission is due to
FIG. 2. Dependence of nitrogen concentration on growth temperature in bound exciton recombination at isolated nitrogen atoms.9
GaAsP:N. The nitrogen atom pairs make deep radiative centers named
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 6268 J. Appl. Phys., Vol. 91, No. 10, 15 May 2002 T. Sato and M. Imai

NNi in GaAsP, similar to those in GaP due to the large elec-

tronegativity of the nitrogen atom.9 The peak intensities in
the 4.2 K PL spectra increased with increasing nitrogen con-
centration, becoming high at 6.2⫻1018 cm⫺3 where some
structure could still be observed. When the nitrogen concen-
tration was increased further to 2.3⫻1019 cm⫺3, the domi-
nant band shifted drastically from the A line, NN1-pair and
NN3-pair bands to the nitrogen-related broad band at a peak
wavelength of 602 nm. This broad band did not have a well-
defined phonon replica. The total emission showed a redshift
relative to the E x . The broad dominant band could be taken
as the band edge of the GaAsP alloy including nitrogen.5 The
bandgap would be reduced relative to the E x . Furthermore, a
drastic drop in the intensities of the A line, NN1-pair and
NN3-pair bands was also observed. This drop is thought to
have two possible explanations. First, when the nitrogen con-
centration exceeds 1⫻1019 cm⫺3, some fraction of the
atomic nitrogen probably begins to stop acting as an isoelec-
tronic trap.10 The other possible explanation is that a large
number of defects are generated. In previous work, a large
number of inclined dislocations were observed in GaP:N
with nitrogen concentration of above 1⫻1019 cm⫺3 grown
by hydride VPE, and this generation of dislocations could be
explained partly by GaN precipitation.11 Confirming this
possibility for GaAsP:N, etch pits were observed in the top
layers using the spectra shown in Fig. 3, as these correspond
to the dislocations.12 The dislocation densities in the top lay-
ers with nitrogen concentrations of 2.3⫻1019, 6.2 FIG. 4. EL spectra at room temperature for GaAsP:N with various nitrogen
⫻1018, 1.3⫻1018, and 7.0⫻1017 cm⫺3, were 0.6⫻105 , 1.8 concentrations measured at 20 mA. E x are calculated by the compositions in
the top layers using Eq. 共6兲 in Ref. 9, and are indicated by the arrows. The
⫻105 , 1.7⫻105 , and 1.1⫻105 cm⫺2, respectively. This con- broken line shows the relative luminosity curve. The EL spectra were cor-
firms that generation of dislocations caused by high nitrogen rected for the system response, and normalized for maximum intensity.
doping did not occur even in the top layer with a nitrogen
concentration of 2.3⫻1019 cm⫺3. Similar behavior was dis-
played in the 77 K PL spectra for GaP:N, and no dislocations centration is increased to 6.2⫻1018 cm⫺3, the nitrogen-
were observed using cross-sectional transmission electron related broadband appears in the EL spectrum becoming
spectroscopy in the GaP:N with a nitrogen concentration of dominant at a peak wavelength of 610 nm, while the inten-
⬎1⫻1020 cm⫺3. This supports the idea that the drop was sities of the A line, NN1-pair and NN3-pair bands decrease
not caused by the generation of defects. and their structure can no longer be seen. As the nitrogen
concentration is increased further to 2.3⫻1019 cm⫺3, the EL
spectrum shows a nitrogen-related broadband with a peak
B. Electroluminescence spectrum
wavelength of 630 nm, in which the color is red, while an
The EL spectra of GaAsP LEDs at room temperature NN3-pair band appears slightly in the shorter wavelength
with various nitrogen concentrations are shown in Fig. 4. E x side of the dominant band. When the nitrogen concentration
values denoted with arrows in the EL spectra are calculated exceeds 5⫻1018 cm⫺3, the total emission in these EL spec-
from x using Eq. 共6兲 in Ref. 9. The broken line shows the tra shows a progressive redshift relative to E x with increas-
relative luminosity curve. The EL spectra were corrected for ing nitrogen concentration. This nitrogen-related broadband
the system response, and normalized for maximum intensity. could be taken as the band edge of the GaAsP alloy including
The EL spectrum with a nitrogen concentration of 2.8 nitrogen.5 The bandgap is reduced with increasing nitrogen
⫻1018 cm⫺3 shows a dominant band at 588 nm with a broad concentration. The EL spectrum for the GaAsP LED without
shape meaning that the color of the emitted light is yellow, a nitrogen shows a dominant peak E gx at 567 nm, which is due
soft tone to the eye. Two important features in the EL spectra to free exciton-recombination emission,9 and a Zn–O band
of the GaAsP:N LEDs with a nitrogen concentration of appears clearly at 690 nm. The Zn–O band is also just vis-
above 1⫻1018 cm⫺3 are the absence of any significant red ible in the spectrum for the GaAsP:N LED with a nitrogen
Zn–O pair band which is frequently present in green LEDs concentration of 4.5⫻1017 cm⫺3. The Zn–O band is of a
grown by liquid phase epitaxy, and the shift to longer wave- wavelength with a much lower eye response relative to that
lengths as the nitrogen concentration is increased. When the of the dominant band.
EL spectrum shifts to the longer wavelength side, the bright- A meaningful method for characterizing the spectrum in
ness is found to decrease in accordance with the relative terms of a single parameter would be to use the dominant
luminosity curve shown in Fig. 4. When the nitrogen con- wavelength ␭ D defined as the center of the spectrum which
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 J. Appl. Phys., Vol. 91, No. 10, 15 May 2002 T. Sato and M. Imai 6269

FIG. 6. Brightness vs nitrogen concentration in GaAsP:N LEDs. The bright-

ness measurement was made at 50 mA at room temperature.
FIG. 5. Peak and dominant wavelengths and FWHM of EL spectra for
GaAsP:N vs nitrogen concentration.

of the E gx band emission is shorter than that of the A line and

has been corrected for the spectral response of the system NN3-pair band emissions. A further increase in nitrogen con-
and then multiplied by the eye response. Figure 5 shows that centration beyond 2⫻1018 cm⫺3 results in a drastic decrease
the peak wavelength (␭ p ) increases gradually with increas- in the EL decay time. This decrease is caused by the fact that
ing nitrogen concentration before increasing sharply beyond the dominant band emission shifts from the A line and
5⫻1018 cm⫺3. An abrupt increase in ␭ P is found at 1 NN3-pair to the N-related band emissions. The band structure
⫻1018 cm⫺3, because the NN3-pair band emission increases then begins to change from indirect to direct bandgap
relative to A line band emission and the peak of the dominant behavior.13
band shifts to the peak of the NN3-pair band. ␭ D increases The emission efficiency ␩ is expressed as ␩
gradually with increasing nitrogen concentration and then ⫽C ␥ n ␶ ELN t , where C is a constant, ␥ is the hole injection
increases sharply beyond 5⫻1018 cm⫺3. When ␭ D exceeds efficiency into the n side, n is the majority carrier concentra-
about 600 nm, ␭ D becomes shorter than ␭ P due to the de- tion, ␶ EL is the EL decay time which is assumed to be the
crease in eye response in accordance with the relative lumi- minority carrier lifetime, and N t is the nitrogen
nosity curve. The full width at half-maximum 共FWHM兲 of concentration.14 Figure 8 shows that the brightness increases
the dominant bands increases slightly from 111 to 129 meV with increase in product, ␶ ELN t , where the nitrogen concen-
with increasing nitrogen concentration until the nitrogen con- tration is selected to be below 5⫻1018 cm⫺3. The brightness
centration has increased to 5⫻1018 cm⫺3. Further increase is well expressed by the equation. It is essential to optimize
in nitrogen concentration results in the FWHM abruptly ␶ ELN t to obtain high light output in the LEDs. The results
shifting to about 170 meV above a nitrogen concentration of mean that precise control of the nitrogen concentration and
5⫻1018 cm⫺3, where it can be seen to be almost constant, good quality of the layers are needed to achieve the desired
because the EL emission begins to shift from the A line and LED performance.
NN3-pair to the nitrogen-related broadband emission. In addition, the fact that GaAsP:N LEDs showed a red-
shift in the EL spectrum in this study, should be the subject
C. Brightness of discussion to determine whether they are promising or not
for use in red LEDs. GaNx P1⫺x was reported as suitable for
The nitrogen concentration in GaAsP:N LEDs has a ma-
jor effect on not only the emission spectrum, but more im-
portantly on the brightness. Brightness in foot-lambert 共FtL兲
takes into account the eye response as a function of the emis-
sion wavelength. The brightness of the LEDs is seen to in-
crease with increase in nitrogen concentration until it peaks
at 1 to 3⫻1018 cm⫺3, as shown in Fig. 6. This value is close
to a nitrogen concentration of 4⫻1018 cm⫺3, at which the
luminous efficiency in the VPE green GaP:N LEDs peak.6
Further increase in nitrogen concentration results in a drastic
decrease in the brightness due to a decrease in the luminous
efficiency and shift of the spectra to longer wavelengths. The
EL decay time in the GaAsP:N LEDs strongly depends on
the nitrogen concentration, as shown in Fig. 7, in a similar
fashion to that of the brightness shown in Fig. 6. The EL
decay time increases sharply with nitrogen concentration un-
til it peaks at 1 to 2⫻1018 m⫺3, because the EL decay time FIG. 7. EL decay time vs nitrogen concentration in GaAsP:N LEDs.
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 6270 J. Appl. Phys., Vol. 91, No. 10, 15 May 2002 T. Sato and M. Imai

FIG. 8. Brightness vs product, ␶ ELN t in GaAsP:N LEDs, where the nitrogen

concentration is selected to be below 5⫻1018 cm⫺3. FIG. 9. Relative light output after aging vs nitrogen concentration in
GaAsP:N LEDs. The LEDs were aged under a stress current, dc 100 mA at
room temperature for 168 h. The relative light output was measured at 30
LED application because of the direct bandgap behavior and mA at room temperature.
strong PL emission, and GaN0.011P0.989 red LEDs grown on
GaP substrates were successfully fabricated.15 The
GaAs1⫺x Px :N top layer with a nitrogen concentration of V 0 is the forward voltage biased to the junction, e is the
2.3⫻1019 cm⫺3 had the composition x⫽0.866, and is there- elementary charge, k is the Boltzmann constant, and T is the
fore expressed as Ga共As0.134P0.866兲0.999N0.001. The peak wave- absolute temperature.16 n⫽1 and n⫽2 indicate the diffusion
length in the EL spectrum for the Ga共As0.134P0.866兲0.999N0.001 current and space charge recombination current, respectively.
LED is 630 nm, and this corresponds to that of the As the recombination current usually increases after aging, n
GaAs0.35P0.65 :N0.001 LED shown in Fig. 4. The FWHM of is found to shift from 1 to 2. When the series resistance R of
the dominant band in the EL spectrum for the the LEDs is considered, the operated forward voltage to the
GaAs0.134P0.866 :N LED is 170 meV, which is larger than the LED V f is expressed as V f ⫽V 0 ⫹R•I f . When I f is constant,
129 meV for the GaAs0.35P0.65 :N LED. The the second term becomes constant. Therefore, a drop in V f at
Ga共As0.134P0.866兲0.999N0.001 LEDs are only 15% as bright as 10 ␮A after aging qualitatively reveals the degree of increase
the GaAs0.35P0.65 :N with the same LED structure. This in the recombination current. The drop is seen to apparently
would be due to the fact that the GaAsP quaternary alloy decrease with an increase in the nitrogen concentration, as
includes nitrogen. The Ga共As0.134P0.866兲0.999N0.001 LED was shown in Fig. 11. It should be pointed out that the deteriora-
not determined in this study to be suitable for red LED ap- tion of the light output is mainly caused by the increase in
plications. the recombination current. Figure 12 shows the logarithmic
EL spectra for the GaAsP:N LEDs with nitrogen concentra-
tions of 6.2⫻1018 and 4.5⫻1017 cm⫺3 before and after ag-
D. Reliability
ing. These are normalized by the peak intensities of the
Nobody has satisfactorily investigated the dependence of dominant band. When the nitrogen concentration is increased
degradation of GaAsP:N LEDs on the nitrogen concentra-
tion. Light output has been used for this reliability study and
this is not corrected for eye response. Figure 9 shows the
dependence of the relative light output after aging on the
nitrogen concentration. The LEDs were aged under a stress
current, dc 100 mA at room temperature for 168 h. The rela-
tive light output was measured at 30 mA at room tempera-
ture. It is clear that the relative light output increased with
increase in nitrogen concentration. The LEDs with a nitrogen
concentration of above 5⫻1018 cm⫺3 deteriorated slightly,
in contrast to those LEDs with a nitrogen concentration of
below 1⫻1018 cm⫺3, which rapidly deteriorated. Figure 10
shows the aging test results with various nitrogen concentra-
tions. The LEDs were aged under a stress current, dc 100 mA
at room temperature. The relative light output was measured
at 30 mA at room temperature. The relative light output rap-
idly decreased within 24 h and then decreased gradually after
FIG. 10. Aging test results of the GaAsP:N LEDs with various nitrogen
a further 24 h, in the order of the nitrogen concentrations.
concentrations. The LEDs were aged under a stress current, dc 100 mA at
The forward current I f at the junction is expressed as I f room temperature. The relative light output was measured at 30 mA at room
⫽I 0 • 关 exp(eV0 /nkT)⫺1兴, where I 0 is the saturation current, temperature.
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 J. Appl. Phys., Vol. 91, No. 10, 15 May 2002
FIG. 11. Drop in V f at 10 ␮A after aging vs nitrogen concentration in
GaAsP:N LEDs.
to 6.2⫻1018 cm⫺3, the EL spectrum after aging shows no
change. When the nitrogen concentration is decreased to
4.5⫻1017 cm⫺3, the EL spectrum after aging shows a drastic
decrease in the Zn–O band relative to the dominant band,
and no change in the dominant band. The decrease in the
Zn–O band after aging is thought to be evidence of the dif-
fusion of impurity ions into the space charge region at the
junction.17 In LEDs with a nitrogen concentration of below
5⫻1017 cm⫺3, especially those without nitrogen, the de-
crease in the Zn–O bands contributes partly to the drop in
the light output after aging, as the Zn–O bands in the EL
spectra appear before aging, and decrease drastically after
aging.
It is speculated that degradation of GaAsP:N LEDs is
caused by diffusion of interstitial Zn ions as is proposed by
Longini.18 The Zn interstitials exist in the diffused p ⫹ layer
with high concentration and are ionized during operating un-
der the forward current. The Zn ions in the p ⫹ side rapidly
diffuse to the space charge region where the concentration of
FIG. 12. Logarithmic EL spectra at room temperature for GaAsP:N LEDs
with nitrogen concentrations of 6.2⫻1018 and 4.5⫻1017 cm⫺3 before and
after aging measured at 20 mA at room temperature.
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T. Sato and M. Imai 6271
the Zn ions quickly saturates. The electric field in the region
prevents most of the Zn ions from diffusing into the n side
across the junction. The Zn ions partly diffuse across the
junction and the electric field strength is reduced. This reduc-
tion has the effect of increasing the recombination current.
The diffusion produces a deterioration of the junction. The
Zn ions probably precipitate in the space charge region and
new defects form from these defects in the vicinity of the
junction to generate nonradiative recombination centers.19
The Longini model accounts for the degradation process of
the LEDs, but cannot explain the dependence of the degra-
dation on nitrogen concentration. The diffusion of the Zn
ions in the p ⫹ side during operation is supposedly sup-
pressed with the increase in nitrogen concentration. The Ga
vacancies (V Ga) would enhance the diffusion of the Zn
ions.18 When the nitrogen concentration is increased, the ni-
trogen possibly increases to occupy the Ga sites reducing the
V Ga , or to create some complex defects with the V Ga so that
some fraction of the V Ga cannot act to enhance the diffusion.
Another explanation might be that the interstitials of Zn cre-
ate neutral complexes. An acceptor-H complex model was
proposed for hole compensation of p-type GaN.20 The inter-
stitial Zn on the p ⫹ side is assumed to act as a donor. In our
model, it could be proposed that substitutional nitrogen at-
oms bind to electrons from the Zn acceptors due to the large
electronegativity of nitrogen atoms, and the Zn acceptors
create acceptor-Zn neutral complexes with the interstitials of
Zn. As a result, the diffusion of the Zn ions under operation
is suppressed as the nitrogen concentration increases.
IV. CONCLUSIONS
The effects of nitrogen on GaAsP:N LEDs grown by
hydride VPE are described. The PL and EL spectra, bright-
ness, and reliability were investigated systematically as a
function of the nitrogen concentration, from 0 共without nitro-
gen兲 to 2.3⫻1019 cm⫺3. When the nitrogen concentration
was increased to 2.3⫻1019 cm⫺3, a redshift was observed in
the 4.2 K PL spectra, where the broad emission was taken as
the band edge emission. The characteristics of the LEDs
were seen to significantly depend on the nitrogen concentra-
tion. When the nitrogen concentration exceeded 5
⫻1018 cm⫺3, the EL spectra showed a redshift and the
brightness and EL decay time drastically decreased with in-
creasing nitrogen concentration, because the band structure
began to gradually change from indirect to direct behavior.
The highest brightness was obtained at 1 to 3⫻1018 cm⫺3
and was strongly depended on the product ␶ ELN t . Precise
control of the nitrogen concentration and good quality of the
layers are needed to achieve suitable LED performance. The
reliability can be improved with an increase in nitrogen con-
centration. A degradation model for the LEDs has been in-
cluded in this article. The study demonstrated that nitrogen
concentration significantly affects the characteristics of the
LEDs. The results should prove very useful in improving the
quality of the layers for actual LED devices.
 6272 J. Appl. Phys., Vol. 91, No. 10, 15 May 2002 T. Sato and M. Imai

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