SEMICONDUCTORS AND SEMIMETALS. VOL.

52

CHAPTER7

Sic-Based UV Photodiodes and

Light-Emitting Diodes
J . Edmond. H . Kong. G. Negley. it4. Leonard.
K. Doverspike. W. Weeks. A . Suvorov.
D . Waltz. and C. Carter. Jr.
INC.
CREE RBSWRCH.
DURHAM.NC

I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
I1. S i c Blue LEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
1. Epitaxy and Device Fabrication . . . . . . . . . . . . . . . . . . . 286
2. Device Performance . . . . . . . . . . . . . . . . . . . . . . . . 287
I11. Sic GREENLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . 288
1. Epitaxy and Ion Implantation . . . . . . . . . . . . . . . . . . . . 288
2. Device Performance . . . . . . . . . . . . . . . . . . . . . . . . 289
IV . UV PHOTODIODES . . . . . . . . . . . . . . . . . . . . . . . . . . 290
1. Device Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . 290
2. Electrical Characteristics . . . . . . . . . . . . . . . . . . . . . . 292
3 . Optical Responsivity . . . . . . . . . . . . . . . . . . . . . . . . 294
4. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
V. GROUP111-NITRIDES ON 6H-Sic . . . . . . . . . . . . . . . . . . . . 297
I . Epitaxial Growth, Characterization, and Device Fabrication . . . . . . . 291
2. Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
3. Photoluminescence . . . . . . . . . . . . . . . . . . . . . . . . . 300
4. GUN: S i c Blue LEDs . . . . . . . . . . . . . . . . . . . . . . . 302
5 . Electrical Static Discharge Survivability . . . . . . . . . . . . . . . . 305
VI. SUMMARY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306

I. Introduction

S i c has been investigated as a short-wavelength optoelectronic material

since the early years of semiconductor development .As a result of the 3.0-eV
bandgap of 6H.SiC, any color light-emitting diode (LED) in the visible
283
Copyright 0 1998 by Academic Press
All rights of reproduction in any form reserved .
ISBN 0-12-752160-7
m80-8784 $25.00
284 J. EDMONDET AL.

spectrum can be achieved in this material. Despite its indirect bandgap,

which makes light emission relatively inefficient, many scientificallyinterest-
ing and some commercially successful emitters have been developed. Dmit-
riev et al. [l] demonstrated a red-green-blue LED display made from a
1 x 1-cm single-crystal wafer of 6H-SiC. Ion implanatation and epitaxial
techniques were employed to achieve the three LED colors. No information
on the efficiency of the devices was given. Vodakov et a!. [2] demonstrated
a green LED in 6H-SiC by implanting A1 into an n-type epilayer 10 to 30 pm
thick and grown by sublimation epitaxy. The A1 implant produced the
p-type region of the p - n junction and simultaneously generated lumines-
cence centers. The resulting LEDs emitted green with a peak wavelength of
530 nm. The output power was in the range of 5 to 15 pW.
Development of 6H-SiC blue LEDs was for many years a major research
effort at Siemens Research Laboratory, various labs in the former Soviet
Union, and a number of Japanese labs, in particular Sanyo Electric Co., Ltd.
Several of these groups released blue LEDs as products. The highest
external quantum efficiency (qext)reported by these groups was achieved by
Hoffmann et af. [3] (Siemens) using a high-resistivity transparent p-type
substrate with contacts made to via-etched topside p and light-emitting
+

compensated n-type epilayers. The epitaxial layers were deposited via

liquid-phase epitaxy (LPE). This nontraditional two-topside contact device
design resulted in a maximum qeX1of -2 x However, typical commer-

-
cial devices with a vertical device configuration exhibited much lower values:
qexl 0.3 - 0.4 x with excessive forward voltage (4-8 V) as a result of
the low optical transparency and high electrical resistivity of the p-type
substrates employed. Koga et a/. [4] of Sanyo introduced a device also
grown by LPE utilizing an n-type substrate. A light-emitting compensated
n-layer was grown, followed by a high-resistivity player with poor current
and therefore light-spreading characteristics. To compensate for this prob-
lem, the chip was inverted from a traditional junction up-configuation with
the p-contact face down and a polished n-substrate face up. This provided
for uniform light emission in the shape of the p-contact imaged through the
chip. The lower resistivity and higher optical transparency of the n-substrate

-
yielded an improvement over the Siemens device with regard to lower
forward voltage, 4 V, and higher vex, of 1 x for commercial devices.
This nontraditional chip configuration, however, made it difficult to package
with standard silver epoxy mounting without shorting the junction.
The wide bandgap of Sic also make it an excellent ultraviolet (UV)
detector. The earliest published research on Sic UV photodiodes utilized
diffusion of A1 into n-type 6H substrates [ S ] . This process resulted in
high-leakage devices with corresponding low quantum efficiency. Glasow et
al. [ 6 ] improved on this initial design by utilizing N ion implantation to
 7 Sic-BASED UV PHOTODIODES AND LIGHT-EMITTING
DIODES 285

form a very shallow (0.05 pm) n+-p junction in a 5-pm p-type epitaxial layer
grown on a p-type substrate. This research resulted in devices with a
maximum quantum efficiency of 75% at a peak wavelength (A,) of 280 nm
at room temperature. However, the reverse-bias dark current density was
excessive, on the order of A/cm2 at - 10 V at room temperature.
A related and very rapidly growing application for Sic in optoelectronics
is its use as a substrate for group III-nitride LED and laser structures.
Higher efficiency blue and green LED emission has been achieved with the
direct bandgap alloy system AlN-InN-GaN, which has a structural and
chemical compatibility with Sic substrates. To date, most researchers have
employed sapphire as a substrate, which also has a structural and chemical
compatibility with GaN, but has two major shortcomings: (1) sapphire is
electrically insulating and (2) it has a 16% lattice mismatch with GaN. This
requires two topside contacts to pass curent through the p - n junction and
results in a high dislocation density in the device structure, on the order of
lo9 cm-’. Sic has a lattice mismatch of 3.5% with GaN and is conductive,
which allows for the fabrication of a vertical device structure for nitride-
based LEDs. Cree Research uses 6H-Sic substrates for commercial produc-
tion of nitride-based LEDs, while the other two commercial sources of
super-bright blue LEDs employ sapphire.
Nakamura [7] of Nichia Chemical has demonstrated InGaN single
quantum well (SQW) LEDs grown on sapphire emitting from violet to
orange. The external quantum efficiency of these devices are the highest
recorded for the InGaN system. As the indium fraction of the InGaN SQW
increases, the efficiency of the LED decreases from 10% at 400 nm ( 14%
N

In) to 1.2% at 600 nm ( N 77% In). Based on this research, Nichia Chemical
released blue and green SQW LEDs into production in 1996.The blue LED
with an active layer composition of In,~,,Ga,,,,N has a typical output of
2.5 mW at a peak wavelength of 470 nm and a bandwidth of 30 nm. The
green version, with an active-layer composition of Ino,53Gao.47N,has a
typical output of 1.5 mW at a peak wavelength of 525 nm and a bandwidth
of 40 nm.
Koike et al. [S] of Toyoda Gosei Co. demonstrated asymmetric double
heterostructures (ADHs) of AlGaN/InGaN/GaN blue and InGaN/GaN
MQW UV LEDs. The active layer of the blue LED is In,,,,Ga,,,,N
co-doped with Zn and Si, which results in an emission peak of 450 nm and
a bandwidth of 70nm. In production, this device has a typical output of
2 mW at 20 mA. The multiple quantum well emitter employed five wells of
In,~,,Ga,.,2N/GaN bounded by AlGaN.
This chapter describes the development, fabrication, characterization, and
some applications of 6H-Sic homojunction blue and green LEDs and UV
photodiodes at Cree Research, Inc. In addition, electrical and optical
286 J. EDMOND ET AL.

properties of nitride layers grown on SIC substrates will be presented along

with the current status of blue LEDs fabricated from this material system.

11. Sic Blue LEDs

1. EPITAXYAND DEVICE
FABRICATION

Cree Research produces the only commercially available S i c blue LED.

This device utilizes an n-type 6H substrate with a resistivity of 0.02 to

- -
0.04R-cm. Prior to epitaxial growth, the wafer is cut and polished to a
thickness of 300 pm, with an orientation of 3.5" tilted off-axis along the
(1120) direction. The diameter of commercial wafers is presently 30 mm.
Epitaxial growth is achieved via chemical vapor deposition (CVD) as
opposed to LPE. This provides for greater control of dopant profiles and
layer thicknesses. An n-type layer is first grown, followed by a compensated

FIG. I . SEM micrograph of a typical Cree 6H-Sic blue LED.

 7 Sic-BASED UV PHOTODIODES AND LIGHT-EMITTING
DIODES 287

p-type layer doped with N and Al. The blue light is generated via radiative
recombination between N donors and A1 acceptors in this layer. It was
determined by the present authors that p-compensated material is more
efficient for light emission than n-compensated, as employed by previous
researchers. This may be a result of the higher mobility and thus recombina-
tion lifetime of electrons in Sic. A p+-layer with a resistivity of 1 to 2 Q-cm
is deposited on the p-compensated layer, which serves both as a contact and
as a current-spreading layer. The p - n junction is delineated via mesa etching
with NF, in a reactive ion etch mode. The ohmic contact to this top layer
is Ti/Al, followed by Ti/Au as a bond pad. The contact to the n-substrate is
Ni. Both contacts are sintered to the Sic at 850 to 900°C.
Figure 1 shows a scanning electron microscopy (SEM) micrograph of
Cree's typical Sic blue LED chip. The chip size is 225 x 225pm, with a
thickness of 250 pm. The top p+-layer is 20 to 30 pm thick, which increases
the escape probability and current spreading in the device. To further
increase the light output, the surfaces of the chip are also roughened, as
shown in the micrograph.

PERFORMANCE
2. DEVICE

As mentioned previously, the 6H polytype of S i c has an indirect bandgap

of -3.OeV. The proposed light generation mechanism for Cree's LEDs is
phonon-assisted donor-acceptor (D-A) pair recombination between nitro-
gen donors and aluminum acceptors. This doping scheme results in a device

-
that emits light with a peak wavelength of -470nm, with a spectral
halfwidth (An,) of 70 nm. Figure 2a shows the relative spectral emission
versus wavelength for a Cree blue LED operating at a forward current of

-
20mA measured in an integrating sphere. As shown, the peak emission is
-470nm with An, 70 nm and a dominant wavelength of -481 nm. The
resultant spectral purity is 82%. The radiant flux or optical power output
N

-
of this device is -34pW. The typical output power is between 25 and
35 pW for a forward current of 20 mA at 3.2 V. This represents an external
quantum efficiency of 0.05 to 0.07%. With respect to photometric units, the
die luminous intensity is -0.5 millicandela (mcd), for a radiant flux output

-
of 34pW. The corresponding luminous intensity of a T @packaged lamp
with a viewing angle of 16" is 35 mcd.
The effect of increasing forward current to 50 mA on the radiant flux and
corresponding value of the external quantum efficiency is shown in Fig. 2b.
As shown, the radiant flux increases in a sublinear fashion with increasing
current. This translates into a decreasing external efficiency, also shown in
this illustration. This sublinear behavior is most probably due to the onset
 J. EDMONDET AL.

400 450 500 550 600 650 700 I) 10 20 311 40 so 60

Wavelength (nm) Forward Current (mA)

(4 (b)

FIG. 2. Typical (a) emission spectra and (b) current-dependent output of 6H-Sic blue LEDs.

of decreasing D-A pair recombination or pair saturation and an increase in

lower efficiency recombination events at higher energy. By increasing the
D-A pair density, it is believed that a more linear relationship between light
output and drive current can be achieved, as well as an overall increase in
the efficiency of the device.
Another important aspect of S i c blue LEDs is their stability in light
output over time. Using a stress current of 50 mA at room temperature, the

-
typical 24-hr degradation is -1%. After 10,OOO hr, the degradation is
typically 10 to 15%-better than most commercial green and red LEDs
produced today.

111. SIC Green LEDs

1. EPITAXYAND ION IMPLANTATION

N-type 6H substrates with a resistivity of 0.02 to 0.04Q-cm were em-

ployed as the base substrate for epitaxial growth and ion implantation. An
n-type epitaxial layer was grown via CVD to a thickness of 3 to 5pm and
a carrier concentration of IOl5 to 10'6cm-3. To form the p-type layer, ion
implantation of either A1 or Ga was then performed. The typical implant
conditions were a dose of 2 to 5 x 10'6cm-2 and energy of 40 to 90keV.
During implantation, the wafer was maintained at a temperature of 1700 to
1800°C. This prevented the Sic from becoming amorphous from the
 7 Sic-BASED UV PHOTODIODES A N D DIODES
LIGHT-EMITTING 289

high-dose implant. After implantation, the surface had a thin C-rich layer,
which was easily removed via ashing with an oxygen plasma. A p+-layer
with a resistivity of 1 to 2 0-cm and a thickness of 20 pm was epitaxially
grown on the p-type Al-implanted layer as a contact and a current-
spreading layer. The chip fabrication process was the same as described for
the blue LED.

2. DEVICEPERFORMANCE

-
As a result of the high-temperature implant, A1 diffuses into the Sic and
thus the p-n junction is located 1pm below the implanted surface. This
is nearly an order of magnitude deeper than the A1 implant range at 90 keV.
This enhanced diffusion was investigated by Suvorov et al. [9] for A1
implanted at 40 keV and a dose of 2 x loi6cm-2 into Sic at 1800°C. Their
work concluded that the radiation-enhanced diffusion coefficient was 2
orders of magnitude higher than the thermally activated diffusion coefficient
as a result of an Si vacancy-rich near-surface layer formed by this implant
condition.
Defects generated within a few diffusion lengths of the p - n junction
electroluminescence (EL) in the green region of the visible spectrum. Figure
3a shows the relative spectral emission versus wavelength for this device

-
operating at a forward current of 20 mA, measured in an integrating sphere.
As shown, the peak emission is 530 nm, with a bandwidth of 85 nm. As -
50 0.5 -5
40 0.4 2
.-
5- 30
h

g
0.3 W
2 E
E; E
2 20
I
0.2 9
s b
2
-
a
10 0.1
e
0 O P
400 450 500 550 600 650 700 0 10 20 30 40 50 60

Wavelength (nm) Forward Current (mA)

(4 (b)

FIG.3. Typical (a) emission spectra and (b) current-dependent output of 6H-Sic green LEDs.
290 J. EDMONDET AL.

a result of this broad emission peak, the spectral purity is very low (-45%).
The typical output power is about the same as for Cree’s 6H-Sic blue
LED-between 25 and 35 p W for a forward current of 20 mA at 3.2 V. -
With respect to photometric units, however, the die luminous intensity is a
factor of 2 higher than the blue LED (1.2 mcd), for a radiant flux output of

-
33 pW. The corresponding luminous intensity of a T 13-packaged lamp with
a viewing angle of 16‘ is 85 mcd.
The effect of increasing forward current to 50 mA on the radiant flux and
corresponding value of the external quantum efficiency is shown in Fig. 3b.
As shown, the radiant flux at 1-mA forward current is nearly 10 pW, a factor
of 5 higher than for the S i c blue LED at this current. The value of qextis
0.4% at this operating current, which is very high for an indirect gap
material. If this efficiency were maintained to 20mA, the output would be
nearly 200 pW. However, as shown, the efficiency drops drastically with
increasing current. This behavior is most probably due to a small recom-
bination cross-section produced by the ion-implantation process. If the
volume of centers could be increased, the saturation behavior would not be
so severe. This could be done in two ways. The easiest method would be to
increase the chip size and thus reduce the current denisty. If the chip had a
junction area 6 times the area employed in this research, the brightness
would indeed be nearly 200pW at 20mA. However, a 550 x 550-pm LED
chip is neither practical nor economical. The other method to increase the
recombination volume would be to increase the thickness of the active
region of the device. A method to achieve this is not obvious because the
exact mechanism for the EL in this device is not well understood.

IV. UV Photodiodes

1. DEVICE FABRICATION

The most common Sic-based UV photodiode today utilizes a p-type 6H

substrate with a resistivity of 1 to 10 Q-cm, which is prepared for epitaxy as
previously described for Cree’s blue LED. The epitaxial junction is produced
b! first growing a predominantly Al-doped p-type layer followed by a
predominantly nitrogen-doped n-type layer. The doping and thickness of
these layers can be varied to alter the responsivity of the devices. The doping

-
in the background p-layer is typically between 1 and 5 x 10I6cm-3, with a
thickness of 0.4 to 5.0 pm. The n-layer is heavily doped to 1019cm-3, with
a thickness of -0.1 to 0.35pm. The devices are fabricated using a mesa
geometry to delineate the p-n junction. Typical sizes vary from
0.3 x 0.3 mm’ to 3 x 3 mm’, depending on the signal requirements of the
application. The junction is passivated with dry thermally grown SiO,.
 7 Sic-BASED uv PHOTODIODES AND LIGHT-EMITTING
DIODES 291

SiO, Ni/Au contact

p-type 6H-Sic substrate

AWiAu contact

FIG. 4. Schematic showing the structure of a typical 6H-Sic UV detector.

Contact materials for the p-side and n-side are A1 and Ni, respectively. The
metals are sintered to the Sic at 850 to 900°C to obtain ohmic contacts.
Figure 4 shows a schematic of a commercial Sic UV detector produced
by Cree Research. As shown in this illustration, the top n-type layer is
thinned to -0.1 pm from the 0.35-pm as-grown layer. This is important for

FIG. 5. SEM micrograph of a typical 6H-Sic UV detector.

292 J. EDMONDET AL.

two reasons. First, Ni when sintered as described, reacts to a depth of

-0.25 pm, shorting the top n-type to the underlying p-type region. There-
fore, the top n-layer must exceed 0.25pm. Second as a result of the high
optical absorbance and surface recombination velocity of the n+-epilayer,
the responsivity of the device is enhanced by reducing its thickness from 0.35
to 0.1pm [lo]. To accomplish both conditions, the layer is selectively
thinned beyond the region of the Ni contact centered on the top layer via
reactive ion etching, using NF, as shown in Fig. 4.
Figure 5 is an SEM image of the aforementioned chip, showing the
structure described previously. The cross-shaped center Ni contact reduces
the active region of the device by -2%. The center square metallization is
the wire bond pad, which consists of a metal stack of Ti/Pt/Au with a
thickness of 0.1, 0.1, and 2 pm, respectively. This metal scheme provides for
a reliable high-temperature contact with excellent adhesion and bondability.
The backside metallization employed is also Ti/Pt/Au, which can be easily
brazed to an Au-plated header for hermetic packaging.

2. ELECTRICAL
CHARACTERISTICS

a. Dark Current
As mentioned, an advantage of S i c for UV detection is its extremely low
reverse dark current, even at elevated temperatures. Figure 6a shows the
reverse-bias dark-current density versus voltage as a function of temperature
for a typical 6H-Sic UV photodiode. The active junction is square with an
area of 0.04cm2. For many applications, a photodiode is operated at a
reverse bias of - 1.0 V, taking advantage of the fact that reverse current
increases almost linearly with the increase in incident radiation. Since the
sensitivity of the device depends on the level of background or dark current,
it should be kept to a minimum for a high signal-to-noise level. As

-
shown in Fig. 6a, the dark current is extremely low at -l.OV, being
lo-" A/cm2, even at a temperature of 473 K. At the highest voltage

-
measured (-lOV), dark current density increased from
3x A/cm2 when increasing the temperature from 473 to 623 K. This
relationship is plotted as a function of temperature in Fig. 6b. Here, the
to

dark-current density at - 10 V as a function of temperature is a straight-line

function, with an activation energy of 0.60eV. Brown et al. [lo] showed
similar values of reverse dark current for devices in their research, using
epitaxially grown junctions. Data for the ion-implanted detectors [6] is
included in Fig. 6b for comparison purposes. As shown, the devices reported
herein exhibit orders of magnitude lower leakage than implanted UV
detectors in 6H-Sic.
 7 Sic-BASED DIODES
UV PHOTODIODES AND LIGHT-EWTING 293

I E-07 I E+OO 0 This Work

g IE-01
IE-02
IE-03
zh IE-04
.-,h IE-09 IE-05
;3 IE-06
a' 2
5
IE-07
L
IE-I0
5 IE-08
I
V
3 IE-09
s
IE-l I n IE-10
0 2 4 6 8 1012 1.4 1.6 1.8 2.0 2.2
Reverse Voltage (V) tOOUlT (K)

FIG. 6. Logarithmic dark-current denisty versus (a) reverse voltage at D 473 K, 0 523 K,
0 573 K, A 623 K, and (b) inverse temperature for 6H-Sic UV detectors.

b. Power Generation Characteristics

Another important electrical characteristic to consider for a photodiode

is the ability to produce power during illumination. This mode of operation
is typically utilized in solar cell operation and is referred to as the
photovoltaic mode. At zero bias, the current generated is termed the
short-circuit current ( I s c )because it represents the photocurrent generated in
the absence of an external load. As a load is applied to the device, a voltage
and current will be output until the junction potential is reached. At this
point, the reverse current decreases until no current flows through the
device. The voltage at this point is termed the open-circuit voltage (Voc).
Within the I-V region, there is a maximum region of power output referred
to as the maximum power rectangle. The parameters I , and V, correspond
to the current and voltage, respectively, for the maximum power output P,
( = I , KJ
Figure 7 shows the I-V characteristics of a 3 x 3-mm2 Sic UV power
photodiode illuminated with radiation in the 200 to 350-nm range and a
power of 7 x W/cm2. At OV, I,, was approximately 0.47mA. This
curve was generated by measuring the voltage across a variable load resistor
and varying the resistance while keeping the illumination constant. The
output current remained relatively level, to about 0.5 V, where it then started
to decrease. This phenomenon is typically the result of a high internal device
resistance. Since the series resistance of the device is on the order of 10 to
20 Q, an additional internal resistance dominates the device in this region.
It may be a result of deep trap levels in the bandgap activating at a
particular voltage. At I , = 0, V,, is approximately 2.3 V. The value of P ,
294 J. EDMOND
ET AL.

0.4
Im

0.3

0.2

0.1

0.0
0 1
* voc
3
Photovoltage (V)

Erc;. 7 Relatronship between the photocurrent generated versus photovoltage output for a
3 x 3mm' 6H-SiC photodiode. The incident light energy was 7 x W/cm*, with a
wavelength In the range of 200 to 350 nm.

occurs at I,,, = 0.35 mA and V, = 1.35 V, or 0.47 mW. The maximum power
rectangle is indicated by the shaded area in Fig. 7.

RESPONSIVITY
3. OPTICAL
(1. Efect of Epilayer Thickness

In addition to the thickness of the n f cap layer discussed earlier, two

factors that can contribute to the responsivity of photodiodes are the
thickness of the underlying p-layer of an n t - p device and the temperature
of operation. The depletion region of the detector is predominantly in the
lower doped p-layer. When UV light is absorbed, electron-hole pairs are
generated within the depletion region itself and in the p-layer bulk. Those
carriers, in this case electrons, within a diffusion length, L,, of the depletion
region are swept by the large electric field of the p - n junction. These carriers
are collected in a given circuit and generate current or voltage.
 7 Sic-BASED UV PHOTODIODES AND DIODES
LIGHT-EMITTING 295

Brown et al. [lo] employed modeling techniques to determine L,, fitting

experimental results of various Sic detectors to theory. From their results,
the diffusion length of electrons in p-type S i c is 1.8 f 0.4 pm. This is smaller
than the estimate made by Glasow et al. [6], whereby a value for L, of 3 pm
was calculated from a lifetime of 20ns for electrons and holes and an
electron mobility of 200cm2/V-s. Brown’s value does not depend on any
assumptions regarding carrier lifetime or mobility.
The effect of p-layer thickness on the responsivity and quantum efficiency
of S i c UV detectors is shown in Fig. 8. The player thicknesses employed
were 0.4, 1.2, and 3.0 pm, with a junction depth of -0.1 pm. For all of the
devices, the peak quantum efficiency was -80%. The effect of player
thickness is to shift the peak response and overall long-wavelength response.
This is important if the objective is to produce nearly solar-blind UV
detectors. For the 3-pm-thick p-layer, the peak response occurs at 280 nm.
This response curve is very similar to that observed by Brown et al. [lo],
-
for a player thickness of 5 pm, which exhibited a peak response at 275 nm.
Decreasing the layer to 1.2 and 0.4 pm shifts the peak response to 260 nm
and 250 nm, respectively. In doing so, the long-wavelength response is
N
-
greatly reduced.

200

I50

I00

50

0
200 250 300 350 400 450

Wavelength (nm)
FIG.8. The effect of p-layer thickness on the responsivity and quantum efficiency of S i c
+
UV detectors. The p-layer thicknesses are 0.4 pm, 0 1.2 pm,and 0 3.0 pm.
2% J. EDMONDET AL.

The reduction in longer wavelength response with decreasing player

thickness can be understood when considering diffusion length and the
dependence of the absorption coefficient on wavelength in Sic. As deter-
mined by Choyke and Patrick [Ill], the absorption coefficient of S i c

-
increases sharply with increasing energy, or decreasing wavelength, of
radiation above the optical bandgap energy of 3 eV. For players thicker
than L,, carriers generated as far away from the depletion layer edge as L,
contribute to the photoresponse of the device. Since the absorption coeffi-
cient is smaller at longer wavelengths just below the absorption edge,
carriers generated by these wavelengths have a chance to contribute. When
the thickness is decreased to less than L,, in this case 1.2 pm, fewer carriers
are generated at the longer wavelengths ( > 250 nm) and thus a lower signal
results. Below 250 nm, the absorption coefficient appears to dominate, which
results in nearly identical photoresponse curves for all thicknesses of
players.

h. Efect oj- Operating Temperature

The responsivity and quantum efficiency of UV detectors as a function of

operating temperature are shown in Fig. 9. The temperatures tested were
223. 300, 498, and 623K. As shown, there is a shift in the peak and

wavelengths. The peak response increases from -

long-wavelength response to higher responsivity values at longer

- 268 nm at 223 K to
299 nm at 623 K. This corresponds to a energy decrease from 4.63 to
4.15 eV over this temperature range, which corresponds to 1.2 x lop3eV/K.

-
This is a result of the shift in bandgap with temperature. The indirect
bandgap decreases from 3.03 eV at 223 K to -2.88 eV at 623 K, corre-
sponding to a rate of 3.8 x 1W4eV/K [lo]. This is a factor of - 3 lower
than experimentally observed from the shift in the peak response. Therefore,
the peak response does not change at the same rate as the indirect bandgap.
The indirect bandgap could be measured via the long-wavelength cut-off.
Unfortunately the necessary narrow bandpass filters to measure this were
not available at the time of this experiment. For all of the measurement
temperatures, the peak quantum efficiency was between 82 and 96%. These
results show the effectiveness of 6H-Sic as a UV photodiode, even to 623 K.

4. APPLICATIONS

High-temperature S i c UV photodiodes may have a significant impact in

many application areas. Improvement in combustion control is anticipated
with the ability to sense flames in aircraft engines, building boiler systems,
 7 Sic-BASED UV PHOTODIODES AND LIGHT-EMITTING
DIODES 297

Wavelength (nm)

FIG. 9. The effect of measurement temperature on the responsivity and quantum efficiency
+
of Sic UV detectors. The temperatures tested were a 2 2 3 K, 300 K, 0 498 K, and 623 K.

and industrial processes. Air quality monitoring and UV dosimetry for

industrial processes are other important application areas. A small, low-
power, temperature-insensitive UV detector would enable the construction
of rugged, self-contained, UV detector systems for use in remote-sensing
applications. The availability of an array detector, sensitive to the near and
middle UV, could be important to imaging applications, including atmo-
spheric UV remote sensing, combustion control, and, potentially, missile
plume detection and tracking.

V. Group 111-Nitrides on 6H-Sic

GROWTH,
1. EPITAXIAL CHARACTERIZATION, AND DEVICE
FABFUCATION

High-quality GaN, AlGaN, and InGaN alloy thin films were epitaxially
grown on the Si-face of 6H-Sic substrates with a diameter of 41 mm via
metal-organic chemical vapor deposition (MOCVD). The substrates were
n-type with a typical resistivity of 0.02 to 0.04R-em. The non-indium-
containing films were grown in the temperature range of lo00 to 1050°C and
298 J. EDMOND ET AL.

decreased to 700 to 900°C for the InGaN layers. N-type and p-type doping
was achieved with the introduction of Si and Mg, respectively.
Room-temperature photoluminescence (PL) was employed to optically
characterize undoped and doped GaN, AlGaN, and InGaN layers. A
LO-mW, 325-nm He-Cd laser with a spot size of -50pm in diameter was
used as the excitation source. These layers were combined in device
structures to form LEDs.
Following growth of either an insulating or conducting buffer layer,
Si-doped GaN was grown as a base layer for the double heterojunction
(DH) structure. The D H light-emitting region was formed using a GaN
active layer bordered by p - and n-A1GaN with an A1 composition of 8 to
12%. A p-type GaN contact layer was deposited as the capping layer. The
LEDs were fabricated with a p-type Au contact centered on the chip topside
for wire bonding. The backside ohmic contact to the S i c was Ni sintered at
900 to 1OOO"C in an inert atmosphere. All devices were fabricated using a
mesa geometry and passivated with SO,.
Room-temperature EL measurements were performed on blue LEDs
using a Photoresearch Model PR703A Spectrascan Spectroradiometer Sys-
tem from 390 to 730nm. The total optical output power of the devices was
determined with the use of an integrating sphere attachment. The external
quantum efficiency as a function of drive current was also determined. The
current voltage characteristics were measured with a Tektronix 370 Curve
Tracer. A room-temperature Hall effect using A1 and Au ohmic contacts for
the respective rz- and p-type layers was also performed. The dislocation
density in the films ( - 10' cm-') was determined by transmission electron
microscopy measurements.

2. HALLEFFECT

GaN epilayers grown on 6H-SiC substrates were controllably doped in

-
the carrier concentration ranges of l o i 5 to loi9cm-3 for n-type, and 1015
to 6 x 10"cm-3 for p-type, respectively, as determined by Hall and
current-voltage measurements. Figures 10a and 10b show temperature-
dependent Hall effect data for a 2-pm-thick n-type GaN layer doped with Si
grown on 6H-Sic. Figure 10a shows the variation in electron concentration
and also resistivity as a function of reciprocal temperature. At 300 K, the
carrier concentration and resistivity values were 1.35 x 10'' cm-3 and
0.016 R-cm, respectively. At lower temperatures, the carrier concentration
saturated due to impurity band conduction. Figure 10b shows the Hall
mobility as a function of temperature. The 300-K mobility of 293 cm*/V-sec
is comparable to the highest value reported at this carrier concentration and
indicates the high quality of the epitaxial layer.
 7 Sic-BASED uv h3OTODIODES AND LIGHT-EMITTING
DIODES 299

IE+19 0.10 1000

-
?
-5 h
E
Y
-

$P
.-
C

6
I

G E
8 .-3 0
;.
5 .;, , -
'j
U
L.
c0: a s
a"
IE+18 0.01 100
0 2 4 6 8 10 12 10 I00 I 00(

(a) (b)
FIG. 10. Temperature-dependent Hall effect data for an Si-doped GaN layer grown on Sic.
The (a) donor concentration and resistivity at 300K were 1.35 x 1018cm-3 and 0.016R-cm,
respectivley, with (b) a mobility of 293cmz/V.s.

Figures l l a and l l b show Hall data for a typical Mg-doped p-GaN

top-contact layer. At 300 K, the carrier concentration and resistivity values
for p-type GaN were 6 x loi7cm-3 and 1.3 0-cm, respectively. The mobil-
ity of this layer was 8 cm2/V-sec,which is a typical value reported by other
researchers for p-type GaN.

IE+20 IE+03

T: I ~! ! ! ! ! ! I
-g IE+IY I E+02

.--
c
0
m
IE+IX IE+OI
s
3
22 IE+17 1E+OO
i?

IE+16 IE-01

Frc. 11. Temperature-dependent Hall effect data for a Mg-doped GaN layer grown on Sic.
The (a) hole concentration and resistivity at 300K were 6.1 x lO"cm-' and 1.3Q-cm,
respectively, with (b) a mobility of 8 cm'/V. s.
300 J. EDMONDET AL.

3. PHOTOLUMINESCENCE

Room-temperature PL spectra of undoped and Mg-doped GaN films

were measured. PL spectra of undoped GaN epilayers exhibit an emission
dominated by the band-edge exciton of 3.41eV (Fig. 12a). The defect
luminescence at 2.2eV was not observed. PL spectra of a Mg-doped GaN
epilayer are shown in Fig. 12b. The peak emission is at 435 nm. The peak
emission wavelength changes with Mg doping concentration, as observed on
Mg-doped GaN films grown on sapphire substrates by other researchers
E121.
Figure 13 shows room-temperature PL spectra for undoped AI,Ga, -,N
layers with an A1 composition in the range of 0 to 10%. As shown,

-
room-temperature PL of pure GaN on S i c has a characteristic peak at
366.4 nm and an FWHM of 30 to 40 meV. As the percentage of A1 was
increased to 5, 7. and 10% in the epilayer, the peak emission shifted to 351.5,
346.2, and 337.5 nm, respectively. The emission halfwidth also increased
slightly with increasing A1 composition, which is typically an indication of
degradation in material quality. Growth conditions were optimized to
reduce the 2.2-eV luminescence and was thus not observed in any of the
layers. In addition to these, AlGaN layers with A1 composition up to 22%
have been achieved.
Figure 14 shows room-temperature PL spectra for undoped In,Ga, -xN
layers, with an In composition in the range of 15 to 48%. As shown, the

Temp = 300 K 100

. 435.4

g 75
x
.-
UI

=u
C

SO
-
v

'
-
.-
m

25

0
300 400 500 600 300 400 SOD hOO
Wavelengrh (nm) Wavelength (nm)

FIG. 12. Room-temperaturePL spectra of (a) undoped GaN and (b) Mg-doped GaN.
 7 Sic-BASED uv PHOTODIODES AND LIGHT-EMITTING
DIODES 301

I00

15

50

25

0
340 3 60 380 400

Wavelength (nm)
FIG. 13. Room-temperature PL spectra for undoped Al,Ga,-,N layers with A1 composi-
tions in the range of 0 to 10%.

FIG. 14. Room-temperature PL spectra for InGaN layers with an In composition in the
range of 15 to 48%.
302 J. EUMOND ET AL

underlying GaN on S i c has a characteristic peak at 366.4nm. At a

composition of Ino.15Gao.85N,a peak in the UV at 395 nm was observed,
with an FWHM of 1 1 nm. As the indium concentration was increased to 22,
33. and 48%. the emission peak red shifted from deep blue to green. The
corresponding peak wavelengths were 426, 460, and 509 nm, while the
bandwidth of the emission was 18, 24, and 32 nm, respectively. This increase
in bandwidth is typically an indication of degradation in material quality.
As can be seen in the PL spectra, the defect luminescence near 550 nm was
weak compared to the luminescence from the InGaN layers.

4. GaN: S i c BLUELEDs

Two types of LED structures were grown and compared for light
emission and forward operating voltage. Cree’s initial production of blue
LEDs fabricated on S i c substrates was released in mid-1995 and employed
a highly resistive buffer layer consisting of a high concentration of Al. To
bypass this resistive layer between n-Sic and n-GaN, a shorting ring was
applied that allowed for vertical current flow from the top p-type GaN layer
to the chip backside. The most recent epitaxy structure and chip design
takes full advantage of the high conductivity of S i c by employing a
conducting AlGaN buffer layer with a low A1 percentage.
Figure 15 shows a schematic diagram of the two types of blue LEDs
discussed: (a) insulating buffer and (b) conductive buffer. As shown in both
structures, the AlGaN/GaN/AlGaN DH is grown on n-GaN separated from
the ii-SiC substrates by a strain-relieving buffer layer. In Fig. 15a, the buffer
layer is substantially AlN and electrically isolates the GaN from the Sic.
This requires the use of a shorting ring, which spans the n-GaN to an Ni

shorting ring
condFcting buffer layer (AIGaN)
\

insulating b

i - i ~ 15 Schematic showing the difference between the (a) insulating and (b) conducting
buffer layer GaN SIC LEDs.
 7 Sic-BASED uv PHOTODIODES AND LIGHT-EMITTING
DIODES 303

ohmic contact on the perimeter of the topside of the Sic chip. This ring not
only complicates the chip fabrication process by adding four photoresist
steps, but also absorbs light being emitted by the chip itself. As shown in
Fig. 15b, this shorting ring structure is eliminated when an AlGaN conduc-
tive buffer is employed. This results in a vertical chip that is smaller in size,
more efficient, and easier to fabricate.
Figure 16 is an SEM image of the two chip types. The insulating buffer
chip shown in Fig. 16a is 300 x 300pm with a square bond pad in the
center. The shorting ring can be seen on the chip periphery extending in

FIG.16. SEM images showing the (a) insulating and (b) conducting buffer layer G a N Sic
blue LEDs.

3000
h

5x
2500
h C
I
4
.
.-
x 2000
.-
..
M
2
I500

IOO(1

500

0
300 400 500 600 700 0 10 20 30 40

Wavelength (nm) Forward Current (mA)

FIG. 17. Optical characterization of GaN:SiC blue LEDs showing (a) a peak emission
wavelength of 430 nm from 10 to 40 mA drive current and (b) an output of 1.7 mW at 20 mA,
corresponding to an external quantum efficiency of 3%.
304 J. EDMONDET AL.

-20pm. By eliminating this ring, as shown in Fig. 16b, the chip size is
reduced to 260 x 260pm. In this design, a round bond pad was employed,
which is more of an industry standard.
The output characteristics of a blue LED utilizing a high-quality AlGaN/
GaN/AlGaN double heterojunction on S i c are shown in Figs. 17a and 17b.
The peak emission from this device is 430 nm, with a bandwidth of 65 nm
(Fig. 17a), characteristic of a deep blue. The maximum output power
observed for the insulating buffer LED is 1.7mW at 20mA, which corre-
sponds to an external quantum efficiency of 3% (Fig. 17b). Presently, the
output power is typically 800 pW at 20 mA for production devices. For the
same epilayer emission efficiency, the output of the conductive buffer chip
increases 25 to 50% as a result of eliminating the shorting ring contact.
The I-V characteristics of both chip types are shown in Fig. 18. As shown
for the insulating buffer LED, the forward operating voltage (V,) using the
shorting ring geometry is as low as 3.45V at 20mA. The dominant
resistance is from the p-type contact. From the forward-bias I-V character-
istics, the total resistance of the chip is 8 to 10a. Attributing all the
resistance to the specific contact resistance ( p c ) ,the value of pc for the p-type
contact was < 3 to 4 x R-cm2 for this device. The operating voltage of

40

30

20

10

-10

-20

-30

-5 -4 -3 -2 -1 0 1 2 3 4 5

Voltage (V)

FIG. 18. The current-voltage characteristics of an insulating (IB) and conducting (CB)
buffer layer GaN:SIC blue LED.
 7 Sic-BASED UV PHOTODIODES AND LIGHT-EMITTING
DIODES 305

the conductive buffer chip was slightly higher than the insulating buffer
device: 3.66V at 20mA. This may be a result of the heterobarrier between
the n-Sic substrate and n-AlGaN buffer layer. Work is being performed to
reduce this heterobarrier, and thus overall Vf,of the device.

5. ELECTRICAL DISCHARGE
STATIC SURVIVABILITY

Another important parameter that has been a reliability issue in nitride

LEDs is electrostatic discharge (ESD) survivability. Both of the commercial
DH LED products on sapphire include a warning of the sensitivity of these
devices. Other types of LED materials, including Gap, AlGaAs, AlInGaP,
and Sic, show no sensitivity to ESD. In this study, G a N Sic LEDs were
tested for ESD sensitivity by applying a reverse-bias pulse up to 2000 V and
measuring any change in the reverse-bias leakage current at - 10V. This
type of test simulates the discharge from a human body and is commonly
employed for ESD testing.
DH LEDs on sapphire typically failed the ESD test at <5OOV. The
GaNSiC LEDs were tested to 6000V, at which point the plastic lamp
encapsulant broke down. Earlier GaN: Sic LEDs showed sensitivity similar
to those grown on sapphire. By optimizing the MOCVD growth par-
ameters, nearly 100% of the G a N Sic chips will now withstand >2000V,
which exceeds the human body model. The improved ruggedness of GaN
on Sic is likely due to the lower defect density of this structure as compared
to GaN on sapphire.

VI. Summary

While both blue and green 6H-Sic LEDs have been developed to the
point of commercial viability, with the blue being a relatively successful
product, the brightness and efficiency of these devices is far below that of
the group 111-nitride-based blue and green LEDs developed by Nichia
Chemical, Cree, and others in the past few years. As a result, the future of
emitters that use Sic as the active structure appears to be quite limited.
However, 6H-Sic is an excellent substrate for heteroepitaxial growth of
111-nitrides, and Cree’s line of G.SiC LEDs is based on nitride structures
grown on 6H-Sic. As such, Sic will continue to play a major role in future
super-bright visible emitters and UV detectors.
306 J. EDMONDET AL.

A c KNOWLEDGMENTS

This research was performed at Cree Research, Inc., and partially funded
by the Defense Advanced Research Projects Agency under contract numbers
N00014-95-C-0038, MDA972-95-C-0016, and F 19628-96-C-0066. The
authors would like to thank Mark Edmond for aiding in producing the
SEM images of the LED chips.

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