Title of Invention

A METHOD OF FABRICATING A LIGHT EMITTING DEVICE"

Abstract When a p-type MgxZn1-xO-type layer (2) is grown based on a metal organic vapor-phase epitaxy process, the p-type MgxZn1-xO-type layer (2) is annealed in an oxygen-containing atmosphere during and/or after completion of the growth of the p-type MgxZn1-xO-type layer (2). In addition, a vapor-phase epitaxy process of a semiconductor layer is proceed while irradiating ultraviolet light to the surface of a substrate to be grown and source gasses. In addition, when a MgxZn1-xO-type buffer layer that is oriented so as to align the c-axis thereof to a thickness-wise direction is formed by an aotmic layer epitaxy process, a metal monoatomic layer is grown at first. In addition, a ZnO-base semiconductor active layer (33) is formed by using a semiconductor material mainly composed of ZnO containing Se or Te. A light emitting device is formed by using these techniques.
Full Text DESCRIPTION
A METHOD OF FABRICATING A LIGHT EMITTING DEVICE.
TECHNICAL FIELD
This invention relates to a light emitting device and a
method of fabricating the same.
BACKGROUND ART
There have long been demands for high-luminance, light
emitting device capable of causing short-wavelength emission in
the blue light region. Such light emitting device has recently
been realized by using AIGalnN-base materials. Rapid progress
has also been made in applying the device to full-color, light
emitting apparatuses or to display apparatuses by combining it
with red and green high-luminance, light emitting devices. Use
of the AIGalnN-base material, however, inevitably raises the
costs because the material contains Ga and In as major
components, both of which are relatively rare metals. One of
other major problems of the material is that the growth
temperature thereof is as high as 700 to 1,000°C, and thus
consumes a considerably large amount of energy for the
production. This is undesirable not only in terms of cost
reduction, but also in terms of being against the stream of the
times where discussions on energy saving and suppression of
global warming are prevailing. Japanese Laid-Open Patent
Publication No. 2001-44500 proposes a light emitting device
having a more inexpensive ZnO-base compound semiconductor
layer heteroepitaxially grown on a sapphire substrate. Japanese
Laid-Open Patent Publication No. 11-168262 discloses a two-
dimensional-array planar light emitting device using a light
emitting layer portion composed of oxides of Zn and Mg, or alloy
thereof.
In addition, an InAIAsP/lnGaAsP compound semiconductor
laser typically for use in transponders for submarine optical fiber
cables, of which specifications such as crystal defect density or
the like are very strictly regulated in order to realize a high
output and an high durability.
In all of these devices, semiconductor layers composing the
light emitting layer portion are formed by a vapor-phase epitaxy
process such as sputtering, molecular beam epitaxy (MBE) or
metal organic vapor phase epitaxy (MOVPE).
There is a problem that oxide layers of Zn and Mg are very
likely io cause oxygen deficiency, and they inevitably tend to
have an n-type conductivity, so that it is intrinsically difficult to
obtain the crystal having only a less amount of n-type carrier
(electrons) as a conductive carrier. Nevertheless, in the
fabrication of the electronic devices disclosed in the above-
described patent publications, it is essentially necessary to form
oxide layers of Zn and Mg having a p-type conductivity. These
oxide crystals, however, tend to have an n-type conductivity due
to oxygen deficiency as described in the above, and it has long
been believed as very difficult to form the p-type crystal or non-
doped, semi-insulating crystal used for the active layer. One
possible method may be such as adding p-type dopant, but
conversion of an n-type conductivity of a material into a p-type
conductivity needs a large amount of dopants in order to
compensate the whole portion of the existing n-type carriers and
to excessively generate p-type carriers, so that problems in
stability, reproducibility and uniformity of the electric
characteristics remain unsolved.
Even for the case where the light emitting device is to be
fabricated by a vapor-phase epitaxy process using any compound
semiconductors other than the oxides of Zn and Mg (referred to
as ZnO-base oxide or MgZnO-base oxide, hereinafter), only a
tiny crystal defect ascribabie to variation in reaction efficiency of
the source gases may cause failure especially in the
aforementioned InAIAsP/lnGaAsP compound semiconductor laser,
for which a very high level of quality is required, and may
considerably lower the production yield.
ZnO-base oxide can be obtained by a vapor-phase epitaxy
in a vacuum environment, where heteroepitaxial growth process
using a substrate of a different origin, such as sapphire, is
unconditionally adopted because of difficulty in bulk single
crystal growth. It is therefore necessary to interpose an
appropriate buffer layer between the substrate and the light
emitting layer portion in order to attain a desirable crystallinity of
the light emitting layer portion as described in the above. The
aforementioned Japanese Laid-Open Patent Publication No.
2001-44500 discloses a method in which the buffer layer (contact
layer) is formed by MBE (Molecular Beam Epitaxy) process or
MOVPE (Metalorganic Vapour Phase Epitaxy) process similarly to
the light emitting layer to be formed in succession.
The MBE process, however, cannot readily suppress
generation of the oxygen deficiency due to its low pressure in the
growth atmosphere, so that it is very difficult for the process to
form the ZnO-base oxide layer which is indispensable for
composing the light emitting device. On the other hand, the
MOVPE process can arbitrarily vary partial pressure of oxygen
during the growth, and thus can suppress generation of the
oxygen elimination or oxygen deficiency by raising the
atmospheric pressure to some extent. In the MOVPE process
generally proceeded in a continuous manner, even if any
accidental irregularity such as deficiency or dislocation of the
atoms should occur, the layer growth for the next layer and
thereafter continuously proceed while leaving the irregularity
unrepaired, so that the process could not always ensure a
desirable quality of the buffer layer which governs the crystal
quality of the light emitting layer portion, and this has
consequently been making it difficult to obtain the device having
an excellent light emission efficiency.
The aforementioned ZnO-base oxide will have a larger band
gap energy as alloy composition x of MgO (magnesium oxide) to
ZnO (zinc oxide) increases. For the case where the ZnO-base
semiconductor light emitting device, which comprises an MgZnO-
type oxide, is configured based on the double heterostructure, it
is therefore a general practice to compose the active layer with
ZnO in view of ensuring more effective confinement of carriers
injected thereto. The MgZnO-type oxide can be formed by the
MOVPE process or MBE process as described in the above, but
the formation process thereof is highly causative of oxygen
deficiency of the MgZnO-type oxide and can readily result in
degradation of crystallinity of the active layer composed of ZnO.
This consequently expands total half value width of the emission
wavelength range ascribable to the active layer, reduces the
emission intensity, and suppresses the emission efficiency for
specific wavelength to be desired.
A first subject of the invention is, therefore, to provide a
method of fabricating a light emitting device having a ZnO-base
oxide layer, capable of growing the p-type oxide layer in a
reproducible and stable manner.
A second subject of the invention is to provide a method of
fabricating a light emitting device capable of drastically raising
reaction efficiency of the source gases when the semiconductor
layer composing the light emitting layer portion is formed by a
vapor-phase epitaxy process, and of readily realizing
semiconductor layers having a conductivity type which have not
conventionally been obtainable, and having only a less amount of
crystal defects and being high in quality.
A third subject of the invention is to provide a method of
fabricating a light emitting device capable of realizing a high-
quality, light emitting layer portion composed of a ZnO-base
oxide, and to provide also a light emitting device obtainable by
the method.
A fourth subject of the invention is to provide a light
emitting device using a ZnO-base oxide, of which active layer
can be formed with a high quality in an exact manner, and is
further to provide a high-performance, blue-color light emitting
device at low costs.
DISCLOSURE OF THE INVENTION
(First Invention)
A first invention is to solve the aforementioned first subject,
and is to provide a method of fabricating a light emitting device
having a light emitting layer portion which includes a p-type
MgxZn1-xO (where, 0=x=1) layer, wherein the p-type MgxZn1-xO
layer is grown by a metal organic vapor-phase epitaxy process
while supplying organometallic gases, an oxygen component
source gas and a p-type dopant gas into a reaction vessel, and is,
annealed during and/or after completion of the growth thereof in
an oxygen-containing atmosphere.
In the first invention, the p-type MgxZn1-xO layer grown by a
metal organic vapor-phase epitaxy process is annealed in the
oxygen-containing atmosphere during and/or after completion of
the growth. This effectively prevents the oxygen deficiency from
occurring, and successfully obtains a crystal having a less
amount of n-type carrier. It is therefore no more necessary to
add an excessive amount of p-type dopant for compensating the
n-type carrier, and this makes it possible to obtain the light
emitting device containing the p-type MgxZn1-xO layer, excellent
in the stability, reproducibility and uniformity in the electrical
characteristics.
In order to obtain a high-luminance, light emitting device, it
is effective to compose the light emitting layer portion so as to
have a double heterostructure as described in the next. That is,
the light emitting layer portion is configured so as to have a
structure in which an n-type cladding layer, an active layer, and a
p-type MgxZn1-xO (where, 0 =x=1) layer are stacked in this
order. The method of fabricating a light emitting device
according to the first invention herein characteristically
comprises:
an n-type cladding layer growing step for growing the n-
type cladding layer; and
an active layer growing step for growing the active layer;
and
a p-type cladding layer growing step for growing the p-type
cladding layer by a metal organic vapor-phase epitaxy process
while supplying organometallic gases, an oxygen component
source gas and a p-type dopant gas into a reaction vessel, and
annealing the p-type cladding layer during and/or after
completion of the growth thereof in an oxygen-containing
atmosphere. This method is successful in realizing, a device
showing high emission intensity specific to the double
heterostructure.
The light emitting layer portion can be configured so that
the n-type cladding layer composed of an n-type MgzZn1-xO
(where, 0=z=1) layer, the active layer composed of a MgyZn1-yO
(where, 0 ^ yy) layer, and the p-type cladding layer
composed of a p-type MgxZn1-xO (where, 0=x=1) layer are
stacked in this order. In the n-type cladding layer formation step
herein, organometallic gases and an oxygen component source
gas are supplied into the reaction vessel so as to allow the n-
type cladding layer to grow on the substrate based on a meta!
organic vapor-phase epitaxy process. The active layer growing
step herein is a step for growing the active layer on a substrate
by a metal organic vapor-phase epitaxy process while supplying
organometallic gases and an oxygen component source gas into
the reaction vessel, and includes a step for annealing the layer
during and/or after completion of the growth thereof in an
oxygen-containing atmosphere.
In the above-described method in which the active layer
composed of the MgyZn1-yO layer and the p-type cladding layer
composed of the p-type MgxZn1-xO layer are formed by a metal
organic vapor-phase epitaxy process, the annealing carried out
during and/or after completion of the growth of these layers can
effectively prevent the oxygen deficiency from occurring within
the layers, and is successful in readily obtaining the crystal
having only a less amount of n-type carrier. It is therefore no
more necessary for the p-type cladding layer to be added with an
excessive amount of p-type dopant for compensating the n-type
carrier, and it is made possible for the active layer to suppress
the carrier concentration and to raise the emission recombination
efficiency. This is also advantageous in that it can largely
reduce the costs, because all layers composing the light emitting
layer portion can be composed using the inexpensive MgZnO-
base oxide material. On the other hand, the growth process for
the n-type cladding layer does not adopt the aforementioned
annealing to thereby intentionally produce the oxygen deficiency
(note that a composite oxide obtained by partially replacing Zn in
ZnO with Mg is occasionally abbreviated as MgZnO in the
description below, this by no means indicates a condition of
Mg:Zn:O = 1:1:1, where the same will apply also to the second to
fourth inventions).
It is now preferable to suppress the oxygen deficiency
concentration in the p-type MgZnO layer or MgZnO active layer
to as low as 10 sites/cm3 or below (0 site/cm3 not precluded). In
this case, it is very difficult for RF sputtering and molecular beam
epitaxy (MBE) to suppress generation of the oxygen deficiency,
since pressure in the growth atmosphere in these processes are
as low as 10"4 Torr to 10"2 Torr (1.3332X 10-2 Pa to 1.3332 Pa),
so that it is substantially impossible for these methods to grow
the p-type MgZnO layer. On the contrary, a vapor-phase epitaxy
process based on the MOVPE process can arbitrarily vary oxygen
partial pressure during the growth, and thus can suppress
generation of the oxygen elimination or oxygen deficiency by
raising the atmospheric pressure to some extent.
When the annealing for suppressing generation of oxygen
deficiency is carried out, it is preferable to reduce as possible
the amount of supply of the organometallic gases than the
amount of supply adopted for the case where the layer growth is
a matter of preference, and it is more preferable to interrupt the
supply, in view of suppressing generation of the oxygen
deficiency in the layers. The oxygen-containing atmosphere
during the annealing can be created by introducing the oxygen
component source gas (same as that used for the layer growth
based on the MOVPE process) into the reaction vessel, which is
efficient because the annealing can be completed within the
same reaction vessels used for the layer growth.
The annealing may be carried out after completion of the
layer growth, but it may be difficult for the annealing after the
completion to fully remove the oxygen deficiency which remains
deep inside the layer if the oxygen deficiency is accidentally
formed in the process of the layer growth. It is therefore
effective to carry out the annealing during the layer growth, and
more preferably to alternatively repeat the intermittent layer
growth and the annealing in the oxygen-containing atmosphere
for the purpose of more effective suppression of the oxygen
deficiency. In this case, the aforementioned repetition of the
intermittent layer growth and annealing will be more efficient if
the layer to be annealed is grown while continuously supplying
the oxygen component source gas and intermittently interrupting
supply of the organometallic gases, to thereby make use of the
time duration of interrupted supply of the organometallic gases
as an effective duration of the annealing.
Next, the annealing for suppressing the oxygen deficiency
for the p-type MgZnO layer or the MgZnO active layer must be
carried out in the oxygen-containing atmosphere having an
oxygen partial pressure higher than dissociation oxygen pressure
of MgZnO (where, oxygen-containing molecules other than O2 are
to be included after converting the component oxygen into O2).
In an atmosphere having an oxygen partial pressure lower than
the dissociation oxygen pressure of MgZnO, it is impossible to
prevent the oxygen deficiency from occurring due to promoted
decomposition of MgZnO. The oxygen partial pressure adaptable
to the annealing is more preferably 1 Torr (133.32 Pa) or above
While there is no special limitations on the upper limit of the
oxygen partial pressure, the pressure is preferably set within a
range not causative of unnecessary rise in costs of the annealing
facility (typically set at 7,600 (1.013 MPa) Torr or around for the
annealing in the reaction vessel).
(Second Invention)
A second invention is to solve the aforementioned second
subject, and is to provide a method of fabricating a light emitting
device having a step of growing a semiconductor layer for
composing a light emitting layer portion in vapor phase by
introducing source gases in a reaction vessel having a substrate
disposed therein, and by allowing a semiconductor material
generated based on chemical reactions of the source gases to
deposit on the main surface of the substrate, wherein a vapor-
phase epitaxy process of the semiconductor layer is proceeded
while irradiating ultraviolet light to the source gases introduced
in the reaction vessel.
Because the chemical reactions for producing the
semiconductor material from the source gases is promoted by
ultraviolet irradiation in the second invention, the semiconductor
material will be less causative of crystal defects or the like
during deposition on the main surface of the substrate, and will
readily realize the semiconductor layer having only a less amount
of crystal defects.
In the production of the semiconductor material through the
chemical reactions of the source gases, a reaction system
containing the source gases needs be transferred into a reactive
transition state having a high enthalpy. If the amount of energy
required for causing transfer to the transition status is not
supplied, unreacted or incompletely-reacted components of the
source gases will increase components causing adsorption within
the layer and will be causative of the crystal defects. Although
the necessary energy might be supplemented by heat energy,
this requires rise in the temperature of the system. An
excessive rise in the temperature of the substrate however ruin
adsorption ratio of the semiconductor material contributable to
the crystal growth, and undesirably results in formation of the
layers only having a large amount of crystal defects. In contrast,
combined use of the ultraviolet irradiation described in the above
is successful in securing a necessary and enough energy for
completing the generation reactions of the semiconductor
material without excessively raising the temperature of the
system, and in forming the semiconductor layer having only a
less amount of crystal defects.
in this case, one possible system is such as having a
ultraviolet light source disposed so as to oppose with the main
surface of the substrate, in which the source gases are supplied
between the substrate and the ultraviolet light source while
irradiating ultraviolet light towards the main surface. This is
successful in selectively accelerating the generation reactions of
the semiconductor material from the source gases in the vicinity
of the main surface of the substrate. Ultraviolet light irradiated
to the substrate is once absorbed by the substrate, and can
highly activate the outermost portion of the layers under growth
based on the light excitation effect. More specifically, it is
supposed that a highly activated status similar to that obtainable
by the layer growth under a high temperature is locally realized
in the outermost portion of the layers, and this makes it possible
to efficiently proceed the layer growth while suppressing thermal
decomposition of the source gas components in the vapor phase.
In one rational method of irradiating ultraviolet light to the
source gases or the substrate in the reaction vessel, a part of the
wall portion of the reaction vessel opposing to the main surface
of the substrate is configured as a transparent wall portion, the
ultraviolet light source is disposed outside the reaction vessel,
and ultraviolet light from the ultraviolet light source is irradiated
towards the main surface through the transparent wall portion.
According to this configuration, the ultraviolet light source can be
disposed outside the reaction vessel, and this prevents the light
source per se from being adversely affected by corrosion or
deposited reaction products, and elongates the service life of the
apparatus.
Although any vapor-phase epitaxy processes may be
applicable so far as they can correlate the chemical reactions to
tne layer growth, a metal organic vapor-phase epitaxy (MOVPE)
process is particularly preferable because of its potential of
efficiently growing a high-quality oxide semiconductor or
compound semiconductor. While the MBE process is one
possible method other than the MOVPE process, the MOVPE
process can more advantageously be adopted to the formation of
the oxide semiconductor layer described below because it is
more unlikely cause the oxygen deficiency.
In a metal organic vapor-phase epitaxy process, the
semiconductor layer composed of the metal oxide can be formed
by using organometallic gases and an oxygen component source
gas as the source gases, based on chemical reactions of the
organometallic gases with the oxygen component source gas. In
the formation of the oxide semiconductor, any unreacted or
incompletely-reacted oxygen component source gas incorporated
into the layer by adhesion will be causative of the oxygen
deficiency after elimination of the component. The oxygen
deficiency emits an electron as a carrier, and thus inevitably
makes the conductivity type of the resultant layer n-type. This is
a serious non-conformity in formation of p-type layer or insulating
(non-doped) layer indispensable for forming the light emitting
layer portion. Adoption of the second invention herein is
successful in effectively suppressing generation of the oxygen
deficiency. The oxide semiconductor layer thus formed is
exemplified by MgxZn1-xO (where, 0 = x = 1) layer. Use of the
MgxZn1-xO layer makes it possible to readily form a light emitting
device capable of ensuring high luminance light emission in the
blue light region or ultraviolet region.
Adoption of the second invention is successful in effectively
suppressing the oxygen deficiency, and is consequently
successful in readily obtaining the crystal having only a less
amount of n-type carrier. It is therefore no more necessary to
add an excessive amount of p-type dopant for compensating the
n-type carrier, and this makes it possible to obtain the light
emitting device containing the p-type MgxZn1-xO layer, excellent
in the stability, reproducibility and uniformity in the electrical
characteristics.
More specifically, the light emitting layer portion can be
configured so as to have a double heterostructure in which the n-
type cladding layer composed of an n-type MgzZn1-zO (where,0=
z=1) layer, the active layer coimposed of a MgyZn1-yO (where, 0
=yy) layer, and the p-type cladding layer composed of a p-
type MgxZn1-xO (where, 0=x=1) layer are stacked in this order.
In this case, the n-type cladding layer can readily be formed by
supplying the organometallic gases and an oxygen component
source gas into the reaction vessel, without specifically
irradiating ultraviolet light. The active layer can be formed by
supplying the organometallic gasses and an oxygen component
source gas into the reaction vessel with irradiating ultraviolet
light. The p-type cladding layer can be formed by additionally
supplying a p-type dopant gas in the process similar to that for
the active layer.
Also in the second invention, it is preferable to suppress
the oxygen deficiency concentration in the p-type MgZnO layer or
MgZnO active layer to as low as 10 sites/cm3 or below (0
site/cm3 not precluded), and a vapor-phase epitaxy process
based on the MOVPE process is preferable in view of
suppressing the oxygen deficiency. ,,
The second invention is also applicable to fabrication of
compound semiconductor light emitting devices other than those
using the MgZnO-base oxide, such as InAIAsP/lnGaAsP
compound semiconductor light emitting device (laser device, in
particular).
(Third Invention)
A third invention is to solve the aforementioned third
subject, and includes a method of fabricating a light emitting
device and thus-fabricated, light emitting device. The method of
fabricating a light emitting device of the third invention is such as
fabricating a light emitting device having a light emitting layer
portion composed of an MgaZn1-aO-type (where, 0=a=1) oxide,
wherein a buffer layer is formed on a substrate, the buffer layer
having at least an MgaZn1-aO-type oxide layer on the contact side
with the light emitting layer portion, and the light emitting layer
18
portion is grown on the buffer layer;
the MgaZn1-agO-type. oxide layer has wurtzite crystal
structure in which metal atom layers and oxygen atom layers are
alternatively stacked in the direction of the c-axis, the buffer
layer is grown so as to orient the c-axis of the wurtzite crystal
structure to the thickness-wise direction, and so as to form a
metal atom layer as a metal monoatomic layer on the substrate
by the atomic layer epitaxy, and then to form the residual oxygen
atom layers and metal atom layers.
The light emitting device of the third invention is such as
having a light emitting layer portion composed of an MgaZn1-aO-
type (where, O=a=1) oxide and formed on a substrate, and
having a buffer layer formed between the substrate and the light
emitting layer portion, the buffer layer having at least an MgaZn1-
aO-type oxide layer on the contact side with the light emitting
layer portion;
the MgaZn1-aO-type oxide layer has wurtzite crystal
structure in which metal atom layers and oxygen atom layers are
alternatively stacked in the direction of the c-axis; and
the buffer layer has the c-axis of the wurtzite crystal
structure oriented to the thickness-wise direction, has a single
atom layer portion as a metal monoatomic layer formed in contact
with the substrate, and has the residual oxygen atom layers and
metal atom layers alternatively stacked successive to the metal
monoatomic layer.
In the third invention, the entire portion or at least a portion
on the contact side with the light emitting layer portion of the
buffer layer formed on the substrate is composed of an MgaZn1-
aO-type oxide (where, alloy composition a is not always same
with that of the light emitting layer portion, and the oxide may
occasionally be referred to as MgZnO-type oxide or simply as
MgZnO, while omitting indication of the alloy composition a).
Because the portion on the junction interface side of the buffer
layer and the light emitting layer portion have basically the same
crystal structure (wurtzite crystal structure) and the same
component system, local irregularity of the crystal structure due
to interaction between the components over the junction interface
becomes less likely to occur, and this is advantageous in
realizing the light emitting layer portion having a desirable
crystal Iinity. Typically the entire portion of the buffer layer may
be composed of the MgZnO-type oxide. This makes it possible to
carry out a vapor-phase epitaxy process of the buffer layer and
light emitting layer portion in the same facility in an extremely
simple manner.
In the third invention, the buffer layer is formed particularly
so as to form a metal atom layer as a metal monoatomic layer on
the substrate by the atomic layer epitaxy (ALE) process, and
then to form the residual oxygen atom layers and metal atom
layers. By adopting the ALE process, formation of the metal
atom layer can be saturated once a single atomic layer is
completed (so-called, self-termination function), and the atoms
arranged in the layer are less likely to cause any irregularity
such as deficiency or dislocation. By forming a single layer of
the less-irregular metal atom layer and then forming the
succeeaing metal atomic layers and oxygen atom layers, it is
made possible to obtain the buffer layer having an excellent
crystallinity. This consequently improves the crystallinity of the
light emitting layer portion formed thereon, and is advantageous
in realizing a high-performance, light emitting device. By
adopting the above-described method, the light emitting device of
the third invention will have the c-axis of the wurtzite crystal
structure oriented to the thickness-wise direction, will have the
single atom layer portion in contact with the substrate formed as
a metal monoatomic layer, and will have the residual oxygen
atom layers and metal atom layers alternatively formed in
succession to the metal monoatomic layer. Thus-configured
buffer layer has an excellent crystallinity, and this makes it
possible to realize the light emitting layer portion having only a
less amount of defects and irregularity, and having a desirable
emission efficiency.
The ALE process can be carried out in a form of a metal
organic vapor-phase epitaxy (MOVPE) process in which an
organometallic compound gas and an oxygen component source
gas are supplied in a reaction vessel having a substrate disposed
therein. More specifically, only an organometallic compound gas,
which serves as a source material for the metal atom layer, is
allowed to flow through the reaction vessel to thereby form the
first metal atom layer for composing the buffer layer so as to be
saturated by a single atom layer, to thereby form a metal
monoatomic layer. As shown in Fig. 16A, organometallic
compound (MO) molecule causes decomposition or elimination of
organic groups bound thereto, and allows its metal atom to
chemically adsorb onto the substrate. Under the ALE process,
the metal atom is adsorbed while keeping a part of its organic
groups unremoved, and as shown in Fig. 16B, forms the metal
atom layer so as to orient the residual organic group towards the
upper surface. Once the first single atomic layer is completed,
thus-oriented organic groups can inhibit adhesion of newly-
coming metal atoms and can fully exhibit the self-termination
function, so that the atoms arranged in the layer will become very
unlikely to cause irregularities such as deficiency and dislocation.
In the MOVPE process, oxygen partial pressure during the
growth can arbitrarily be varied, so that generation of the oxygen
elimination or oxygen deficiency is effectively avoidable by
raising the atmospheric pressure to some extent. This
consequently makes it possible to form the p-type MgaZn1-aO
layer indispensable for the light emitting device, in particular the
p-type MgaZn1-aO layer such as having a density of oxygen
deficiency of as small as 10 sites/cm3 or below. The smaller
density of oxygen deficiency is the better (that is, 0 site/cm3 not
precluded).
When the MOVPE process is adopted, composition of the
entire portion of the buffer layer using MgZnO-type oxide is
advantageous, because the buffer layer and light emitting layer
portion can be grown sequentially in the same reaction vessel
only by adjusting ratio of the organometailic gasses and oxygen
component source gas. This is also advantageous in that the
purging of the vessel between growth processes for the buffer
layer and light emitting layer portion needs only a short time as
compared with the case where the buffer layer is formed using
different materials such as GaN, or the purging per se is
omissible.
Also in the third invention, it is effective to grow the light
emitting layer portion so as to have a double heterostructure as
described below, in order to obtain a high-luminance, light
emitting device. That is, the double heterostructured, light
emitting layer portion is formed on the buffer layer by
sequentially stacking a first-conductivity-type cladding layer (p-
type or n-type) composed of MgaZn1-aaO-type oxide, an active
layer, and a second-conductivity-type cladding layer (n-type or p-
type) having a conductivity type different from that of the first-
conductivity-type cladding layer, in this order.
(Fourth Invention)
A fourth invention is to provide a light emitting device for
solving the fourth subject. The light emitting device has a double
heterostructured, light emitting layer portion which comprises an
active layer and cladding layers, wherein the active layer is
composed of a Group II-VI compound semiconductor containing
Zn as a Group II element, and containing O together with Se or
Te as a Group VI element, and the cladding layers are composed
of MgxZn1-xO-type (where, 0=x=1) oxide.
In the double hetero-type, ZnO-base semiconductor light
emitting devices composed of an MgZnO-base oxide, those
having the active layer composed of ZnO, having a band gap
energy of 3.25 eV, causes light emission in near violet color. To
adjust the band gap energy suitable for blue-color light emission,
it is necessary to add some impurity to the ZnO active layer to
thereby form impurity levels, or to configure the active layer
using a ZnO-base alloyed compound semiconductor having a
smaller band gap energy than ZnO has.
To achieve blue-color light emission with high emission
efficiency, it is necessary for the active layer to satisfy the
above-described constitutional conditions, and to stabilize the
crystallinity. In view of stabilizing the crystallinity of the active
layer composed of a ZnO-base semiconductor mainly containing
ZnO, an essential point resides in that how successfully the
oxygen deficiency can be suppressed when the active layer is
stacked by epitaxially growing the ZnO-base semiconductor
typically based on the MOVPE or MBE process.
The active layer in the fourth invention is formed using
Group II-VI compound semiconductor (aforementioned ZnO-base
semiconductor) containing Zn (zinc) as a Group II element, and
containing O (oxygen) together with Se (selenium) or Te
(tellurium) as a Group VI element, and this makes it possible to
introduce Se or Te, which belongs to the same Group with oxygen,
into the oxygen-deficient sites. For the case where the
introduced Se or Te acts as an impurity, Zn-Se pair or Zn-Te pair
is supposed to form a deeper impurity level than ZnO forms, so
that blue-color light emission with a higher efficiency than that
given by ZnO-base semiconductor can be obtained.
In the active layer composed of ZnO-base semiconductor,
Se or Te introduced into the oxygen-deficient sites may not exist
in a form of impurity, but may form a local crystal structure of
ZnOSe or ZnOTe which is different from ZnO. Both of the ZnOSe
crystal and ZnOTe crystal have smaller band gap energies as
compared with that of ZnO crystal, and can form the active layer
capable of blue-color light emission at a higher efficiency. The
emission possibly obtained via the impurity levels results in
saturation of effect of improving the emission efficiency due to a
limited range of formation of Zn-Se pair or Zn-Te pair which is
causative of the impurity levels. On the other hand, the emission
possibly obtained via the bands formed by the ZnOSe crystal or
ZnOTe crystal results in further increase in the emission
efficiency.
The double heterostructure adopted for the light emitting
device of the fourth invention is such as having the active layer,
which is composed of the aforementioned Se- or Te-containing,
ZnO-base semiconductor, sandwiched between the cladding
layers which are composed of MgxZn,-xO-type (0=x=1) oxide
having a band gap energy larger than that of the active layer.
The MgxZn1-xO-type (0=x=1) oxide will have a larger band gap
energy as MgO alloy composition x increases, but will also have
a larger insulating property, increase in MgO alloy composition x,
therefore, makes it difficult to dope an effective number of
carriers into the cladding layer. It is in particular difficult for ZnO,
having an n-type conductivity in a non-doped status, to form the
p-type cladding layer which should be doped with p-type carriers.
In contrast to that the active layer has been formed by using ZnO,
the active layer in the fourth invention is formed by using the Se-
or Te- containing, ZnO-base semiconductor having a band gap
energy smaller than that of ZnO, so that it is made possible to
configure the cladding layer using the MgxZn1-xO-base oxide of
which ZnO or MgO alloy composition x is suppressed to a low
level. This consequently makes it possible to dope an effective
number of carriers into the cladding layer, to dope an effective
number of carriers also into the active layer, and to improve the
emission efficiency.
When the active layer is composed of ZnOSe crystal or
ZnOTe crystal, the ZnOSe crystal or ZnOTe crystal will have a
smaller band gap energy as the ratio of Se or Te to O increases,
and thus the emission wavelength becomes shorter. A band gap
energy suitable for blue-color light emission falls within a range
from 2.52 to 3.15 eV, where the largest band gap energy of 3.15
eV suitable for blue-color light emission can be attained typically
by adjusting a ratio of O and Se to 61:39 for the ZnOSe crystal,
and by adjusting a ratio of O and Te to 81:19 for the ZnOTe
crystal. Because ZnO has a band gap energy of 3.25 eV, the
cladding layer can be formed by using ZnO without suppressing
the carrier confinement effect in the active layer. By composing
the cladding layer with ZnO, the cladding layer and active layer
will have ZnO as a major constituent thereof, and this not only
makes it possible to improve working efficiency in the fabrication,
but also makes it unnecessary to use excessive Mg, and
contributes to cost reduction.
Beside the above-described blue-color light emission, it is
also possible to obtain band gap energy suitable for emission at
longer wavelength regions such as blue-green to green regions,
by adjusting ratio of Se and Te to O in the ZnOSe crystal or
ZnOTe crystal. Since the band gap energy of the active layer in
this case is smaller than that suitable for blue-color light
emission, the cladding layer can be composed by using ZnO.
The active layer of the ZnO-base semiconductor light
emitting device of the fourth invention can be configured as
having a multi-layered structure in which sub-layers composed of
ZnSe or ZnTe are inserted in a main layer composed of ZnO so
as to be distributed over the thickness-wise direction.
As described in the above, when the active layer is formed
by epitaxially growing ZnO-base semiconductor, crystallinity of
the active layer can be improved by introducing Se or Te, which
belongs to the same Group with oxygen, to oxygen-deficient sites.
It is also possible to shift the emission wavelength of the active
layer to the longer wavelength region. While the active layer
may be configured as a single layer composed of Se- or Te-
containing ZnO-base semiconductor, adoption of the above-
described, multi-layered structure, which is typified by a structure
in which the sub-layers composed of ZnSe or ZnTe, and having a
width not larger than that of a. unimolecular layer of the active
layer, are inserted in a main layer composed of ZnO, ensures the
effects described in the next. Thus-formed sub-layer can
function as a S doped layer and can localize Se or Te in the
thickness-wise direction, and this makes it possible to enhance
effect of introducing Se or Te to the oxygen-deficient sites. This
enhances binding tendency with Zn in the closest vicinity, and
raises probability of forming Zn-Se pair or Zn-Te pair, or of
forming ZnOSe crystal or ZeOTe crystal. Even if the devices are
not introduced into the oxygen-deficient sites, it is made possible
to prevent non-luminescent center caused by unmatched
interface or dislocation, by suppressing formation of different
crystal phases such as ZnSe and ZnTe. If the coverage ratio of
the sub-layer is controlled so as to be smaller than a
unimolecular layer of the active layer, Se or Te is successfully
prevented from depositing as an impurity rather than being
incorporated into the oxygen-deficient sites.
Because the number of layers of the sub-layers to be
inserted into the active layer can properly be selected depending
on the band gap energy, and more specifically on the ratio of Se
or Te to O in the ZnOSe crystal or ZnOTe crystal for composing
the active layer, and is not specifically limited. It is, however,
preferable of course that effect of introduction of Se or Te can
uniformly extend over the active layer in view of obtaining a
uniform light emission therefrom. It is therefore preferable to
form the sub-layers so as to be distributed over the thickness-
wise direction, and typically in a periodical manner.
Other conditions commonly applicable to the first to fourth
inventions will be described.
The growth of the p-type MgZnO layer or MgZnO active
layer based on the MOVPE process can more advantageously be
proceeded under an atmosphere conditioned at a pressure of 10
Torr (1.3332 kPa) or above, so as to more effectively suppress
generation of the oxygen deficiency during the film formation,
and to obtain the p-type MgZnO layer or MgZnO active layer
having desirable characteristics. It is more preferable herein to
adjust oxygen partial pressure (including any other oxygen-
containing molecules other than O2, after converting component
oxygen to O2) to 10 Torr (1.3332 kPa) or above. For the case
where the n-type MgZnO layer is formed on the buffer layer, and
further thereon the MgZnO active layer and p-type MgZnO layer
is formed, any oxygen deficiencies generated in the n-type
MgZnO may be causative of irregularity or the like in the MgZnO
active layer and p-type MgZnO layer formed thereafter, so that it
is preferable that also the n-type MgZnO layer is grown so as to
suppress the oxygen deficiency as possible. In this case, the n-
type MgZnO layer is added with an n-type dopant so as to have
the conductivity type of n-type. On the other hand, for the case
where the p-type MgZnO layer is formed on the buffer layer, and
further thereon the MgZnO active layer and n-type MgZnO layer
are formed, it is also allowable to intentionally form the oxygen
deficiency in the n-type MgZnO layer so as to have an n-type
conductivity.
To make MgaZn1-aO to have a p-type conductivity, it is
necessary to add an appropriate p-type dopant as described in
the above. As the p-type dopant, either one of, or two or more of
N, Ga, Al, in, Li, Si, C, and Se are available. Among these, use
of N is particularly preferable in view of obtaining desirable p-
type characteristics. As the metal element dopant, either one of,
or two or more of Ga, Al, In and Li are available, where Ga is
particularly effective. Combined addition of these dopants with N
can ensure desirable p-type characteristics in a more reliable
manner.
To ensure sufficient emission characteristics, p-type carrier
concentration in the p-type MggZn1-aO layer preferably falls
within a range from 1 x10-6 sites/cm3 to 8x1018 sites/cm3. The p-
type carrier concentration less than 1 x1 016 sites/cm3 may make it
difficult to obtain a sufficient emission luminance. On the other
hand, the p-type carrier concentration exceeding 8x1018 sites/cm3
may excessively increase the amount of p-type carriers injected
to the active layer, and this is causative of increase in p-type
carrier not contributable to the light emission due to reverse
diffusion into the p-type MgaZn1-aO layer, or injection into the n-
type cladding layer after getting over the potential barrier, to
thereby lower the emission efficiency. Also for the n-type
MgaZn1-aO layer, it is preferable to adjust n-type carrier
concentration within a range from 1x1016 sites/cm3 to 8x1018
sites/cm3 based on the same reason.
Examples of materials available for substrate include
aluminum oxide, gallium oxide, magnesium oxide, gallium nitride,
aluminum nitride, silicon, silicon carbide, gallium arsenide,
indium-tin composite oxide and glass. Particularly preferable
forms of the substrate include the followings. As shown in Fig. 2,
MgaZn1-aO-type oxide has wurtzite crystal structure comprising
metal atom layers and oxygen atom layers alternatively stacked
in the direction of c-axis, where the oxygen atoms follow a
hexagonal atomic arrangement. The substrate is, therefore,
preferably an oxide single crystal substrate in which oxygen
atoms follow the hexagonal atomic arrangement, and the C-plane
((0001) plane) of the hexagonal atomic arrangement is exposed
to the main surface, in terms of improving crystal matching with
the buffer layer, and of obtaining the light emitting layer portion
with a desirable crystal Unity/ In this case, the buffer layer is
composed of the MgaZn1-aO-type oxide over the entire portion
thereof, and is formed on the main surface of the oxide single
crystal substrate so as to orient the c-axis of its wurtzite crystal
structure in the thickness-wise direction. Examples of such oxide
single crystal substrate include those composed of corundum-
structured oxide, where a sapphire substrate is one specific
example thereof.
As shown in Fig. 15, in an oxide having corundum-type
structure, a lattice of oxygen (O) atoms has a hexagonal atomic
arrangement, and in the direction of c-axis thereof, O atom (ion)
layers and metal atom (ion: shown as Al in the drawing) layers
are alternatively stacked. In this crystal structure, one of both
atomic layers appearing on both ends in the direction of c-axis
will always be an oxygen atom layer plane, and the other will
always be a metal atom layer plane. The O atom layer plane has
the same O atomic arrangement with the O atom layer in the
wurtzite crystal structure except for difference in the lattice
constants. For the case where the main surface of the oxide
single crystal substrate having such crystal structure will have
formed thereon the buffer layer comprising MgaZn1-aO-type oxide
having the wurtzite crystal structure, a junction structure having
better matching property can be obtained by stacking the metal
atom layer of the buffer layer on the main surface of the
substrate composing the O atom layer plane.
It is to be noted that it is also allowable to grow the light
emitting layer portion on the A-plane of the sapphire substrate as
disclosed in Japanese Laid-Open Patent Publication No. 2001-
44500, and this is effective to a certain extent in terms of
planarization of the crystal growth surface. Because the A-plane
of the sapphire substrate has metal atoms and oxygen atoms
exposed thereon in a mixed manner, the general continuous-
growth-type MOVPE process may raise probability of causing
adsorption of oxygen atoms and zinc atoms at the same time on
the A-plane ((11-20) plane). This is more likely to cause
irregularity in the stacking of the buffer layer grown based on the
c-axis orientation, and is not always successful in obtaining a
high-quality buffer layer and light emitting layer portion. Use of
the ALE process, as in the third invention, is now successful in
obtaining a high-quality buffer layer and, consequently, the light
emitting layer portion in a highly reproducible manner, because
the metal monoatomic layer can be formed also on the A-plane in
a forced manner.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Fig. 1 is a conceptual drawing of a double heterostructured,
light emitting layer portion including a p-type MgZnO layer:
Fig. 2 is a schematic drawing of a crystal structure of
MgZnO;
Fig. 3 is a schematic drawing of an arrangement of the
metal ions and oxygen ions in the MgZnO layer;
Fig. 4 is a schematic band chart of a light emitting device
using a junction structure of Type-I band lineup;
Fig. 5A is schematic drawings for explaining a growth
process of the light emitting layer portion of the light emitting
device having a type shown in Fig. 4 in Embodiment 1 of the
invention;
Fig. 5B is a schematic sectional view of a reaction vessel
shown in Fig. 5A;
Fig. 6 is a drawing for explaining an exemplary fabrication
process of the light emitting device having a type shown in Fig.
4;
Fig. 7A is a drawing for explaining operation of the method
of fabricating the light emitting device of the Embodiment 1 of the
invention;
Fig. 7B is an explanatory drawing as continued from Fig.
7A;
Fig. 7C is an explanatory drawing as continued from Fig.
7B;
Fig. 8A is a drawing of a first example of a supply
sequence for an organometallic gas and an oxygen component
source gas in the process shown in Fig. 5A;
Fig. 8B is a drawing of a second example of the same;
Fig. 8C is a drawing of a third example of the same;
Fig. 8D is a drawing of a fourth example of the same;
Fig. 9A is a drawing of a fifth example of the same;
Fig. 9B is a drawing of a sixth example of the same;
Fig. 10A is a schematic band chart of a light emitting
device using a junction structure of Type-I and Type-ll band
lineups;
Fig. 10B is a schematic band chart of another example;
Fig. 11A is a schematic drawing for explaining a vapor
phase growth apparatus for growing the light emitting layer
portion using a ultraviolet lamp based on the MOVPE process in
Embodiment 2 of the invention;
Fig. 11B is a schematic drawing of a modified example of
Fig. 11A;
Fig. 12 is a conceptual drawing of a vapor-phase epitaxy
process for forming the light emitting layer portion using
ultraviolet laser beam;
Fig. 13 is a schematic drawing showing a specific example
of the light emitting device of Embodiment 3 of the invention;
Fig. 14A is a drawing for explaining an exemplary
fabrication process of the light emitting device shown in Fig. 13;
Fig. 14B is a drawing of a process step as continued from
Fig. 14A;
Fig. 14C is a drawing of a process step as continued from
Fig. 14B;
Fig. 15 is a schematic drawing of corundum-type crystal
structure;
Fig. 1 6A is a drawing for explaining operation of a method
of fabricating a light emitting device of Embodiment 3 of the
invention;
Fig. 16B is a drawing for explaining operation as continued
from Fig. 16A;
Fig. 16C is a drawing for explaining operation as continued
from Fig. 16B;
Fig. 16D is a drawing for explaining operation as continued
from Fig. 16C;
Fig. 17 is a drawing exemplifying a temperature control
sequence and gas supply sequence in the process steps shown
in Figs. 1 4A to 14C;
Fig. 1 8A is a drawing for explaining effect of configuring a
mixed metal atom layer as a metal monoatomic layer grown by
the ALE process;
Fig. 18B is a drawing for explaining the effect as continued
from Fig. 18A;
Fig. 18C is a drawing for explaining the effect as continued
from Fig. 18B;
Fig. 19A is a drawing for explaining an example in which a
metal composition gradient layer is configured as a buffer layer;
Fig. 19B is a drawing for explaining the metal composition
gradient layer shown in Fig. 19A;
Fig. 20A is a schematic sectional view showing a stacked
structure of a first example of the ZnO-base semiconductor light
emitting device of Embodiment 4 of the invention;
Fig. 20B is a schematic sectional view showing a stacked
structure of a second example of the same;
Fig. 21 is a schematic sectional view showing a stacked
structure of an exemplary electrode formation status of the ZnO-
base semiconductor light emitting device of the fourth
embodiment of the invention; and
Fig. 22 is a schematic sectional view showing a stacked
structure of another exemplary electrode formation status
differed from Fig. 4.
BEST MODE FOR CARRYING OUT THE INVENTION
Best modes for carrying out the invention will be explained
referring to the drawings.
(Embodiment 1)
Fig. 1 is a drawing schematically showing a stacked
structure of the essential portion of the light emitting device of
the first invention, and the device has a light emitting layer
portion in which an n-type cladding layer 34, an active layer 33
and a p-type cladding layer 2 are stacked in this order. The p-
type cladding layer 2 is composed as a p-type MgxZn1-xO layer (0
=x=1: may occasionally be referred to as p-type MgZnO layer 2.
hereinafter). In the p-type MgZnO layer 2, a trace amount of
either one of, or two or more of N, Ga, Al, In and Li, for example,
are contained as a p-type dopant. The p-type carrier
concentration is adjusted within a range from 1 x1 016 sites/cm3 to
8x1 018 sites/cm3 as described in the above, and more specifically
within a range from 1017 sites/cm3 to 1018 sites/cm3 or around.
Fig. 2 is a schematic drawing of a crystal structure of
MgZnO, where so-called wurtzite structure is shown. In this
structure, oxygen-ion-packed planes and metal-ion- (Zn ion or Mg
ion) packed planes are stacked along the direction of the c-axis
alternatively, and as shown in Fig. 3, the p-type MgZnO layer 2 is
formed so as to align the c-axis thereof along the thickness-wise
direction. Formation of a vacancy due to omission of an oxygen
ion causes oxygen deficiency, and consequently produces
electrons as n-type carriers. Excessive formation of such oxygen
deficiency undesirably increases the n-type carriers, to thereby
ruin p-type conductivity. it is therefore important that how
completely the oxygen deficiency can be suppressed in order to
form the p-type MgZnO layer.
The p-type MgZnO layer 2 can be formed by the MOVPE
process. Principle of the MOVPE process per se is publicly
known. The aforementioned p-type dopant is added during a
vapor-phase epitaxy process. The p-type MgZnO layer 2 is
annealed during or after completion of a vapor-phase epitaxy
process in an oxygen-containing atmosphere. The annealing is
successful in suppressing elimination of oxygen ions, and in
obtaining a desirable p-type MgZnO layer 2 having only a small
amount of oxygen deficiency. It is also effective to carry out the
growth of the p-type MgZnO layer 2 under an atmospheric
pressure of 10 Torr (1.3332 kPa) or above in terms of
suppressing generation of the oxygen deficiency.
Now referring back to Fig. 1, the active layer 33 is
composed of a material having an appropriate band gap
depending on desired emission wavelength. For example, for
those available for visible light emission, materials having band
gap energies Eg (3.10 eV to 2.18 eV or around), capable of
causing light emission in a wavelength range of 400 nm to 570
nm, are selected. Although this range covers emission
wavelength from violet region to green region, those having band
gap energies Eg (2.76 eV to 2.48 eV or around) capable of
causing light emission in a wavelength range of 450 to 500 nm
are selected in particular for the case where blue-color light
emission is desired. On the other hand, those having band gap
energies Eg (4.43 eV to 3.10 eV or around) capable of causing
light emission in a wavelength range of 280 nm to 400 nm are
selected in particular for the case where ultraviolet emission is
desired.
The active layer 33 can be formed typically using a
semiconductor capable of forming a Type-I band lineup between
itself and the p-type MgZnO layer. An example of such active
layer 33 is an MgyZn1-yO layer (where, 0=yy: referred to
as MgZnO active layer, hereinafter). It is to be noted now that "a
Type-I band lineup is formed between the active layer and the p-
type MgZnO layer" means a junction structure, as shown in Fig. 4,
in which the individual energy levels of the bottom of the
conduction band and the upper end of the valence band Ecp, Evp
of the p-type cladding layer (p-type MgZnO layer 2), and the
individual energy levels of the bottom of the conduction band and
the upper end of the valance band ECi, Evi of the active layer
satisfy the following relations of inequality:
ECi Evi > Evp ••• (2)
In this structure, specific barrier will appear for both of the
forward diffusion of holes from the active layer 33 to the n-type
cladding layer 34, and the forward diffusion of electrons (n-type
carriers) to the p-type cladding layer 2. If the material for the n-
type cladding layer 34 is appropriately selected so as to form
Type-I band lineup between the active layer 33 and the n-type
cladding layer 34, similarly to as shown in Fig. 4, the active layer
will have formed therein well-forrmed potential barriers both at the
bottom of the conduction band and the upper end of the valence
band, and will enhance confinement effect both for electrons and
holes. This consequently results in more enhanced effects of
promoting carrier recombination and of improving emission
efficiency. While AIGaN or the like is available for the n-type
cladding layer 34, n-type MgzZn1-zO layer (where 0 = z = 1:
occasionally also referred to as n-type MgZnO layer",
hereinafter) is " more advantageous, because this makes it
possible to form all layers composing the light emitting layer
portion with MgZnO-base oxide material (such light emitting layer
portion will be referred to as "full-oxide-type, light emitting layer
portion, hereinafter), so that it is no more necessary to use rare
metals such as above-described Ga and In (dopants excluded),
which contributes to a considerable cost reduction. Height of the
potential barriers on both sides of the active layer can be
equalized by making the alloy compositions of the n-type MgZnO
layer 34 and the p-type MgZnO identical. Thickness t of the
active layer 33 is selected so as to avoid decrease in the carrier
density in the active layer 33 and excessive increase in the
amount of carriers passing through the active layer 33 based on
the tunneling effect, and is typically adjusted within a range from
30 nm to 1,000 nm.
In the MgZnO active layer 33, a value of alloy composition
y can also serve as a factor which determines band gap energy
Eg. For example, the value is selected in a range of 0=y=0.5
for the case where ultraviolet emission over a wavelength of 280
nm to 400 nm is desired. The potential barrier height thus
formed is preferably 0.1 eV to 0.3 eV or around for light emitting
diode, and 0.25 eV to 0.5 eV or around for semiconductor laser
light source. This value can be determined by selecting the alloy
compositions x, y and z of the p-type MgxZn1-xO layer 2, MgyZn1-
yO active layer 33, and n-type MgzZn1-20 layer 34.
The following paragraphs will describe one exemplary
process for fabricating the light emitting device having the
aforementioned full-oxide-type, light emitting layer portion. First,
as shown in (a) of Fig. 6, a GaN buffer layer 11 is epitaxially
grown on a sapphire substrate 10, and a p-type MgZnO layer 52
(typically of 50 nm thick), an MgZnO active layer 53 (typically of
30 nm thick), and an n-type MgZnO layer 54 (typically of 50 nm
thick) are formed in this order (inverted order of the growth also
acceptable). The epitaxial growth of the individual layers can be
carried out by the MOVPE process as described in the above. It
is to be noted that, MBE in the context of this specification
include not only MBE in a narrow sense in which both of a metal
element component source and a non-metal element component
source are used in solid forms, but also include MOMBE (Metal
Organic Molecular Beam Epitaxy) using the metal element
component source in a form of organometallic compound and the
non-metal element component source in a solid form; gas source
MBE using the metal element component source in a solid form
and the non-metal element component in a gas form; and
chemical beam epitaxy (CBE) using the metal element component
source in a form of organometallic compound and the non-metal
element component source in a gas form.
All of the p-type. MgZnO layer 52, MgZnO active layer 53
and the n-type MgZnO layer 54 can continuously be formed by
the MOVPE process using the same source materials and in the
same reaction vessel as shown in Fig. 5A. In this case, the
growth is preferably allowed to proceed at slightly lower
temperatures, typically at 300°C to 400°C, so as to reduce
reactivity with the GaN buffer layer (not shown in Fig. 5A), and to
raise the lattice matching property. The substrate can be heated
using a heater embedded in a susceptor for holding the substrate,
as shown in Fig. 5B.
Examples of the major materials for composing the
individual layers are such as follows:
• oxygen component source gas: preferably supplied in a form
of oxidative compound gas in view of suppressing an excessive
reaction with organometallic compounds described later, although
oxygen gas is allowable, typified by N2O, NO, NO2 and CO,
where N2O (nitrous oxide) adopted in this embodiment;
Zn source (metal component source) gas: dimethyl zinc
(DMZn), diethyl zinc (DEZn), etc.; and
Mg source (metal component source) gas: bis-
cyclopentadienyl magnesium (Cp2Mg), etc.
Examples of the p-type dopant gas include the followings;
• Li source gas: n-butyl lithium, etc.;
• Si source gas: silicon hydrides such as monosilane;
• C source gas: hydrocarbons (typically alkyl containing one or
more C atoms); and
• Se source gas: hydrogen selenide, etc.
One or more selected from the group consisting of Al, Ga
and In can be allowed to function as excellent p-type dopants
when added together with N. Examples of the dopant gas include
the followings:
• Al source gas: trimethyl aluminum (TMAI), triethyl aluminum
(TEAI), etc.;
Ga source gas: trimethyl gallium (TMGa), triethyl gallium
(TEGa), etc.; and
• In source gas: trimethyl indium (TMIn), triethyl indium (TEIn),
etc.
For the case where N is used as a p-type dopant together
with a metal element (Ga), the p-type MgZnO layer is grown
while supplying a gas which serves as an N source together with
an organometallic gas which serves as a Ga source. In
particular in this embodiment, N2O used as an oxygen component
source also serves as an N source.
The individual source gases are fed into the reaction vessel
after being appropriately diluted with a carrier gas (nitrogen gas,
for example). Ratio of flow rates of the organometallic compound
gases MO which respectively serves as Mg source and Zn source
is controlled using mass flow controllers MFC or the like,
corresponding to variety in the alloy composition of the individual
layers. Also flow rates of N2O, which is an oxygen component
source gas, and a p-type dopant source gas are controlled by the
mass flow controllers MFC.
The n-type MgZnO layer 54 can be grown by a method in
which oxygen deficiency is intentionally produced so as to attain
n-type conductivity, where it is effective to lower the atmospheric
pressure (lower than 10 Torr (1.3332 kPa), for example) than that
in the cases where the MgZnO active layer 53 and the p-type
MgZnO layer 52 is formed. It is also allowable to form the layer
by separately introducing an n-type dopant. It is still also
allowable to increase ratio of Group II to Group VI elements
(supply II/VI ratio) of the source materials.
For the growth of the MgZnO active layer 53 and p-type
MgZnO layer 52, a unique method capable of suppressing oxygen
deficiency as described in the next is adopted. That is, as
expressed by two patterns (a) and (b) shown in Fig. 5A, the layer
is grown while continuously supplying an oxygen component
source gas (N2O), whereas intermittently interrupting supply of
the organometallic gases, to thereby make use of the time
duration of interrupted supply of the organometallic gases as an
effective duration of the annealing for suppressing generation of
the oxygen deficiency, or for repairing the undesirably generated
oxygen deficiency.
The oxygen deficiency is caused by elimination of oxygen
during the layer growth. To suppress the oxygen deficiency, it is
therefore essential to fully react metal ions (Zn and Mg) derived
from the organometallic gases with oxygen derived from the
oxygen component source gas. Because bond energy between
oxygen and Zn or Mg is relatively large oxygen once bound with
the metals in a stoichiometric manner will become less likely to
be eliminated again. It is, however, considered that oxygen
tends to be eliminated in an intermediate state where the
reaction is not fully completed, and that the layer growth at the
lower temperature region as described in the above is
particularly causative of the oxygen deficiency due to the
incomplete reaction.
It is therefore preferable, as shown in Fig. 7A, to proceed
the layer growth only to an extremely small thickness so as to
prevent the oxygen deficiency from being incorporated deep
inside the layer, and then, as shown in Fig. 7B, to anneal the
layer while interrupting the supply of the organometallic gases
but continuing only the supply of the oxygen component source
gas (N2O), because the reaction between unreacted portions of
the oxygen component source gas and organometallic metal
gases is promoted, and the formation of the oxygen deficiency is
suppressed. Even if the oxygen deficiency should generate, it is
expected that the oxygen component source gas decomposes
and generated oxygen is adsorbed so as to repair the oxygen
deficiency. After completion of the annealing over a duration of
time necessary and sufficient for fully expressing these effects,
the supply of the organometallic compound gas is restarted as
shown in Fig. 7C, to thereby further continue the layer growth.
These processes are repeated thereafter. Fig. 8A shows an
exemplary supply sequence of the organometallic gases (MO)
and the oxygen component source gas. Growth of the MgZnO
active layer 53 and the p-type MgZnO layer 52 can be proceeded
basically in a similar manner, except that the dopant gas is not
supplied for the former, but supplied only for the latter.
In this case, it is necessary that the surface of the layers
during the annealing is kept at a temperature higher by 100°C or
more than the layer growth temperature and lower than the
melting point of the oxide (700°C in this embodiment), in order to
promote decomposition of the oxygen component source gas,
rearrangement of the adsorbed! oxygen for repairing the oxygen
deficiency, and binding reaction with metal ions already
incorporated within the layer. The temperature higher by less
than 100°C than the layer growth temperature may result in only
an insufficient effect of suppressing the oxygen deficiency. On
the other hand, it is self-evident that the temperature exceeding
the melting point of the oxide is nonsense. Because the
annealing temperature is set higher than the substrate
temperature in the layer growth, it is convenient to use a
separate heater specialized for the annealing, besides a heater
for heating the substrate. The separate heater is exemplified by
an infrared lamp in Fig. 5A.
Once the oxygen deficiency is formed in the newly-grown
portion of the layer, it is advantageous to anneal the layer before
the oxygen deficiency is buried in view of smoothly repairing it
under milder conditions. It is therefore effective to set a unit of
the discontinuous (intermittent) layer growth to monoatomic layer
(adjacent oxygen packing layer and metal ion packing layer are
deemed to comprise monoatomic layer) or around. Introduction
period s for the organometallic compound gas is thus set so as to
afford an amount of introduction of the gas necessary for the
growth of the monoatomic layer.
The introduction of the organometallic compound gases
may be effected in a period s" longer than the period s for
forming a complete monoatomic layer as shown in Fig. 9A, or
may be effected in a shorter period s" as shown in Fig. 9B, so far
as it falls within a range from 0.5 atomic layers to 2 atomic layers.
The introduction period s less than 0.5-atomic-layers-equivalent
time may lower the fabrication efficiency, and the exceeding 2-
atomic-layers-equivalent time may reduce the merit of the
intermittent layer growth, because time of annealing for
suppressing the oxygen deficiency becomes too long. The
introduction time s of the organometallic compound gases is,
therefore, preferably set considering the time required for
reaction of oxygen atoms with the metal atoms, and relaxation of
strain in the crystal lattice.
On the other hand, the annealing time needs some
consideration. The reaction per se between the metal atom and
oxygen atom completes within a relatively short time, but an
additional time is substantially necessary for purging of the
organometallic gas out from the reaction vessel in order to
ensure uniform reaction (while actual variation pattern of flow
rate should always show transient periods in which flow rate of
the organometallic gas varies with time, when switched from the
annealing period including the purge-out time, the transient
periods are not illustrated in Figs. 8A to 8C, and Figs. 9A and 9B
for simplicity). Assuming now that the sectional area of the
reaction vessel allowing the gas flow as 20 cm2 as shown in Fig.
5B, a total gas volume as 50 liters/min (converted value for the
standard state), and a length of the heated portion including the
substrate along the gas flow direction as 5.0 cm, a minimum
necessary time for the purging is calculated as 0.002 seconds.
However, the time for purging of 0.002 seconds is practically
insufficient, because it is technically difficult to keep a signal
input/output cycle of a gas sequencer precisely as short as less
than 0.1 seconds, and a stagnation layer is formed in the vicinity
of the inner wall of the reaction vessel and at the heated portion
including the substrate, where the flow rate is slower. It is
therefore preferable to set an interruption time for the
introduction of the organometallic compound as long as 1 second
or more so as to tolerate the mechanical accuracy. Specific
conditions for the annealing typically relate to a nitrogen flow
rate of 10 liters/min (converted value for the standard state), N2O
flow of 1 liter/min (converted value for the standard state), a
layer surface temperature of 700°C, a pressure of 760 Torr
(101.3 kPa), and a retention period for one cycle of 5 to 15
seconds.
It is also allowable to keep supply of a small amount of the
organometallic compound gas during annealing period, as shown
in Fig. 8B, rather than completely interrupting the supply, so far
as the suppressive effect for the oxygen deficiency will not
largely be ruined. It is also allowable to reduce the supply
volume of the oxygen component source gas from the supply
volume during the layer growth as shown in Fig. 8C, because
oxygen during the annealing period is necessary only in an
amount consumed for suppressing or repairing the oxygen
deficiency. It is still also allowable to gradually increase or
decrease the amount of supply of the organometallic compound
gas as shown in Fig. 8D, instead of the step-wise variation
shown in Fig. 8A.
During the layer growth while introducing the
organometallic gases, it is effective to keep pressure in the
reaction vessel at 10 Torr (1.3332 kPa) or above. This is more
successful in suppressing the oxygen elimination, and in growing
the MgZnO layer having a less amount of oxygen deficiency. In
particular for the case where N2O is used as the oxygen
component source, the above-described setting of the pressure
successfully prevents N2O from being rapidly dissociated, and
this makes it possible to more effectively suppress generation of
the oxygen deficiency. The higher the atmospheric pressure
rises, the larger a suppressive effect for the oxygen elimination
becomes, where a pressure of only as high as 760 Torr (1atm, or
101.3 kPa) or around may be sufficient for obtaining the effect.
Adoption of a pressure of 760 Torr (101.3 kPa) or below means
that the reaction vessel is conditioned at normal pressure or
reduced pressure, and this requires only a relatively simple seal
structure of the vessel. On the contrary, adoption of a pressure
exceeding 760 Torr (101.3 kPa) means that the vessel is
pressurized, and this requires a slightly stronger seal structure in
order to prevent leakage of the internal gases, and further
requires a pressure-proof structure or the like for the case where
the pressure is considerably high, where the suppressive effect
for the oxygen elimination becomes more distinctive in anyway.
The upper limit of the pressure in this case should be determined
to an appropriate value considering a balance between the cost
of the apparatus and attainable suppressive effect for the oxygen
elimination (typically 7,600 Torr (10 atm, or 1.013 MPa) or
around).
After completion of the growth of the light emitting layer
portion, a metal reflective layer 22 is formed on the n-type
MgZnO layer 54 as shown in (b) of Fig. 6, the sapphire substrate
10 is separated as shown in (c) of Fig. 6, and a transparent
conductive material layer 25 (e.g., ITO film) is formed on the p-
type MgZnO layer 52. Thereafter as shown in (d) of Fig. 6, the
light emitting device 104 is obtained by dicing. It is also
allowable herein to leave the growth substrate such as sapphire
substrate unseparated, and to use it as a part of the device.
The annealing for suppressing the oxygen deficiency for
the MgZnO active layer 53 and p-type MgZnO layer 52 may
collectively be carried out after the layer growth completed. In
this case, it is also allowable to carry out the annealing after the
substrate is transferred to a separate furnace specialized for
annealing different from the reaction vessel. The annealing is
preferably carried out each time the MgZnO active layer 53 and
p-type MgZnO layer 52 are grown. In view of repairing the
oxygen deficiency incorporated into the layer, the annealing is
preferably carried out at a temperature range slightly higher than
that in the case where the layer growth and annealing are
repeated in an intermittent manner. Specific conditions for the
annealing typically relates to nitrogen flow rate of 10 liters/min
(converted value for the standard state), N2O flow rate of 1
liter/min (converted value for the standard state), a layer surface
temperature of 800°C, a pressure of 760 Torr (101.3 kPa), and an
annealing period of 30 minutes.
The active layer 33 shown in Fig. 1 can also be formed
using a semiconductor capable of forming a Type-ll band lineup
between itself and the p-type MgZnO layer 2. An example of
such active layer 33 is an InGaN layer (referred to as InGaN
active layer, hereinafter). It is to be noted now that "a Type-ll
band lineup is formed between the active layer and the p-type
MgxZn1-xO layer" means a junction structure as shown in Fig. 10A,
in which the individual energy levels of the bottom of the
conduction band and the upper end of the valence band Ecp, Evp
of the p-type cladding layer (p-type MgxZn1-xO layer 2), and the
individual energy levels of the bottom of the conduction band and
the upper end of the valance band Eci, Evi of the active layer
satisfy the following relations of inequality:
Eci > Ecp ••• (3)
Evi > Evp ••• (4)
In this structure, no specific barrier will appear for the
forward diffusion of electrons (n-type carriers) from the active
layer to the p-type cladding layer, but a relatively high potential
barrier is formed for the reverse diffusion of holes (p-type
carriers) from the active layer to the p-type cladding layer. This
promotes carrier recombination in the active layer, and can
achieve high emission efficiency. Assuming now that the layer is
expressed as lnaGa1-aN, where a is an InN alloy composition, a
relation of 0.34=a=0.47 is preferably adopted for blue visible
light emission, and a relation of 0=a=0.19 is preferably adopted
for ultraviolet emission.
In this case, the n-type cladding layer 34 preferably uses a
semiconductor capable of forming a Type-I band lineup between
itself and the active layer. An example of such n-type cladding
layer 34 is an n-type AIGaN (AlpGa1-ßN) layer. It is to be noted
now that "a Type-I band lineup is formed between the n-type
53
cladding layer and the active layer" means a junction structure,
as shown in Fig. 10A, in which the individual energy levels of the
bottom of the conduction band and the upper end of the valence
band Eci, EVi of the active layer, and the individual energy levels
of the bottom of the conduction band and the upper end of the
valance band Ecn, Evn of the n-type cladding layer (n-type AIGaN
layer 4) satisfy the following relations of inequality:
Eci Evi > Evn ••• (6)
In this structure, a relatively high potential barrier is
formed for the reverse diffusion of electrons from the n-type
cladding layer to the active layer, and a well-type potential
barrier is formed at the upper end of the valence band
corresponding to the position of the active layer, to thereby
enhance the confinement effect of holes. All of these promote
carrier recombination in the active layer, and consequently
achieve high emission efficiency.
In the structures shown in Fig. 10A, a suppressive effect of
reverse diffusion of holes from the active layer to the p-type
cladding layer can successfully be raised by increasing the
energy barrier height (Evi - Evp) at the upper end of the valence
band. For this purpose, it is effective to raise MgO alloy
composition of the p-type MgxZ1-xO layer 2 (that is, value of x)
composing the p-type cladding layer. The alloy composition x is
determined depending on desired current density, so as not to
cause excessive leakage of the carriers towards the p-type
cladding layer. In a typical case where the active layer 33 is
composed of an InGaN layer, the alloy composition x is
preferably set within a range from 0.05 to 0.2 or around for light
emitting diode, and 0.1 to 0.4 or around for semiconductor laser
light source.
The bottom of the conductive band descends in a step-wise
manner from the active layer towards the p-type cladding layer,
and the electrons not contributed to the emissive recombination
in the active layer then flow into the p-type cladding layer having
a higher carrier concentration, and become no more contributable
to light emission due to Auger recombination or the like. In order
to raise the emission efficiency, it is therefore necessary that
electrons as much as possible recombine with holes before they
flow into the p-type cladding layer, and it is therefore effective to
increase the thickness t of the active layer to a certain level or
above (e.g., 30 nm or above). As shown in Fig. 10B, too small
thickness t of the active layer increases electrons possibly flow
into the p-type cladding layer and become not contributable to
the light emission, and this results in lowered emission efficiency.
On the other hand, increase in the thickness t of the active layer
beyond a necessary level results in lowered carrier density in the
active layer and thus lowers the emission efficiency. The
thickness is thus typically set to 2 µm or below.
In Fig. 10A, it is advantageous in view of suppressing non-
emissive recombination at the junction boundary that a relation of
Ecp > Evi is satisfied similarly for the case where the InGaN
active layer is used, that is, the p-type cladding layer and the
active layer have forbidden bands which overlap with each other.
(Embodiment 2)
The next paragraphs will describe an embodiment of the
second invention. Since the essential portion of the light
emitting device to which the second invention is applicable is
same as described in Embodiment 1, detailed description will be
omitted (see Figs. 1 to 4, and F:igs. 1 OA and 10B). As shown in
(a) of Fig. 6, the GaN buffer layer 11 is epitaxially grown again
on the sapphire substrate 10, and further thereon the p-type
MgZnO layer 52 (typically of 50 nm thick), the MgZnO active
layer 53 (typically of 30 nm thick) and the n-type MgZnO layer 54
(typically of 50 nm thick) are formed in this order (inverted order
of the growth also acceptable). The epitaxial growth of the
individual layers in this embodiment can be carried out by the
MOVPE process similarly to as described in Embodiment 1,
where differences reside in the following points. More
specifically, in the growth of the MgZnO active layer 53 and p-
type MgZnO layer 52 herein, a ultraviolet lamp (e.g., excimer
ultraviolet lamp) as a ultraviolet light source is disposed
opposing to the main surface of the substrate in order to
suppress the generation of the oxygen deficiency, and the source
gases are supplied between the substrate and ultraviolet light
source while irradiating ultraviolet light from the ultraviolet lamp
towards the main surface of the substrate.
Figs. 11 A and 11 B show an apparatus used for vapor-phase
epitaxy process of the light emitting layer portion using the
ultraviolet lamp based on the MOVPE process.. Similarly to as
described previously referring to Fig. 5A, all of the p-type MgZnO
layer, MgZnO active layer and n-type MgZnO layer can
sequentially be formed in the same reaction vessel using the
same source gases. In this case, it is preferable to proceed the
growth at slightly lower temperatures, typically at 300 to 400°C
so as to reduce the reactivity with the GaN buffer layer and raise
the lattice matching property. The substrate can be heated using
a heater embedded in a susceptor for holding the substrate.
The wall portion of the reaction vessel is configured as a
transparent wall portion composed of a quartz glass or the like,
and the ultraviolet lamp is disposed outside the reaction vessel,
so as to effect the ultraviolet irradiation through the transparent
wall portion towards the substrate. The ultraviolet lamp available
herein has an emission wavelength of approximately 172 nm, and
an output power density of approximately 8 mW/cm2 when the
flow rates of N2O and organometallic compound gas are within a
range from 100 cm3/min to 1,000 cm3/min and 10 cm3/min to 100
cm3/min, respectively.
It is supposed that ultraviolet light irradiated to the
substrate is once absorbed by the substrate, and can highly
activate the outermost portion of the layers under growth based
on the light excitation effect. That is, a highly activated status
similarly to as obtained in the layer growth under high
temperatures can locally be realized in the ouiermost portion of
the layer. Also a part of the source gases is brought into a high-
energy transition status (radical, etc.) by the ultraviolet
irradiation. As a consequence, the organometallic gases and
oxygen component source gas (N2O) can react in the vicinity of
the activated outermost portion of the layer, in a stoichiometric
manner without causing unreacted components or the like, and
the layer growth is promoted in a manner less causative of the
oxygen deficiency.
Radicals of the organometallic gases and oxygen
component source gas are unstable in general, and the radicals
ascribable to these components will be converted into other
decomposition products not contributable to the oxide formation
reaction, if a status in which these radicals are brought into a
close vicinity enough for causing reaction is not realized for a
long duration of time. While this kind of decomposition reaction
is more likely to proceed as temperature of the system elevates,
this can be suppressed to a certain extent typically by lowering
the substrate temperature to as relatively low as 400°C or below.
The ultraviolet irradiation can enhance reaction activity in the
vicinity of the main surface of the substrate, and this makes it
possible to readily form the oxide semiconductor layer having
only a less amount of oxygen deficiency even when the substrate
temperature cannot be raised so high for various reasons.
On the other hand, probability of the oxide formation
reaction contributable to the layer growth is higher in the
boundary layer (in which mass transfer is governed by diffusion,
also referred to as stagnation layer), and lower in an area
outside the boundary layer and having a large gas flow rate. It is
thus understood that the larger the flow rate of the gas flowing
through the reaction vessel grows, the thinner the boundary layer
becomes, and the growth speed of the oxide is depressed.
Adjusting now the flow rate of the source gases supplied between
the substrate and the ultraviolet lamp (ultraviolet light source) so
as to be faster on the ultraviolet light source side than that on
the main surface side as shown in Fig. 11 B, the reaction products
become less likely to deposit on the wall portion of the reaction
vessel in the vicinity of the ultraviolet lamp, and this makes it
possible to avoid a nonconformity such that the deposit shadows
ultraviolet light from the light source to thereby degrade the
reaction efficiency. More specifically, as shown in Fig. 11B, a
gas intake port and a gas discharge port of the reaction vessel
are formed so as to be divided into a first gas intake/discharge
port, and a second gas intake/discharge port, and the flow rate is
adjusted so as to make a gas flow rate ?1 on the first gas
intake/discharge port side is faster than a gas flow rate ?2 on the
second gas intake/discharge port side.
The ultraviolet lamp is advantageous in view of ensuring a
large irradiation area, and of allowing the reaction for the oxide
layer formation to proceed in a uniform and efficient manner. On
the other hand, it is also allowable to irradiate a ultraviolet laser
beam in a two-dimensional scanning manner over the substrate
as shown in Fig. 12. This system can use a light convergence
density larger than that available from the ultraviolet lamp, and
thus further enhance the reaction efficiency, in an exemplary
configuration shown in Fig. 12, a laser light source composed as
an excimer laser light source or a semiconductor laser light
source is scanned in the X direction with the aid of a polygon
mirror, and in synchronization therewith a susceptor holding the
substrate is driven in the Y direction, which crosses the X
direction, with the aid of a Y-scanning table, so as to scan over
the entire portion of the main surface of the substrate with the
laser beam in a two-dimensional manner.
The process steps after completion of the growth of the
light emitting layer portion are same as those described in
Embodiment 1 referring to (b) to (d) of Fig.6.
(Embodiment 3)
The next paragraphs will describe an embodiment of the
third invention. Although the essential portion of the light
emitting device to which the third invention is applicable is
almost the same as described in Embodiment 1 (see Figs. 1 to
5A, and Figs. 10A and 10B), it is essential in the third invention
to form the buffer layer as described below. That is, the buffer
layer has the c-axis of the wurtzite crystal structure oriented to
the thickness-wise direction, has a single metal atom layer as a
metal monoatomic layer formed in contact with the substrate, and
has the residual oxygen atom layers and metal atom layers
alternatively stacked successive to the metal monoatomic layer.
An exemplary fabrication process will be explained below.
First as shown in Fig. 13, a buffer layer 111 composed of
MgZnO is epitaxially grown on the sapphire substrate 10, and
further thereon an n-type MgZnO layer 34 (typically of 50 nm
thick), an MgZnO active layer 33 (typically of 30 nm thick) and a
p-type MgZnO layer 32 (typically of 50 nm thick) are formed in
this order (inverted order of the growth or layers 32 to 35 also
acceptable). These layers can be grown by the MOVPE process.
By the MOVPE process, all of the buffer layer 111, n-type
MgZnO layer 34, MgZnO active layer 33 and p-type MgZnO layer
32 can continuously be formed by the MOVPE process using the
same source materials and in the same reaction vessel as shown
in Figs. 14A to 14C. Temperature in the reaction vessel is
adjusted using a heating source (an infrared lamp in this
embodiment) so as to promote the chemical reactions for the
layer growth. Major source materials for the individual layers
and style of feeding thereof are the same as those described in
Embodiments 1 and 2.
The buffer layer 111 is grown as descried in the next. Fig.
17 shows a control sequence of temperature in the reaction
vessel and introduction of the individual gases in this
embodiment. The substrate 10 on which the layers are grown is
a sapphire (i,e., single crystal alumina) substrate having the c-
axis as the principal crystal axis, where the main surface on the
oxygen-exposed plane side shown in Fig. 15 is used as a layer
growth plane. Prior to the layer growth, the substrate 10 is
thoroughly annealed under an oxidative gas atmosphere. The
oxidative gas may be any of those selected from O2,CO and N2O,
where N2O is selected in this embodiment so as to be used also
as the oxygen component source gas in the layer growth
described later. For the case where the annealing is carried out
in the reaction vessel for the MOVPE process, preferable
conditions for the annealing relate to a temperature of 750°C or
above (but lower than the melting point of the substrate), and an
annealing time of 30 minutes or more. It is, however, also
allowable to shorten the above described annealing time it the
surface of the substrate can be cleaned to a satisfactory level by
wet cleaning or the like.
After completion of the annealing, the substrate
temperature is lowered to a first temperature which is set to 250
to 300oC (set to 350°C herein) as shown in Fig. 17 in order to
suppress generation of the oxygen deficiency, while keeping the
oxidative gas atmosphere After the temperature is stabilized at
a set value, supply of the oxidative gas is interrupted, and the
gas is then thoroughly purged out by replacing the inner
atmosphere of the reaction vessel with nitrogen gas. It is
preferable to set the purging time to 5 seconds or longer,
although variable depending on shape and capacity of the
reaction vessel.
Next, as shown in Figs. 14A and 16A, the organometallic
gas MO is supplied into the reaction vessel, and the first metal
atomic layer which composes a part of the buffer layer 111 is
formed as a monoatomic layer by the ALE process. As previously
explained in the above, growth of the monoatomic layer in the
ALE process saturates once a single atomic layer is completed
based on the self-termination function, and no more growth of the
metal atomic layer would occur even if the supply of the
organometallic compound gas MO is continued.
Thereafter the supply of the organometallic gas MO is
interrupted, the gas is thoroughly purged out by replacing the
inner atmosphere of the reaction vessel with nitrogen gas, and as
shown in Fig. 16C, N2O is introduced as the oxygen component
source gas (and also as a gas for creating the oxidative
atmosphere), and the oxygen atom layer is formed only by a
single atomic layer by the ALE process. This results in the
formation of the MgZnO layer only by a single atomic layer on the
substrate 1 0.
The temperature in the reaction vessel is thereafter
increased to a second temperature which is set to 400 to 800°C
(set to 750°C herein) as shown in Fig. 17 while keeping the
oxidative gas atmosphere, and also keeping the organometallic
gas continuously supplied, so as to form the residual portion of
the buffer layer by the general MOVPE process as shown in Figs.
14B and 16D. In this process, the buffer layer 111 having an
excellent planarity can be obtained by growing the layer at a
speed of 0.1 nm/sec or around until a thickness of 10 nm or
around is attained, and thereafter at a speed of 1 nm/sec. In
view of obtaining the buffer layer excellent both in the
crystailinity and planarity, it is also preferable to grow a plurality
of layers from the first layers by the ALE process.
Although the buffer layer 111 of this embodiment is formed
as a simple oxide layer comprising ZnO, it may also be formed as
a composite oxide layer of MgZnO having an appropriate alloy
composition harmonized with the alloy composition of the
adjacent layer on the light emitting-portion side. The Al atom
layer located just below the outermost oxygen atom layer of the
sapphire substrate comprises, as shown in Fig. 18A, two Al atom
sites AI-1 and AI-2, which differ from each other in the distance
to the oxygen layer. Assuming now that the metal atom layer
formed on the oxygen layer is a Zn atom layer, both sites AI-1
and AI-2 differ in the Coulomb repulsive force between Zn atom
and Al atom located while placing the oxygen layer in between.
For this reason, Zn atoms corresponding to both sites will have
different displacement in the direction normal to the plane of the
oxygen atom layer, and this may causative of irregularity in
stacking of the later-coming layers. To relieve this effect, as
shown in Figs. 18B and 18C, it is effective to form the first single
atomic layer (or a plurality of layers) as a composite oxide layer
which contains Group II atom (e.g., Mg) having a smaller ionic
radius than Zn, or Group II atom (e.g., Ca, Sr, Ba) having a
larger ionic radius by an appropriate ratio, and this can improve
the crystallinity of the light emitting layer portion to be obtained.
It is now also effective, in view of enhancing the above-described
effect, to dispose a compositionr-gradient layer, having metal
cation composition gradated in the thickness-wise direction,
between such composite oxide layer (having a metal cation
composition A) and the cladding layer (having a metal cation
composition B: n-type MgZnO layer 54 herein) formed in contact
with the buffer layer 111, in order to ensure continuity between
both compositions A and B, as shown in Fig. 19A. In an
exemplary case where both of the composite oxide layer and
cladding layer are composed of MgZnO, the composition-gradient
layer can be formed so that composition parameter v varies
continuously between A and B typically as shown in Fig. 19B,
where composition parameter v represents metal cation
composition and is given by v = NMg/(NMg + NZn), where NMg is
molar content of Mg, and NZn is molar content of Zn; A is an
expression of v for the composite oxide layer, and B is that for
the cladding layer.
After the buffer layer 111 is completed, as shown in Fig.
14C, the n-type MgZnO layer 34, MgZnO active layer 33 and p-
type MgZnO layer 32 are formed in this order by the MOVPE
process. These process steps are basically same as those
described in Embodiments 1 and 2.
In this embodiment, after completion of the growth of the
light emitting layer portion, the active layer 33 and the p-type
MgZnO layer 32 are partially removed by photolithography or the
like as shown in Fig. 13, a transparent electrode 125 comprising
indi.um tin oxide (ITO) or the like is formed, a metal electrode 122
is formed on the residual p-type MgZnO layer 32, and the layers
are then diced together with the substrate 10 to thereby produce
the light emitting device 1. It is thus self-evident that the light
emitting device 1 is configured so that the buffer layer 111
composed of MgZnO is formed on the substrate 10, and further
thereon the light emitting layer portion again composed of
MgZnO is formed. Light extraction is therefore available mainly
on the transparent sapphire substrate 10 side.
It is to be noted that the light emitting device can of course
be configured as shown in Fig. 6. In this case, the layers are
formed on the buffer layer 111 in an order inverted from that
shown in Fig. 13, that is, the p-type MgZnO layer 32, MgZnO
active layer 33 and n-type MgZnO layer 34 are formed in this
order. This configuration is advantageous in obtaining the device
having an improved weatherabiility, because a metal layer of
MgZnO composing the light emitting layer portion is exposed only
after the substrate 10 is separated.
(Embodiment-4)-
Fig. 20A and 20B schematically show a stacked structure of
the essential portion of the light emitting device in order to
explain one embodiment of the fourth invention. As shown in Fig.
20A, on a substrate 210, a ZnO buffer layer 211, an n-type
MgZnO-type oxide layer 234, a ZnO-base semiconductor active
layer 233 and a p-type MgZnO-type oxide layer 232 are stacked
by the epitaxial growth process while keeping lattice matching, to
thereby form a double hetero, light emitting layer portion 200.
The ZnO-base semiconductor active \ayer (also simply referred to
as active layer) 233 is composed of a ZnO-base semiconductor
containing Zn as a Group H element, and containing O together
with Se or Te as a Group VI element. Fig. 20A shows the active
layer 233 configured as a single layer, whereas Fig. 20B shows
the active layer 233 having a multi-layered structure in which
sub-layers 237 composed of ZnSe or ZnTe are periodically
inserted in a ZnO main layer 236 while keeping an area width
equivalent to or less than one molecular layer of the active layer
233.
As shown in Fig, 20A, by composing the active layer 233
using a ZnO-base semiconductor containing Se or Te, it is made
possible to introduce Se or Te, which belongs to the same Group

with oxygen, to oxygen-deficient sites, and this is successful in
improving the crystallinity of the active layer 233 and making the
band gap energy thereof well suited to blue-color light emission
as described in the above. On the other hand, as shown in Fig.
20B, by composing the active layer 233 so as to have a multi-
layered structure in which sub-layers 237 composed of ZnSe or
ZnTe are periodically inserted in a ZnO main layer 236, it is made
possible to enhance binding property of thus introduced Se or Te
with the closest Zn. Although Fig. 20B illustrates the sub-layer
237 as having a coverage ratio of 1, it is also allowable to reduce
the coverage ratio to as smaller than 1 in order to prevent se or
Te from being deposited rather than being introduced into the
oxygen-deficient sites. The number ot formation of the sub-
layers 237 can properly be adjusted depending on desired
emission wavelength in the active layer 233.
The substrate 210 shown in the Figs. 20A and 20B may be
such as those used in Embodiments 1 to 3. Although the ZnO
buffer layer 211 can epitaxially be formed by stacking ZnO
crystal, it is also allowable to epitaxially grow either one of ZnS,
ZnSe and ZnTe, and then convert them to obtain the ZnO buffer
layer 211 by annealing under the oxygen-containing atmosphere.
N-type dopant added to the n-type, MgZnO-type oxide layer
234 (also simply referred to as n-type MgZnO layer 234,
hereinafter) and p-type dopant added to the p-type, MgZnO-type
oxide layer 232 (also simply referred to as p-type MgZnO layer
132, hereinafter) may be such as those used in Embodiments 1
o 3.
The epitaxial growth of the individual layers shown in Fig.
!0A can be carried out based on the MOVPE or WBE prccess. it
is to be noted that MBE in the context of this patent specification
nolude not only MBE in a narrow sense in which both of a metal
element component source and a non-metal element component
source are used in solid forms, but also include MOMBE (Metal
Organic Molecular Beam Epitaxy) usmg the metal element
component source in a form of organometallic compound and the
non-metal element component source in a solid form; gas source
MBE using the metal element component source in a solid form
and the non-metal element component in a gas form; and
chemical team epitaxy (CBE) usin9 the metal element component
source in a form of organometalllic compound and the non-metal
element component source in a gas form.
Also the ZnO main layer 236 shown in Fig. 20B can be
formed by the epitaxial growth process similarly to as described
in the above. On the other hand, the sub-layer 237, which is
composed of ZnSe or ZnTe, ami must be adjust to have an
area width equivalent to or less than a single molecular layer of
the active layer 233, can be formed by the ALE (Atomic layer
Epitaxy) process in which a Zn-source gas and Se or Te source
gas, both serve major source materials, are alternatively supplied.
A proper adjustment of flow rates of thus supplied source gases
makes it possible to reduce the coverage ratio of the sub-layer
237 smaller than 1.
Major source materials for the individual layers, except the
Se source and Te source, may be such as those used in the
MOVPE process in Embodiments 1 to 3, and also the basic
process steps are the same as those described in Embodiments
1 to 3. Available Se-source gases include H2Se, and available
Te-source gases include H2Te.
After completion of the growth of the light emitting layer
portion 200, the substrate 210 is lapped and etched, as shown in
Fig. 21, a p-type electrode 223 composed of In and n-type
electrodes 224 composed of Au are respectively formed, the
stack is diced, and the individual electrodes are bonded with Al
wirings, so as to obtain the ZnO-base semiconductor light
emitting device. Light extraction is therefore available mainly on
the p-type MgZnO layer 232 side. In Fig. 21, the light extraction
is, however, not available from the area where the p-type
electrode 223 is formed. It is therefore advantageous to partially
remove the active layer 233 and p-type MgZnO layer 232 by
photolithography or the like as shown in Fig. 22, a transparent
electrode 225 comprising indium tin oxide (ITO) or the like is
formed, a metal electrode 222 is formed on the residual p-type
MgZnO layer 232, and the layers are then diced together with the
sapphire substrate 221 to thereby produce the ZnO-base
semiconductor light emitting device. Light extraction is therefore
available mainly on the transparent sapphire substrate 221 side.

WE CLAIM :
1. A method of fabricating a light emitting device having a light emitting layer portion
which comprises a p-type MgxZn1-xO (where, 0=sx=1) layer, wherein
the p-type MgxZn1-xO layer is grown by a metal organic vapor-phase epitaxy process
while supplying organometallic gases, an oxygen component source gas and a p-type dopant
gas into a reaction vessel, and is annealed during and/or after completion of the growth
thereof in an oxygen-containing atmosphere.
2. A method of fabricating a light emitting device having a light emitting layer portion con-
figured so that an n-type cladding layer, an active layer and a p-type cladding layer com-
posed of a p-type MgxZn1-xO (where, 0=x=1) layer are stacked in this order, comprising:
an n-type cladding layer growing step for growing the n-type cladding layer;
an active layer growing step for growing the active layer; and
a p-type cladding layer growing step for growing the p-type cladding layer by a metal
organic vapor-phase epitaxy process while supplying organometallic gases, an oxygen com-
ponent source gas and a p-type dopant gas into a reaction vessel, and annealing the p-type
cladding layer during and/or after completion of the growth thereof in an oxygen-containing
atmosphere.
3. The method of fabricating a light emitting device as claimed in claim 2, wherein the n-
type cladding layer comprises an n-type MgzZn1-zO (where, 0=z=1) layer, the active layer
comprises MgyZn1-yO (where, 0=yy) layer;
the n-type cladding layer is grown in the n-type cladding layer growing step by
supplying organometallic gases and an oxygen component source gas into the reaction
vessel; and
the active layer growing step is a step for growing the active layer on a substrate by a
metal organic vapor-phase epitaxy process while supplying organometallic gases and an oxy-
gen component source gas into the reaction vessel, and involves a step for annealing the lay-
er during and/or after completion of the growth thereof in an oxygen-containing
atmosphere.

4. The method of fabricating a light emitting device as claimed in claim 1, wherein the
annealing is carried out while interrupting supply of the organometallic gases.
5. The method of fabricating a light emitting device as claimed in claim 1, wherein the
oxygen-containing atmosphere during the annealing is created by introducing the oxygen
component source gas into the reaction vessel.
6. The method of fabricating a light emitting device as claimed in claim 5, wherein the
layer to be annealed is grown while continuously supplying the oxygen component source
gas and intermittently interrupting supply of the organometallic gases, to thereby make use of
the time duration of interrupted supply of the organometallic gases as an effective duration of
the annealing.
7. The method of fabricating a light emitting device as claimed in claim 1, wherein the
oxygen component source gas is supplied in a form of an oxidative compound gas.
8. A method of fabricating a light emitting device having a step of growing a
semiconductor layer for composing a light emitting layer portion in vapor phase by introducing
source gases in a reaction vessel having a substrate disposed therein, and by allowing a
semiconductor material generated based on chemical reactions of the source gases to
deposit on the main surface of the substrate, wherein a vapor-phase epitaxy of the
semiconductor layer is proceeded while irradiating ultraviolet light to the source gases
introduced in the reaction vessel.
9. The method of fabricating a light emitting device as claimed in claim 8, wherein a
ultraviolet light source is disposed so as to oppose with the main surface of the substrate,
and the source gases are supplied between the substrate and the ultraviolet light source
while irradiating ultraviolet light towards the main surface.
10. The method of fabricating a light emitting device as claimed in claim 9, wherein a part
of the wall portion of the reaction vessel opposing to the main surface of the substrate is
configured as a transparent wall portion, the ultraviolet light source is disposed outside the re-
action vessel, and ultraviolet light from the ultraviolet light source is irradiated towards the
main surface through the transparent wall portion.
11. The method of fabricating a light emitting device as claimed in claim 10, wherein flow
rate of the source gases supplied between the substrate and the ultraviolet light source is
graded so as to be faster on the ultraviolet light source side and slower on the main surface
side.
12. The method of fabricating a light emitting device as claimed in any one of claim 8,
wherein a vapor-phase epitaxy is proceeded by a metal organic vapor-phase epitaxy process.
13. The method of fabricating a light emitting device as claimed in claim 12, wherein the
metal organic vapor-phase epitaxy process is proceeded by using organometallic gases and
an oxygen component source gas as the source gases, so as to allow the semiconductor
layer which comprises a metal oxide to grow based on chemical reactions of the
organometallic gases with the oxygen component source gas.
14. The method of fabricating a light emitting device as claimed in claim 13, wherein the
semiconductor layer is MgxZn1-xO (where, 0=x=1) layer.
15. A method of fabricating a light emitting device having a light emitting layer portion com-
posed of an MgaZn1-aO-type (where, 0=a=1) oxide, wherein a buffer layer is formed on a
substrate, the buffer layer having at least an MgaZn1-aO-type oxide layer on the contact side
with the light emitting layer portion, and the light emitting layer portion is grown on the buffer
layer;
the MgaZn1-aO-type oxide layer having wurtzite crystal structure in which metal atom
layers and oxygen atom layers are alternatively stacked in the direction of the c-axis, the
buffer layer being grown so as to orient the c-axis of the wurtzite crystal structure to the
thickness-wise direction, and so as to form a metal atom layer as a metal monoatomic layer
on the substrate by the atomic layer epitaxy, and then to form the residual oxygen atom
layers and the metal atom layers.
16. The method of fabricating a light emitting device as claimed in claim 15, wherein the
atomic layer epitaxy is proceeded in a form of a metal organic vapor-phase epitaxy process in
which organometallic gases and an oxygen component source gas are supplied in a reaction
vessel having the substrate housed therein.
17. The method of fabricating a light emitting device as claimed in claim 15, wherevn the
substrate is an oxide single crystal substrate in which oxygen atoms follow hexagonal atomic
arrangement, and has C-plane of the hexagonal atomic arrangement exposed in the main
surface; and
the entire portion of the buffer layer is formed on the main surface of the oxide single
crystal substrate so as to orient the c-axis of the wurtzite crystal structure to the thickness-
wise direction.
18. The method of fabricating a light emitting device as claimed in claim 17, wherein the
oxide single crystal substrate comprises an oxide having corundum structure, and the buffer
layer is formed on the main surface thereof in which oxygen atoms are exposed.
19. The method of fabricating a light emitting device as claimed in claim 17, wherein the
oxide single crystal substrate is a sapphire substrate.
When a p-type MgxZn1-xO-type layer (2) is grown based on a metal organic
vapor-phase epitaxy process, the p-type MgxZn1-xO-type layer (2) is annealed in an
oxygen-containing atmosphere during and / or after completion of the growth of the p-
type MgxZn1-xO-type layer (2). In addition, a vapor-phase epitaxy process of a
semiconductor layer is proceed while irradiating ultraviolet light to the surface of a
substrate to be grown and source gasses. In addition, when a MgxZn1-xO-type buffer
layer that is oriented so as to align the c-axis thereof to a thickness-wise direction is
formed by an atomic layer epitaxy process, a metal monoatomic layer is grown at first.
In addition, a ZnO-base semiconductor active layer (33) is formed by using a
semiconductor material mainly composed of ZnO containing Se or Te. A light emitting
device is formed by using these techniques.

Documents:

1448-kolnp-2003-granted-abstract.pdf

1448-kolnp-2003-granted-assignment.pdf

1448-kolnp-2003-granted-claims.pdf

1448-kolnp-2003-granted-correspondence.pdf

1448-kolnp-2003-granted-description (complete).pdf

1448-kolnp-2003-granted-drawings.pdf

1448-kolnp-2003-granted-examination report.pdf

1448-kolnp-2003-granted-form 1.pdf

1448-kolnp-2003-granted-form 18.pdf

1448-kolnp-2003-granted-form 3.pdf

1448-kolnp-2003-granted-form 5.pdf

1448-kolnp-2003-granted-letter patent.pdf

1448-kolnp-2003-granted-pa.pdf

1448-kolnp-2003-granted-reply to examination report.pdf

1448-kolnp-2003-granted-specification.pdf


Patent Number 214074
Indian Patent Application Number 01448/KOLNP/2003
PG Journal Number 05/2008
Publication Date 01-Feb-2008
Grant Date 30-Jan-2008
Date of Filing 07-Nov-2003
Name of Patentee SHIN-ETSU HANDOTAI CO,,LTD.
Applicant Address 4-2,MARUNOUCHI 1-CHOME, CHIYODA-KU JAPAN
Inventors:
# Inventor's Name Inventor's Address
1 ISHIZAKI JUN-YA C/0 SHIN ETUSU HANDOTAI CO.,LTD ISOBE R & D CENTER 13-1, ISOBE 2-CHOME ANNAKA-SHI GUNMA JAPAN
PCT International Classification Number B M61
PCT International Application Number PCT/JP02/04127
PCT International Filing date 2002-04-25
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2001-131376 2001-04-27 Japan