U.S. patent application number 15/965014 was filed with the patent office on 2019-01-24 for epitaxial substrate for semiconductor elements, semiconductor element, and manufacturing method for epitaxial substrates for semiconductor elements.
The applicant listed for this patent is NGK INSULATORS, LTD.. Invention is credited to Mikiya ICHIMURA, Yoshitaka KURAOKA, Sota MAEHARA.
Application Number | 20190027359 15/965014 |
Document ID | / |
Family ID | 58662399 |
Filed Date | 2019-01-24 |
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United States Patent
Application |
20190027359 |
Kind Code |
A9 |
ICHIMURA; Mikiya ; et
al. |
January 24, 2019 |
EPITAXIAL SUBSTRATE FOR SEMICONDUCTOR ELEMENTS, SEMICONDUCTOR
ELEMENT, AND MANUFACTURING METHOD FOR EPITAXIAL SUBSTRATES FOR
SEMICONDUCTOR ELEMENTS
Abstract
Provided is an epitaxial substrate for semiconductor elements
which suppresses an occurrence of current collapse. The epitaxial
substrate for the semiconductor elements includes: a
semi-insulating free-standing substrate formed of GaN being doped
with Zn; a buffer layer being adjacent to the free-standing
substrate; a channel layer being adjacent to the buffer layer; and
a barrier layer being provided on an opposite side of the buffer
layer with the channel layer therebetween, wherein the buffer layer
is a diffusion suppressing layer that suppresses diffusion of Zn
from the free-standing substrate into the channel layer.
Inventors: |
ICHIMURA; Mikiya;
(Ichinomiya-shi, JP) ; MAEHARA; Sota; (Nagoya-shi,
JP) ; KURAOKA; Yoshitaka; (Okazaki-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NGK INSULATORS, LTD. |
Nagoya-shi |
|
JP |
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Prior
Publication: |
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Document Identifier |
Publication Date |
|
US 20180247809 A1 |
August 30, 2018 |
|
|
Family ID: |
58662399 |
Appl. No.: |
15/965014 |
Filed: |
April 27, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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PCT/JP2016/079619 |
Oct 5, 2016 |
|
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15965014 |
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62249565 |
Nov 2, 2015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 29/7786 20130101;
H01L 29/7787 20130101; H01L 29/201 20130101; H01L 29/812 20130101;
H01L 29/66462 20130101; H01L 21/205 20130101; C23C 16/34 20130101;
H01L 29/66007 20130101; H01L 21/0254 20130101; H01L 21/02458
20130101; H01L 29/205 20130101; H01L 21/02389 20130101; C30B 29/406
20130101; H01L 29/401 20130101; C23C 16/303 20130101; H01L 21/0262
20130101; H01L 29/207 20130101; H01L 21/0251 20130101; H01L 29/2003
20130101; H01L 29/778 20130101; C30B 19/02 20130101 |
International
Class: |
H01L 21/02 20060101
H01L021/02; C23C 16/34 20060101 C23C016/34; C30B 29/40 20060101
C30B029/40; C30B 19/02 20060101 C30B019/02; H01L 29/20 20060101
H01L029/20; H01L 29/205 20060101 H01L029/205; H01L 29/778 20060101
H01L029/778; H01L 29/66 20060101 H01L029/66 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 14, 2016 |
JP |
2016-005164 |
Claims
1. An epitaxial substrate for semiconductor elements, comprising: a
semi-insulating free-standing substrate formed of GaN being doped
with Zn; a buffer layer being adjacent to said free-standing
substrate and being a group 13 nitride layer that is doped with C
at a concentration equal to or higher than 1.times.10.sup.18
cm.sup.-3 in at least part of said buffer layer in a thickness
direction; a channel layer being adjacent to said buffer layer; and
a barrier layer being provided on an opposite side of said buffer
layer with said channel layer therebetween, wherein said buffer
layer is a diffusion suppressing layer that suppresses diffusion of
Zn from said free-standing substrate into said channel layer, and a
concentration of Zn in said channel layer is equal to or lower than
1.times.10.sup.16 cm.sup.-3.
2. The epitaxial substrate for the semiconductor elements according
to claim 1, wherein said group 13 nitride layer is a GaN layer.
3. The epitaxial substrate for the semiconductor elements according
to claim 1, wherein said group 13 nitride layer is either of a
multi-layered buffer layer, which is formed by laminating two or
more group 13 nitride layers having different compositions, at
least one of said two or more group 13 nitride layers being doped
with C at a concentration of 1.times.10.sup.18 cm.sup.-3 or more,
or a composition gradient buffer layer formed of group 13 nitride
containing two or more group 13 elements each having an existence
ratio being changed in a thickness direction.
4. The epitaxial substrate for the semiconductor elements according
to claim 1, wherein said channel layer is formed of GaN, and said
barrier layer is formed of AlGaN.
5. A semiconductor element, comprising: a semi-insulating
free-standing substrate formed of GaN being doped with Zn; a buffer
layer being adjacent to said free-standing substrate and being a
group 13 nitride layer that is doped with C at a concentration
equal to or higher than 1.times.10.sup.18 cm.sup.-3 in at least
part of said buffer layer in a thickness direction; a channel layer
being adjacent to said buffer layer; a barrier layer being provided
on an opposite side of said buffer layer with said channel layer
therebetween; and a gate electrode, a source electrode, and a drain
electrode being provided on said barrier layer, wherein said buffer
layer is a diffusion suppressing layer that suppresses diffusion of
Zn from said free-standing substrate into said channel layer, and a
concentration of Zn in said channel layer is equal to or lower than
1.times.10.sup.16 cm.sup.-3.
6. The semiconductor element according to claim 5, wherein said
group 13 nitride layer is a GaN layer.
7. The semiconductor element according to claim 5, wherein said
group 13 nitride layer is either of a multi-layered buffer layer,
which is formed by laminating two or more group 13 nitride layers
having different compositions, at least one of said two or more
group 13 nitride layers being doped with C at a concentration of
1.times.10.sup.18 cm.sup.-3 or more, or a composition gradient
buffer layer formed of group 13 nitride containing two or more
group 13 elements each having an existence ratio being changed in a
thickness direction.
8. The semiconductor element according to claim 5, wherein said
channel layer is formed of GaN, and said barrier layer is formed of
AlGaN.
9. A method of manufacturing an epitaxial substrate for
semiconductor elements, comprising: a) a preparation step of
preparing a semi-insulating free-standing substrate formed of GaN
being doped with Zn; b) a buffer layer formation step of forming a
buffer layer to be adjacent to said free-standing substrate; c) a
channel layer formation step of forming a channel layer to be
adjacent to said buffer layer; and d) a barrier layer formation
step of forming a barrier layer in a position opposite to said
buffer layer with said channel layer therebetween, wherein in said
buffer layer formation step, said buffer layer is formed as a
diffusion suppressing layer, which is a group 13 nitride layer that
is doped with C at a concentration equal to or higher than
1.times.10.sup.18 cm.sup.-3 in at least part of said buffer layer
in a thickness direction, that suppresses diffusion of Zn from said
free-standing substrate into said channel layer, so that a
concentration of Zn in said channel layer is equal to or lower than
1.times.10.sup.16 cm.sup.-3.
10. The method of manufacturing the epitaxial substrate for the
semiconductor elements according to claim 9, wherein said group 13
nitride layer is formed of GaN.
11. The method of manufacturing the epitaxial substrate for the
semiconductor elements according to claim 9, wherein said group 13
nitride layer is formed as either of a multi-layered buffer layer
by laminating two or more group 13 nitride layers having different
compositions, at least one of said two or more group 13 nitride
layers being doped with C at a concentration of 1.times.10.sup.18
cm.sup.-3 or more, or a composition gradient buffer layer formed of
group 13 nitride containing two or more group 13 elements each
having an existence ratio being changed in a thickness
direction.
12. The method of manufacturing the epitaxial substrate for the
semiconductor elements according to claim 9, wherein said channel
layer is formed of GaN, and said barrier layer is formed of
AlGaN.
13. The method of manufacturing the epitaxial substrate for the
semiconductor elements according to claim 9, wherein said
free-standing substrate is manufactured by a flux method.
14. The epitaxial substrate for the semiconductor elements
according to claim 2, wherein said channel layer is formed of GaN,
and said barrier layer is formed of AlGaN.
15. The epitaxial substrate for the semiconductor elements
according to claim 3, wherein said channel layer is formed of GaN,
and said barrier layer is formed of AlGaN.
16. The semiconductor element according to claim 6, wherein said
channel layer is formed of GaN, and said barrier layer is formed of
AlGaN.
17. The semiconductor element according to claim 7, wherein said
channel layer is formed of GaN, and said barrier layer is formed of
AlGaN.
18. The method of manufacturing the epitaxial substrate for the
semiconductor elements according to claim 10, wherein said
free-standing substrate is manufactured by a flux method.
19. The method of manufacturing the epitaxial substrate for the
semiconductor elements according to claim 11, wherein said
free-standing substrate is manufactured by a flux method.
20. The method of manufacturing the epitaxial substrate for the
semiconductor elements according to claim 12, wherein said
free-standing substrate is manufactured by a flux method.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation of International Application No.
PCT/JP2016/079619, filed Oct. 5, 2016, which claims the benefit of
U.S. Provisional Application No. 62/249,565, filed Nov. 2, 2015 and
Japanese Application No. 2016-005164, filed Jan. 14, 2016, all of
which are hereby incorporated by reference herein in their
entirety.
TECHNICAL FIELD
[0002] The present invention relates to a semiconductor element,
and particularly to a semiconductor element constituted by using a
free-standing substrate that is made of semi-insulating GaN.
BACKGROUND ART
[0003] Nitride semiconductors, which have direct-transition-type
wide band gap, high breakdown electric field, and high saturation
electron velocity, have been used as light emission devices such as
LED or LD and semiconductor materials for high-frequency/high-power
electronic devices.
[0004] Typical structures of the nitride electronic devices include
high electron mobility transistor (HEMT) structure which is formed
by laminating AlGaN as "a barrier layer" and GaN as "a channel
layer". This structure utilizes a feature that a high concentration
two-dimensional electron gas is generated at an AlGaN/GaN
lamination interface owing to large polarization effects
(spontaneous polarization effect and piezo polarization effect)
inherent in nitride materials.
[0005] The nitride electronic devices are generally manufactured
using different material base substrates such as sapphire, SiC, and
Si which are easily available in a commercial way. However, there
arises a problem that large numbers of defects occurs in a GaN film
which is heteroepitaxially grown on the different material
substrates due to a difference of lattice constant and heat
expansion coefficient between GaN and the different material
substrates.
[0006] In the meanwhile, when the GaN film is homoepitaxially grown
on a GaN substrate, the defect caused by the difference of lattice
constant and heat expansion coefficient described above does not
occur, but the GaN film shows favorable crystalline nature.
[0007] Accordingly, when the nitride HEMT structure is manufactured
on the GaN substrate, mobility of the two-dimensional electron gas
at the AlGaN/GaN lamination interface is enhanced, thus
characteristic improvement of an HEMT element (semiconductor
element) manufactured using the above structure can be
expected.
[0008] However, the GaN substrate manufactured by a hydride vapor
phase epitaxial growth method (HVPE method), which can be
commercially available, generally has an n-type conductivity due to
an oxygen impurity incorporated into a crystal. The conductive GaN
substrate serves as a leakage current pathway between source-drain
electrodes when the HEMT element is driven at high voltage. Thus,
it is preferable to use the semi-insulating GaN substrate to
manufacture the HEMT element.
[0009] It is known to be efficient to perform doping of an element
such as transition metal element (Fe, for example) or group 2
element (Mg, for example) which forms a deep acceptor level in the
GaN crystal to achieve the semi-insulating GaN substrate.
[0010] It is already known that when zinc element (Zn) is adopted
from group 2 element, a high-quality semi-insulating GaN
single-crystal substrate can be achieved (for example, refer to
Patent Document 1). An investigation has been already performed on
diffusion of the Zn element in the GaN crystal, and the diffusion
occurs in a high temperature atmosphere and ease of diffusion
depends on crystallinity of the GaN crystal (for example, refer to
Non-Patent Document 4.) Also known is an aspect that a
high-resistance layer doped with iron (Fe) which is a transition
metal element is formed on a substrate, and an intermediate layer
having a high effect of incorporating Fe is further formed between
the high-resistance layer and an electron transit layer, thereby
preventing Fe being incorporated into the electron transit layer
(for example, refer to Patent Document 2).
[0011] A manufacture of the HEMT structure on the semi-insulating
GaN substrate or a substrate with the semi-insulating GaN film to
evaluate each characteristic has been already performed (for
example, refer to Non-Patent Document 1 to Non-Patent Document
3).
[0012] When the GaN film is epitaxially grown on the
semi-insulating GaN single crystal substrate, which is doped with
the transition metal element or the group 2 element, to form an
epitaxial substrate for the semiconductor elements, there arises a
problem that an acceptor element such as Fe, Mg, and Zn is diffused
in the GaN film and acts as an electron trap in the film, thus
current collapse phenomenon occurs.
PRIOR ART DOCUMENTS
Patent Documents
[0013] Patent Document 1: Japanese Patent No. 5039813 [0014] Patent
Document 2: Japanese Patent Application Laid-Open No.
2013-74211
Non-Patent Documents
[0014] [0015] Non-Patent Document 1: Yoshinori Oshimura, Takayuki
Sugiyama, Kenichiro Takeda, Motoaki Iwaya, Tetsuya Takeuchi,
Satoshi Kamiyama, Isamu Akasaki, and Hiroshi Amano, "AlGaN/GaN
Heterostructure Field-Effect Transistors on Fe-Doped GaN Substrates
with High Breakdown Voltage", Japanese Journal of Applied Physics,
vol. 50 (2011), p.084102-1-p.084102-5. [0016] Non-Patent Document
2: V. Desmaris, M. Rudzinski, N. Rorsman, P. R. Hageman, P. K.
Larsen, H. Zirath, T. C. Rodle, and H. F. F. Jos, "Comparison of
the DC and Microwave Performance of AlGaN/GaN HEMTs Grown on SiC by
MOCVD With Fe-Doped or Unintentionally Doped GaN Buffer Layers",
IEEE Transactions on Electron Devices, Vol. 0.53, No. 9, pp.
2413-2417, September 2006. [0017] Non-Patent Document 3: M. Azize,
Z. Bougrioua, and P. Gibart, "Inhibition of interface pollution in
AlGaN/GaN HEMT structures regrown on semi-insulating GaN
templates", Journal of Crystal Growth, vol. 299 (2007),
p.103-p.108. [0018] Non-Patent Document 4: T. Suzuki, J. Jun, M.
Leszczynski, H. Teisseyre, S. Strite, A. Rockett, A. Pelzmann, M.
Camp, and K. J. Ebeling, "Optical activation and diffusivity of
ion-implanted Zn acceptors in GaN under high-pressure,
high-temperature annealing", Journal of Applied Physics, Vol. 84
(1998), No. 2, pp. 1155-1157.
SUMMARY
[0019] The present invention relates to a semiconductor element,
and particularly to a semiconductor element constituted by using a
free-standing substrate formed of semi-insulating GaN.
[0020] According to the present invention, an epitaxial substrate
for semiconductor elements includes: a semi-insulating
free-standing substrate formed of GaN being doped with Zn; a buffer
layer being adjacent to the free-standing substrate and being a
group 13 nitride layer that is doped with C at a concentration
equal to or higher than 1.times.10.sup.18 cm.sup.-3 in at least
part of said buffer layer in a thickness direction; a channel layer
being adjacent to the buffer layer; and a barrier layer being
provided on an opposite side of the buffer layer with the channel
layer therebetween, wherein the buffer layer is a diffusion
suppressing layer that suppresses diffusion of Zn from the
free-standing substrate into the channel layer, and a concentration
of Zn in said channel layer is equal to or lower than
1.times.10.sup.16 cm.sup.-3.
[0021] According to another aspect of the present invention, a
semiconductor element includes: a semi-insulating free-standing
substrate formed of GaN being doped with Zn; a buffer layer being
adjacent to the free-standing substrate and being a group 13
nitride layer that is doped with C at a concentration equal to or
higher than 1.times.10.sup.18 cm.sup.-3 in at least part of said
buffer layer in a thickness direction; a channel layer being
adjacent to the buffer layer; and a barrier layer being provided on
an opposite side of the buffer layer with the channel layer
therebetween, wherein the buffer layer is a diffusion suppressing
layer that suppresses diffusion of Zn from the free-standing
substrate into the channel layer, and a concentration of Zn in said
channel layer is equal to or lower than 1.times.10.sup.16
cm.sup.-3.
[0022] According to still another aspect of the present invention,
a method of manufacturing an epitaxial substrate for semiconductor
elements includes: a) a preparation step of preparing a
semi-insulating free-standing substrate that is made of GaN being
doped with Zn; b) a buffer layer formation step of forming a buffer
layer to be adjacent to the free-standing substrate; c) a channel
layer formation step of forming a channel layer to be adjacent to
the buffer layer; and d) a barrier layer formation step of forming
a barrier layer in a position opposite to the buffer layer with the
channel layer therebetween, wherein in the buffer layer formation
step, the buffer layer is formed as a diffusion suppressing layer,
which is a group 13 nitride layer that is doped with C at a
concentration equal to or higher than 1.times.10.sup.18 cm.sup.-3
in at least part of said buffer layer in a thickness direction,
that suppresses diffusion of Zn from the free-standing substrate
into the channel layer, so that a concentration of Zn in said
channel layer is equal to or lower than 1.times.10.sup.16
cm.sup.-3.
[0023] According to the present invention, the semiconductor
element in which the current collapse is reduced while using a
semi-insulating GaN free-standing substrate can be achieved.
[0024] Thus, it is an object of the present invention to provide an
epitaxial substrate for semiconductor elements which suppresses an
occurrence of current collapse.
BRIEF DESCRIPTION OF DRAWINGS
[0025] FIG. 1 is a drawing schematically illustrating a
cross-sectional structure of an HEMT element 20.
[0026] FIG. 2 is a drawing illustrating a concentration profile of
Zn element and C element in an epitaxial substrate according to an
Example 1.
[0027] FIG. 3 is an enlarged view in a neighborhood of an interface
between a GaN buffer layer and a GaN substrate in FIG. 2.
[0028] FIG. 4 is a drawing illustrating a concentration profile of
Zn element and C element in an epitaxial substrate according to a
Comparative Example 1.
[0029] FIG. 5 is an enlarged view in a neighborhood of an interface
between a C-doped GaN buffer layer and a GaN substrate in FIG.
4.
[0030] FIG. 6 is a drawing illustrating a concentration profile of
Zn element and C element from a surface of a barrier layer 4 in a
depth direction in an Example 7.
[0031] FIG. 7 is a drawing illustrating a concentration profile of
Zn element and C element from a surface of a barrier layer 4 in a
depth direction and a secondary ion signal profile of Al element in
an Example 8.
DESCRIPTION OF EMBODIMENT(S)
[0032] Group numbers of a periodic table in the present
specification are according to the explanation of group numbers 1
to 18 in the nomenclature of inorganic chemistry revised in 1989 by
the international union of pure applied chemistry (IUPAC). Group 13
refers to, for example, aluminum (Al), gallium (Ga), and indium
(In), group 14 refers to, for example, silicon (Si), germanium
(Ge), tin (Sn), and lead (Pb), and group 15 refers to, for example,
nitrogen (N), phosphorous (P), arsenic (As), and antimony (Sb).
[0033] <Summary of Epitaxial Substrate and HEMT Element>
[0034] FIG. 1 is a drawing schematically illustrating a
cross-sectional structure of an HEMT element 20 as one embodiment
of a semiconductor element according to the present invention,
which includes an epitaxial substrate 10 as one embodiment of an
epitaxial substrate for semiconductor elements according to the
present invention.
[0035] The epitaxial substrate 10 includes a free-standing
substrate 1, a buffer layer 2, a channel layer 3, and a barrier
layer 4. The HEMT device 20 comprises a source electrode 5, a drain
electrode 6, and a gate electrode 7 disposed on the epitaxial
substrate 10 (on the barrier layer 4). The ratios of the respective
layers in FIG. 1 do not reflect the actual ones.
[0036] The free-standing substrate 1 is a GaN substrate which is
doped with 1.times.10.sup.18 cm.sup.-3 or more of Zn and has a
(0001) plane orientation, and has a resistivity of 1.times.10.sup.2
.OMEGA.cm or more at room temperature and has semi-insulation
properties. Although a size of the free-standing substrate 1 is not
particularly limited, the free-standing substrate 1 preferably has
a thickness of approximately several hundreds of .mu.m to several
mm in consideration of, for example, ease of handling (grasping and
movement, for example). The free-standing substrate 1 can be
manufactured by a flux method, for example.
[0037] The free-standing substrate 1 formed by the flux method is
obtained by the following processes briefly of: immersing a seed
substrate in a melt containing metal Ga, metal Na, metal Zn, and C
(carbon) in a growing vessel (alumina crucible) disposed to be
horizontally rotatable in a pressure vessel; keeping a
predetermined temperature and a predetermined pressure in the
growing vessel with introducing nitrogen gas, while horizontally
rotating the growing vessel; and then separating a GaN single
crystal, which is resultantly formed on the seed substrate from the
seed substrate. A so-called template substrate in which a GaN thin
film is formed on a sapphire substrate by a MOCVD method can be
preferably used as the seed substrate.
[0038] The buffer layer 2 is a layer having a thickness of
approximately 50 to 1000 nm, (adjacently) formed on one main
surface of the free-standing substrate 1. In the present
embodiment, the buffer layer 2 is formed at a temperature
substantially the same as a formation temperature of the channel
layer 3 and the barrier layer 4, differing from a so-called
low-temperature buffer layer formed at a low temperature lower than
800.degree. C.
[0039] In the epitaxial substrate 10 according to the present
embodiment, the buffer layer 2 is provided as a diffusion
suppressing layer to suppress diffusion of Zn, with which the
free-standing substrate 1 is doped, into the channel layer 3 and
further into the barrier layer 4 on the channel layer 3 at a time
of manufacturing the epitaxial substrate 10. The buffer layer 2, as
a preferred example, is constituted by a layer formed of group 13
nitride containing C doped at a concentration of 1.times.10.sup.18
cm.sup.-3 or more in at least a part of a range in the thickness
direction.
[0040] In the above case, the buffer layer 2 may be a single layer,
which is wholly formed of group 13 nitride containing C doped at
the concentration of 1.times.10.sup.18 cm.sup.-3 or more, or may
have a configuration that at least one layer of a multi-layered
buffer layer, which is formed of two or more group 13 nitride
layers having different compositions, contains the doped C at the
concentration of 1.times.10.sup.18 cm.sup.-3 or more. Examples of
the single layer include, for example, a GaN buffer layer (C-doped
GaN layer) which is wholly made of GaN. Examples of the
multi-layered buffer layer include, for example, a configuration
that a C-doped GaN layer is laminated on a Al.sub.aGa.sub.1-aN
layer (0<a.ltoreq.1). Alternatively, the buffer layer 2 may be
provided by doping C at the concentration of 1.times.10.sup.18
cm.sup.-3 or more in a range of at least a part of a composition
gradient buffer layer, in the thickness direction, which is formed
of group 13 nitride containing two or more group 13 elements (for
example, Ga and Al), each element having an existence ratio (mole
fraction) changed in the thickness direction. An effect brought
about by the buffer layer 2 is described hereinafter.
[0041] Also applicable is an aspect that the buffer layer 2 is
constituted by a layer formed of an Al-doped GaN (Al-doped GaN
layer) or a layer made of AlN. Each of these layers also functions
as a diffusion suppressing layer in a manner similar to the C-doped
GaN layer.
[0042] The channel layer 3 is a layer (adjacently) formed on the
buffer layer 2. The channel layer 3 is formed to have a thickness
of approximately 50 to 5000 nm. The barrier layer 4 is a layer
provided on an opposite side of the buffer layer 2 with the channel
layer 3 therebetween. The barrier layer 4 is formed to have a
thickness of approximately 2 to 40 nm.
[0043] The barrier layer 4 may be formed adjacent to the channel
layer 3 as illustrated in FIG. 1, and in this case, an interface
therebetween is a hetero junction interface. Alternatively, a
spacer layer not shown may be provided between the channel layer 3
and the barrier layer 4, and in this case, a region from an
interface between the channel layer 3 and the spacer layer and an
interface between the barrier layer 4 and the spacer layer is a
hetero junction interface region.
[0044] In any case, as a preferred example, the channel layer 3 is
made of GaN, and the barrier layer 4 is made of AlGaN
(Al.sub.xGa.sub.1-xN, 0<x<1) or InAlN 0<y<1). However,
a combination of the channel layer 3 and the barrier layer 4 is not
limited thereto.
[0045] A formation of the buffer layer 2, the channel layer 3, and
the barrier layer 4 is achieved by the MOCVD method, for example.
In a case where the buffer layer 2 and the channel layer 3 are
formed of GaN and the barrier layer 4 is formed of AlGaN, for
example, the layer formation by the MOCVD method can be performed,
using a publicly known MOCVD furnace capable of supplying organic
metal (MO) source gas for Ga and Al (TMG and TMA), ammonia gas,
hydrogen gas, and nitrogen gas into a reactor, by heating the
free-standing substrate 1 disposed in the reactor to a
predetermined temperature and depositing a GaN crystal and an AlGaN
crystal generated by a gas phase reaction between the organic metal
source gas corresponding to each layer and the ammonia gas on the
free-standing substrate 1 in sequence.
[0046] The source electrode 5 and the drain electrode 6 are metal
electrodes each having a thickness of approximately ten and several
nm to a hundred and several tens of nm. The source electrode 5 and
the drain electrode 6 are preferably formed as multi-layered
electrodes of, for example, Ti/Al/Ni/Au. The source electrode 5 and
the drain electrode 6 have ohmic contact with the barrier layer 4.
The source electrode 5 and the drain electrode 6, as a preferred
example, are formed by a vacuum evaporation method and a
photolithography process. It is preferable to perform a thermal
treatment for several tens of seconds in nitrogen gas atmosphere at
a predetermined temperature of 650 to 1000.degree. C. after forming
the electrodes 5 and 6 to enhance the ohmic contact of those
electrodes.
[0047] The gate electrode 7 is a metal electrode having a thickness
of approximately ten and several nm to a hundred and several tens
of nm. The gate electrode 7 is preferably formed as a multi-layered
electrode of, for example, Ni/Au. The gate electrode 7 has Schottky
contact with the barrier layer 4. The gate electrode 7, as a
preferred example, is formed by a vacuum evaporation method and a
photolithography process.
<Method of Manufacturing Epitaxial Substrate and HEMT
Element>
[0048] (Manufacture of Free-Standing Substrate)
[0049] A procedure of manufacturing the free-standing substrate 1
by the flux method is firstly described.
[0050] Firstly, a c-plane sapphire substrate having a diameter
substantially the same as that of the free-standing substrate 1 to
be manufactured is prepared, and a GaN low-temperature buffer layer
is formed on a surface of the c-plane sapphire substrate to have a
thickness of approximately 10 to 50 nm at a temperature of 450 to
750.degree. C. Subsequently, a GaN thin film having a thickness of
approximately 1 to 10 .mu.m is formed by the MOCVD method at a
temperature of 1000 to 1200.degree. C., thereby obtaining a
MOCVD-GaN template usable as a seed substrate.
[0051] Next, a Zn-doped GaN single crystal layer is formed by a Na
flux method using the MOCVD-GaN template which has been obtained as
the seed substrate.
[0052] Specifically, the MOCVD-GaN template is firstly disposed in
an alumina crucible, and subsequently, the alumina crucible is
filled with 10 to 60 g of metal Ga, 15 to 90 g of metal Na, 0.1 to
5 g of metal Zn, and 10 to 500 mg of C.
[0053] The alumina crucible is put in a heating furnace and heated
for approximately 20 to 400 hours with a furnace temperature of 800
to 950.degree. C. and a furnace pressure of 3 to 5 MPa, and
subsequently cooled to room temperature. After finishing cooling,
the alumina crucible is taken out of the furnace. As a result of
the above procedure, a brown GaN single crystal layer with a
thickness of 300 to 3000 .mu.m is deposited on the surface of the
MOCVD-GaN template.
[0054] The GaN single crystal layer which has been obtained in such
a manner is ground with diamond abrasive grains to planarize a
surface thereof. The Flux-GaN template having the GaN single
crystal layer formed on the MOCVD-GaN template is thereby obtained.
However, the grinding is performed to the extent that a total
thickness of a nitride layer on the Flux-GaN template is
sufficiently kept larger than a targeted thickness of the
free-standing substrate 1 to be obtained eventually.
[0055] Subsequently, by a laser lift-off method in which laser
light is emitted from a side of the seed substrate to perform
scanning at a scan speed of 0.1 to 100 mm/sec., the seed substrate
is separated from the Flux-GaN template. Third harmonic of Nd: YAG
having a wavelength of 355 nm, for example, is preferably used as
the laser light. In the above case, a pulse width may be set to
approximately 1 to 1000 ns and a pulse period may be set to
approximately 1 to 200 kHz. In emitting the laser light, it is
preferable to appropriately collect the laser light to adjust light
density. It is preferable to emit the laser light while heating the
Flux-GaN template from a side opposite to the seed substrate at a
temperature of approximately 30 to 600.degree. C.
[0056] After separating the seed substrate, a grinding processing
is performed on a surface, from which the seed substrate has been
detached, of a laminated structure which has been obtained. The
free-standing substrate 1 formed of GaN containing Zn doped at a
concentration of 1.times.10.sup.18 cm.sup.-3 or more is thereby
obtained.
[0057] (Manufacture of Epitaxial Substrate)
[0058] Subsequently, a manufacture of the epitaxial substrate 10 by
the MOCVD method is described. The epitaxial substrate 10 is
obtained by laminating the buffer layer 2, the channel layer 3, and
the barrier layer 4 in this order under the following condition in
a state where the free-standing substrate 1 is disposed on a
susceptor provided in the reactor in the MOCVD furnace. However,
described as an example of the buffer layer 2 is a case where a
single GaN buffer layer or a multi-layered buffer layer or a
composition gradient buffer layer containing Ga and Al as group 13
element is formed. The formation temperature means a susceptor
heating temperature.
[0059] In the present embodiment, a gas ratio of group 15 to group
13 is a ratio (molar ratio) of a supply amount of ammonia, which is
a group 15 (N) source, to a total supply amount of trimethylgallium
(TMG), trimethylaluminum (TMA), and trimethylindium (TMI), which
are group 13 (Ga, Al, and In) sources. A gas ratio of Al source gas
to group 13 source gas in a case of making the barrier layer 4 of
AlGaN is a ratio (molar ratio) of a supply amount of Al source to a
supply amount of whole group 13 (Ga, Al) sources, and a gas ratio
of In source gas to group 13 source gas in a case of making the
barrier layer 4 of InAlN is a ratio (molar ratio) of a supply
amount of In source to a supply amount of whole group 13 (In, Al)
sources. Both are defined in accordance with a composition (an Al
molar ratio x or an In composition ratio y) of a desired barrier
layer 4.
[0060] Buffer layer 2:
[0061] Formation temperature=900 to 1100.degree. C.;
[0062] Reactor pressure=5 to 30 kPa;
[0063] Carrier gas=hydrogen;
[0064] Gas ratio of group 15 to group 13=100 to 4000;
[0065] Gas ratio of Al source gas to group 13 source gas=0 (in a
case of the GaN buffer layer);
[0066] Gas ratio of Al source gas to group 13 source gas=ranging
from 0 to 1 in accordance with a position in the thickness
direction (in a case of the multi-layered buffer layer or the
composition gradient buffer layer).
[0067] Channel layer 3:
[0068] Formation temperature=1000 to 1200.degree. C.;
[0069] Reactor pressure=15 to 105 kPa;
[0070] Carrier gas=hydrogen;
[0071] Gas ratio of group 15 to group 13=1000 to 10000.
[0072] Barrier layer 4 (in a case of being made of AlGaN):
[0073] Formation temperature=1000 to 1200.degree. C.;
[0074] Reactor pressure=1 to 30 kPa;
[0075] Gas ratio of group 15 to group 13=5000 to 20000;
[0076] Carrier gas=hydrogen;
[0077] Gas ratio of Al source gas to group 13 source gas=0.1 to
0.4.
[0078] Barrier layer 4 (in a case of being made of InAlN):
[0079] Formation temperature=700 to 900.degree. C.;
[0080] Reactor pressure=1 to 30 kPa;
[0081] Gas ratio of group 15 to group 13=2000 to 20000;
[0082] Carrier gas=nitrogen;
[0083] Gas ratio of In source gas to group 13 source gas=0.1 to
0.9.
[0084] (Manufacture of HEMT Element)
[0085] The HEMT element 20 using the epitaxial substrate 10 can be
manufactured by applying a publicly known technique.
[0086] For example, after an element separation processing of
removing a portion of a boundary between individual elements by
performing etching to approximately 50 to 1000 nm, using a
photolithography process and a RIE (reactive ion etching) method,
an SiO.sub.2 film having a thickness of 50 to 500 nm is formed on a
surface of the epitaxial substrate 10 (the surface of the barrier
layer 4), and then the SiO.sub.2 film at locations where the source
electrode 5 and the drain electrode 6 are to be formed is removed
by etching using the photolithography process, thereby obtaining an
SiO.sub.2 pattern layer.
[0087] Next, a metal pattern of Ti/Al/Ni/Au is formed at the
locations where the source electrode 5 and the drain electrode 6
are to be formed by the vacuum deposition method and the
photolithography process, thereby forming the source electrode 5
and the drain electrode 6. The metal layers preferably have
thicknesses of 5 to 50 nm, 40 to 400 nm, 4 to 40 nm, and 20 to 200
nm in this order, respectively.
[0088] Subsequently, a thermal treatment is performed for 10 to
1000 seconds in nitrogen gas atmosphere at a temperature of 600 to
1000.degree. C. to improve the ohmic contact of the source
electrode 5 and the drain electrode 6.
[0089] Then, the SiO.sub.2 film at locations where the gate
electrode 7 is to be formed is removed from the SiO.sub.2 pattern
layer using the photolithography process.
[0090] Furthermore, a Schottky metal pattern of Ni/Au is formed at
the locations where the gate electrode 7 is to be formed by the
vacuum deposition method and the photolithography process, thereby
forming the gate electrode 7. The metal layers preferably have
thicknesses of 4 to 40 nm and 20 to 200 nm, respectively.
[0091] The HEMT element 20 is obtained by the processes described
above.
[0092] (Effect of Buffer Layer)
[0093] As described above, in the HEMT element 20 according to the
present embodiment, the free-standing substrate 1 is formed of GaN
containing Zn doped at the concentration of 1.times.10.sup.18
cm.sup.-3 or more, and the buffer layer 2 is provided to function
as the diffusion suppressing layer to suppress the diffusion of Zn
from the free-standing substrate 1 into the channel layer 3 at the
time of manufacturing the epitaxial substrate 10. Illustrated as an
example of the buffer layer 2 is the layer formed of group 13
nitride containing C doped at the concentration of
1.times.10.sup.18 cm.sup.-3 or more in at least the part of the
range in the thickness direction.
[0094] If the buffer layer 2 is not doped with C under the
concentration condition described above, Zn is diffused from the
buffer layer 2 into the channel layer 3 and further into the
barrier layer 4. In the above case, since Zn functioning as the
acceptor element acts as an electric trap, a current collapse
phenomenon occurs in the HEMT element 20.
[0095] However, in the HEMT element 20 according to the present
embodiment, the occurrence of the current collapse is preferably
suppressed as a result of preferably suppressing the diffusion of
Zn from the free-standing substrate 1 by making the buffer layer 2
of the group 13 nitride layer containing C doped under the
concentration condition described above. More specifically, when
the concentration of Zn in the channel layer is 1.times.10.sup.16
cm.sup.-3 or less, the occurrence of the current collapse is
preferably suppressed in the HEMT element 20.
[0096] The doping of C at the concentration of 1.times.10.sup.18
cm.sup.-3 or more in at least part of the buffer layer 2 in the
thickness direction is based on a fact that the concentration of C
can be changed by appropriately adjusting a formation condition of
the group 13 nitride layer such as the growth temperature, the
reactor pressure, the gas ratio of group 15 to group 13, and the
formation thickness, for example, at the time of forming the group
13 nitride layer by the MOCVD method. C with which the crystal
layer formed by the MOCVD method is doped mainly derives from the
group 13 source, and for example, the supply amount of C changes
with the supply amount of group 13 gas, and stability of C element
in the group 13 nitride crystal is influenced by temperature and
pressure.
[0097] Thus, when the HEMT element 20 according to the present
embodiment is obtained, used in the formation of the buffer layer 2
is the growth condition that the doping of Cat the concentration of
1.times.10.sup.18 cm.sup.-3 or more is performed in at least the
part of the range in the thickness direction, and used in the
formation of the channel layer 3 is the growth condition that such
doping is not performed, for example, the growth condition that the
concentration of C in the channel layer 3 is lower than that of the
buffer layer 2 by two orders or three orders or more of
magnitude.
[0098] As described above, according to the present embodiment, the
semiconductor element capable of suppressing the occurrence of the
current collapse can be obtained while using the semi-insulating
GaN free-standing substrate.
EXAMPLES
Example 1
[0099] (Manufacture of Zn-Doped GaN Single Crystal Substrate by
Flux Method)
[0100] A GaN low-temperature buffer layer is formed to have a
thickness of 30 nm at a temperature of 550.degree. C. on a surface
of a c-plane sapphire substrate having a diameter of 2 inches and a
thickness of 0.43 mm, and subsequently, a GaN thin film having a
thickness of 3 .mu.m is formed by the MOCVD method at a temperature
of 1050.degree. C., thereby obtaining a MOCVD-GaN template usable
as a seed substrate.
[0101] A Zn-doped GaN single crystal layer is formed by the Na flux
method using the MOCVD-GaN template which has been obtained as the
seed substrate.
[0102] Specifically, the MOCVD-GaN template was firstly disposed in
an alumina crucible, and subsequently, the alumina crucible was
filled with 30 g of metal Ga, 45 g of metal Na, 1 g of metal Zn,
and 100 mg of C. The alumina crucible was put in a heating furnace
and heated for approximately 100 hours with a furnace temperature
of 850.degree. C. and a furnace pressure of 4.5 MPa, and
subsequently cooled to room temperature. When the alumina crucible
was taken out of the furnace after finishing cooling, a brown GaN
single crystal layer was deposited on the surface of the MOCVD-GaN
template with a thickness of approximately 1000 .mu.m.
[0103] The GaN single crystal layer which had been obtained in such
a manner was ground with diamond abrasive grains so that the
surface thereof was planarized and the nitride layer formed on a
base substrate had a total thickness of 900 .mu.m. The Flux-GaN
template having the GaN single crystal layer formed on the
MOCVD-GaN template was thereby obtained. When the Flux-GaN template
was viewed with naked eyes, no crack was found thereon.
[0104] Subsequently, by a laser lift-off method in which laser
light was emitted from a side of the seed substrate to perform
scanning at a scan speed of 30 mm/sec., the seed substrate was
separated from the Flux-GaN template. Third harmonic of Nd: YAG
having a wavelength of 355 nm was used as the laser light. A pulse
width was set to approximately 30 ns and a pulse period was set to
approximately 50 kHz. In emitting the laser light, the laser light
was collected to have a circular shape with a diameter of
approximately 20 .mu.m, thereby having light density of
approximately 1.0 J/cm. The laser light was emitted while heating
the Flux-GaN template from a side opposite to the seed substrate at
a temperature of around 50.degree. C.
[0105] After separating the seed substrate, a grinding processing
was performed on a surface, from which the seed substrate had been
detached, of a laminated structure which had been obtained, thereby
obtaining a Zn-doped GaN free-standing substrate having a total
thickness of 430 .mu.m.
[0106] Crystallinity of the Zn-doped GaN substrate which had been
obtained was evaluated with X-ray rocking curve. A half-value width
of (0002) plane reflection was 120 seconds and a half-value width
of (10-12) plane reflection was 150 seconds, both showing favorable
crystalline nature.
[0107] (Manufacture of Epitaxial Substrate by MOCVD Method)
[0108] Subsequently, an epitaxial substrate was manufactured by the
MOCVD method. Specifically, a GaN layer as a buffer layer, a GaN
layer as a channel layer, and an AlGaN layer as a barrier layer
were laminated on the Zn-doped GaN substrate described above in
this order under the following condition. In the present Example, a
gas ratio of group 15 to group 13 is a ratio (molar ratio) of a
supply amount of a group 15 (N) source to a supply amount of group
13 (Ga, Al) sources. The condition for forming the GaN buffer layer
is a condition that it is confirmed in advance that the doping of C
at a high concentration is implemented, and the condition for
forming the GaN channel layer is a condition that it is confirmed
in advance that the doping of C is hardly performed.
[0109] GaN buffer layer:
[0110] Formation temperature=1050.degree. C.;
[0111] Reactor pressure=10 kPa;
[0112] Gas ratio of group 15 to group 13=500;
[0113] Thickness=1000 nm.
[0114] GaN channel layer:
[0115] Formation temperature=1050.degree. C.;
[0116] Reactor pressure=100 kPa;
[0117] Gas ratio of group 15 to group 13=2000;
[0118] Thickness=1000 nm.
[0119] AlGaN barrier layer:
[0120] Formation temperature=1050.degree. C.;
[0121] Reactor pressure=5 kPa;
[0122] Gas ratio of group 15 to group 13=12000;
[0123] Gas ratio of Al source gas to group 13 gas=0.25;
[0124] Thickness=25 nm.
[0125] After the formation of the layers described above, the
susceptor temperature was lowered to around room temperature, and
the internal gas of the reactor was returned to atmospheric
pressure. Then, the epitaxial substrate which had been manufactured
was taken out.
[0126] (Manufacture of HEMT Element)
[0127] Subsequently, the HEMT element 20 was manufactured using the
epitaxial substrate 10. The HEMT element was designed to have a
gate width of 100 .mu.m, a source-gate distance of 1 .mu.m, a
gate-drain distance of 4 .mu.m, and a gate length of 1 .mu.m.
[0128] Firstly, a portion of a boundary between individual elements
was removed by etching to a depth of approximately 100 nm using the
photolithography process and the RIE method.
[0129] Next, the SiO.sub.2 film having a thickness of 100 nm was
formed on the epitaxial substrate, and then the SiO.sub.2 film at
locations where the source electrode and the drain electrode were
to be formed was removed by etching using the photolithography
process, thereby obtaining an SiO.sub.2 pattern layer.
[0130] Next, a metal pattern of Ti/Al/Ni/Au (each having a film
thickness of 25/200/20/100 nm) was formed at the locations where
the source electrode and the drain electrode were to be formed by
the vacuum deposition method and the photolithography process,
thereby forming the source electrode and the drain electrode.
Subsequently, a thermal treatment was performed for 30 seconds in
nitrogen gas atmosphere at a temperature of 825.degree. C. to
improve the ohmic contact of the source electrode and the drain
electrode.
[0131] Then, the SiO.sub.2 film at locations where the gate
electrode was to be formed was removed from the SiO.sub.2 pattern
layer using the photolithography process.
[0132] Furthermore, a Schottky metal pattern of Ni/Au (each having
a film thickness of 20/100 nm) was formed at the locations where
the gate electrode was to be formed by the vacuum deposition method
and the photolithography process, thereby forming the gate
electrode.
[0133] The HEMT element was obtained by the processes described
above.
[0134] (SIMS Evaluation of HEMT Element)
[0135] An element analysis in the depth direction was performed on
the epitaxial substrate of the HEMT element, which had been
obtained, by secondary ion mass spectrometry (SIMS), and each
concentration of the Zn element and the C element was examined.
[0136] FIG. 2 is a drawing illustrating a concentration profile of
the Zn element and the C element in the epitaxial substrate
according to the present Example. FIG. 3 is an enlarged view in a
neighborhood of an interface between the GaN buffer layer and the
GaN substrate in FIG. 2. Results illustrated in FIG. 2 and FIG. 3
show the following matters.
[0137] (1) The GaN substrate is doped with the Zn element at a high
concentration (3.times.10.sup.18 cm.sup.-3).
[0138] (2) Since the concentration of the C element is equal to or
higher than 6.times.10.sup.18 cm.sup.-3 in the GaN buffer layer,
the GaN buffer layer includes a region which contains the C element
at a concentration equal to or higher than 1.times.10.sup.18
cm.sup.-3, and the concentration of the C element is equal to or
lower than approximately 1.times.10.sup.16 cm.sup.-3 in the channel
layer.
[0139] (3) The concentration of the Zn element, which is high in a
portion from the interface between the GaN buffer layer and the GaN
substrate toward a side of the substrate, sharply decreases in the
GaN buffer layer, and reaches to 5.times.10.sup.14 cm.sup.-3 which
is a lower detection limit value of Zn in the measurement by the
secondary ion mass spectrometry (SIMS). That is to say, the
diffusion of the Zn element in the channel layer and the barrier
layer is suppressed.
[0140] (4) A logarithm change ratio of the Zn concentration per
.mu.m (a change ratio of a common logarithm value of the
concentration) in a portion where the Zn concentration is
1.times.10.sup.17 cm.sup.-3 is -74.9.
[0141] (Electrical characteristics evaluation of HEMT element)
[0142] Drain current-drain voltage characteristics (Id-Vd
characteristics) of the HEMT element were evaluated in a DC mode
and a pulse mode (static drain bias Vdq=30V, static gate bias
Vgq=-5V) using a semiconductor parameter analyzer. A pinch-off
threshold voltage was Vg=-3V.
[0143] Adopted as an index for evaluating the current collapse was
a ratio R of the drain current Id.sub.pulseVd=5VVg=2V in the pulse
mode to the drain current Id.sub.DCVd=5VVg=2V in the DC mode in a
case of applying the drain voltage Vd=5V and the gate voltage Vg=2V
(=Id.sub.pulseVd=5VVg=2V/Id.sub.DCVd=5VVg=2V, 0.ltoreq.R.ltoreq.1).
The ratio R was calculated to be 0.93 in the case of the HEMT
element according to the present Example. When the value R is equal
to or larger than 0.7, it can be determined that the current
collapse is small, thus it is determined that the current collapse
is small in the HEMT element according to the present Example.
Comparative Example 1
[0144] The HEMT element was manufactured under the condition
similar to that of the Example 1 except that the growth condition
of the GaN buffer layer was as follows, differing from the Example
1. The condition for forming the GaN buffer layer is a condition
that it is confirmed in advance that an amount of doped C is small
compared with the Example 1.
[0145] GaN buffer layer:
[0146] Formation temperature=1050.degree. C.;
[0147] Reactor pressure=30 kPa;
[0148] Gas ratio of group 15 to group 13=500;
[0149] Thickness=300 nm.
[0150] The SIMS measurement was performed on the HEMT element,
which had been obtained, in the manner similar to the Example 1,
and each concentration of the Zn element and the C element in the
epitaxial substrate was examined.
[0151] FIG. 4 is a drawing illustrating a concentration profile of
the Zn element and the C element in the epitaxial substrate
according to the present Comparative Example. FIG. 5 is an enlarged
view in a neighborhood of an interface between the C-doped GaN
buffer layer and the GaN substrate in FIG. 4. Results illustrated
in FIG. 4 and FIG. 5 show the following state.
[0152] (1) The GaN substrate is doped with the Zn element at a high
concentration in the manner similar to the Example 1.
[0153] (2) The concentration of the C element is equal to or higher
than approximately 2.times.10.sup.17 cm.sup.-3 at a maximum in the
GaN buffer layer, that is higher than that in another regions but
is lower than that in the Example 1, and the concentration of the C
element in the GaN channel layer formed under the same condition as
the Example 1 is approximately 4.times.10.sup.16 cm.sup.-3, that is
higher than that in the Example 1.
[0154] (3) The concentration of the Zn element, which is high in
the portion from the interface between the GaN buffer layer and the
GaN substrate toward the side of the substrate, decreases in the
GaN buffer, however, a degree of reduction thereof is small
compared with that in the Example 1, and, even in the GaN channel
layer, the concentration of the Zn element is equal to or higher
than 5.times.10.sup.16 cm.sup.-3, that is higher than that of the
Example 1 by two orders of magnitude. That is to say, the Zn
element is also diffused in the channel layer.
[0155] (4) A logarithm change ratio of the Zn concentration per
.mu.m (a change ratio of a common logarithm value of the
concentration) in a portion where the Zn concentration is
1.times.10.sup.17 cm.sup.-3 is -7.3.
[0156] The value R of the HEMT element was calculated to be 0.31
under the condition similar to that of the Example 1, and it was
determined that the current collapse was not sufficiently
suppressed in the HEMT element according to the present Comparative
Example.
Examples 2 to 6, Comparative Examples 2 to 5
[0157] The HEMT elements were manufactured under the conditions
similar to that of the Example 1 except that growth conditions of
the GaN buffer layer (the growth temperature, the reactor pressure,
the gas ratio of group 15 to group 13, and the formation
thickness), for example, were variously changed. Then, a
distribution in the depth direction of the Zn concentration and the
C concentration in the HEMT element, which had been obtained, was
obtained by the SIMS measurement, and the value R was
calculated.
[0158] A list of a result thereof is shown by Table 1 together with
the results of the Example 1 and the Comparative Example 1.
TABLE-US-00001 TABLE 1 SIMS measurement Zn concentration Growth
condition of GaN buffer layer from barrier Gas layer/channel ratio
of C layer interface Growth Reactor group 15 Collapse concentration
Logarithm change ratio of in downward temperature pressure to
Thickness evaluation in GaN buffer Zn concentration direction by
[.degree. C.] [kPa] group 13 [nm] Value R layer [cm.sup.-3]
[1/.mu.m] 200 nm [cm.sup.-3] Example 1 1050 10 500 1000 0.93 6
.times. 10.sup.18 -74.9 5 .times. 10.sup.14 Example 2 1050 10 500
300 0.91 6 .times. 10.sup.18 -71.3 6 .times. 10.sup.14 Example 3
1050 20 500 1000 0.88 1 .times. 10.sup.18 -20.0 6 .times. 10.sup.14
Example 4 1050 20 500 300 0.85 1 .times. 10.sup.18 -25.1 1 .times.
10.sup.15 Comparative 1050 30 500 1000 0.51 2 .times. 10.sup.17
-8.9 5 .times. 10.sup.15 Example 2 Comparative 1050 30 500 300 0.31
2 .times. 10.sup.17 -7.3 5 .times. 10.sup.16 Example 1 Example 5
1050 30 200 1000 0.90 1 .times. 10.sup.19 -80.5 6 .times. 10.sup.14
Comparative 1050 30 1000 1000 0.29 8 .times. 10.sup.16 Incalculable
because 2 .times. 10.sup.17 Example 3 Zn concentration is not equal
to or lower than 1 .times. 10.sup.17 cm.sup.-3 Comparative 1050 30
2000 1000 0.21 4 .times. 10.sup.16 Incalculable because 3 .times.
10.sup.17 Example 4 Zn concentration is not equal to or lower than
1 .times. 10.sup.17 cm.sup.-3 Example 6 950 30 500 1000 0.85 1
.times. 10.sup.18 -34.9 7 .times. 10.sup.14 Comparative 1150 30 500
1000 0.25 4 .times. 10.sup.16 Incalculable because 4 .times.
10.sup.17 Example 5 Zn concentration is not equal to or lower than
1 .times. 10.sup.17 cm.sup.-3
[0159] As shown in Table 1, in each case of the Example 1 to the
Example 6 in which the HEMT element was manufactured under the
condition that the concentration of C in the GaN buffer layer was
equal to or higher than 1.times.10.sup.18 cm.sup.-3, the value R
was equal to or larger than 0.85, and the concentration of Zn in
the GaN channel layer was equal to or lower than 1.times.10.sup.15
cm.sup.-3. This result indicates that the HEMT element in which the
current collapse was suppressed was obtained in all of the Example
1 to the Example 6.
[0160] A logarithm change ratio of the Zn concentration per .mu.m
in a portion where the Zn concentration was 1.times.10.sup.17
cm.sup.-3 was -20.0 or less. This indicates that the concentration
of Zn drastically decreases in all of the Example 1 to Example
6.
[0161] In contrast, in each case of the Comparative Example 1 to
the Comparative Example 5 in which the HEMT element was
manufactured under the condition that the concentration of C in the
GaN buffer layer is lower than 1.times.10.sup.18 cm.sup.-3, the
value R stayed at 0.51 at a maximum, and the concentration of Zn in
the GaN channel layer exceeded 1.times.10.sup.16 cm.sup.-3 except
for the Comparative Example 2. This result indicates that the
current collapse is not suppressed in the HEMT element according to
the Comparative Example 1 to the Comparative Example 5.
[0162] The logarithm change ratio of the Zn concentration per .mu.m
in the portion where the Zn concentration was 1.times.10.sup.17
cm.sup.-3 was -8.9 in the Comparative Example 1 and -7.3 in the
Comparative Example 2, however, in the Comparative Example 3 to the
Comparative Example 5, the Zn concentration did not fall below
1.times.10.sup.17 cm.sup.-3, thus the logarithm change ratio could
not be calculated. This result indicates that in the Comparative
Example 1 to the Comparative Example 5, a degree of reduction in
the concentration of Zn is small compared with that in the Example
1 to the Example 6.
Example 7
[0163] In the HEMT element according to the Example 1 to the
Example 6, the concentration of Zn sharply decreases, thus the
concentration of Zn in the channel layer falls below
1.times.10.sup.16 cm.sup.-3 and the current collapse is thereby
suppressed, however, as long as the concentration of Zn
sufficiently falls below 1.times.10.sup.16 cm.sup.-3 at the
neighborhood of the interface (the hetero interface) between the
barrier layer and the channel layer in the channel layer, the
current collapse may be suppressed in some cases even if the degree
of reduction in the Zn concentration is small.
[0164] In the present Example, the epitaxial substrate 10 and
further the HEMT element 20 were manufactured under the condition
similar to that of the Example 1 except that the growth condition
of the buffer layer 2 and the channel layer 3 was as follows,
differing from the Example 1.
[0165] GaN buffer layer:
[0166] Formation temperature=1050.degree. C.;
[0167] Reactor pressure=10 kPa;
[0168] Gas ratio of group 15 to group 13=500;
[0169] Thickness=100 nm.
[0170] GaN channel layer:
[0171] Formation temperature=1050.degree. C.;
[0172] Reactor pressure=100 kPa;
[0173] Gas ratio of group 15 to group 13=2000;
[0174] Thickness=1000 nm.
[0175] FIG. 6 is a drawing illustrating a concentration profile of
the Zn element and the C element from the surface (upper surface)
of the barrier layer 4 in the depth direction obtained by
performing the measurement on the HEMT element, which has been
obtained, in the depth direction by the SIMS measurement under the
condition similar to that of the Example 1. A result illustrated in
FIG. 6 shows the following state.
[0176] (1) The GaN substrate is doped with the Zn element at a high
concentration.
[0177] (2) Since the concentration of the C element is
3.times.10.sup.18 cm.sup.-3 in the buffer layer at a maximum, the
buffer layer includes a region which contains the C element at a
concentration equal to or higher than 1.times.10.sup.18 cm.sup.-3,
and the concentration of the C element is equal to or lower than
approximately 2.times.10.sup.16 cm.sup.-3 in the channel layer. The
concentration of the C element is sharply changed at the interface
between the buffer layer and the channel layer, but is slowly
changed in a portion from the buffer layer toward the GaN
substrate. FIG. 6 shows increase in the concentration of the C
element in a neighborhood of the barrier layer toward the barrier
layer. It is caused by knock-on of elements adhered to a sample
surface.
[0178] (3) The concentration of the Zn element, which is high in a
portion from the interface between the buffer layer and the GaN
substrate toward a side of the substrate, sharply decreases in the
buffer layer, further decreases in the channel layer, and reaches
to 5.times.10.sup.14 cm.sup.-3, which is the lower detection limit
value of Zn in the SIMS measurement, in a region including the
neighborhood of the interface (hetero interface) between the
barrier layer and the channel layer. That is to say, the diffusion
of the Zn element is suppressed.
[0179] (4) A logarithm change ratio of the Zn concentration per
.mu.m (a change ratio of a common logarithm value of the
concentration) in a portion where the Zn concentration is
1.times.10.sup.17 cm.sup.-3 is -15.0.
[0180] The value R of the HEMT element described above was
calculated to be 0.88. That is to say, it is determined that the
current collapse is preferably suppressed also in the HEMT element
according to the present Example.
Example 8
[0181] The epitaxial substrate 10 and further the HEMT element 20
were manufactured under the condition similar to that of the
Example 1 except that the growth condition of the buffer layer 2
and the channel layer 3 was as follows, differing from the Example
1. In the formation of the buffer layer 2 in the above processing,
the formation condition is set in two stages of a first condition
and a second condition, and is switched from the first condition to
the second condition halfway through the formation. This is
intended to form the buffer layer 2 as the multi-layered buffer
layer in which the GaN layer is laminated on the
Al.sub.aGa.sub.1-aN layer (0<a.ltoreq.1) or the composition
gradient buffer layer in which the existence ratio of Al and Ga is
different in the thickness direction. Herein, the first condition
is a condition that the doping of C into the buffer layer 2 is not
actively performed, and the second condition is a condition that
the doping of C into the buffer layer 2 is confirmed. A total
thickness of the buffer layer 2 was set to 110 nm.
[0182] Buffer layer (first condition):
[0183] Formation temperature=1050.degree. C.;
[0184] Reactor pressure=5 kPa;
[0185] Group 13 source gas=Al source and Ga source;
[0186] Gas ratio of group 15 to group 13=2000;
[0187] Gas ratio of Al source gas to group 13 source gas=0.03;
[0188] Growth rate=1 nm/sec.;
[0189] Growth time=10 seconds.
[0190] Buffer layer (second condition):
[0191] Formation temperature=1050.degree. C.;
[0192] Reactor pressure=10 kPa;
[0193] Group 13 source gas=Ga source;
[0194] Gas ratio of group 15 to group 13=500;
[0195] Growth rate=1 nm/sec.;
[0196] Growth time=100 seconds.
[0197] GaN channel layer:
[0198] Formation temperature=1050.degree. C.;
[0199] Reactor pressure=100 kPa;
[0200] Gas ratio of group 15 to group 13=2000;
[0201] Thickness=900 nm.
[0202] FIG. 7 is a drawing illustrating a concentration profile of
the Zn element and the C element from the surface (upper surface)
of the barrier layer 4 in the depth direction obtained by
performing the measurement on the HEMT element, which has been
obtained, in the depth direction by the SIMS measurement under the
condition similar to that of the Example 1 and a secondary ion
signal profile of the Al element in the depth direction (a
distribution of a secondary ion count rate of the Al element in the
depth direction). A result illustrated in FIG. 7 shows the
following state.
[0203] (1) The GaN substrate is doped with the Zn element at a high
concentration.
[0204] (2) The buffer layer includes a region which contains the C
element at a concentration equal to or higher than
1.times.10.sup.18 cm.sup.-3, 6.times.10.sup.18 cm.sup.-3 at a
maximum, and the concentration of the C element is equal to or
lower than approximately 1.times.10.sup.16 cm.sup.-3 in the channel
layer. The concentration of the C element is sharply changed at the
interface between the buffer layer and the channel layer, but is
gradually changed in the portion from the buffer layer toward the
GaN substrate. FIG. 7 shows increase in the concentration of the C
element in a neighborhood of the barrier layer in the channel layer
toward the barrier layer. It is caused by knock-on of elements
adhered to a sample surface.
[0205] (3) The concentration of the Zn element, which is high in a
portion from the interface between the buffer layer and the GaN
substrate toward a side of the substrate, sharply decreases in the
buffer layer, further decreases in the channel layer, and reaches
to 5.times.10.sup.14 cm.sup.-3, which is the lower detection limit
value of Zn in the SIMS measurement, in a region including the
neighborhood of the interface (hetero interface) between the
barrier layer and the channel layer. That is to say, the diffusion
of the Zn element is suppressed.
[0206] (4) A logarithm change ratio of the Zn concentration per
.mu.m (a change ratio of a common logarithm value of the
concentration) in a portion where the Zn concentration is
1.times.10.sup.17 cm.sup.-3 is -13.0.
[0207] (5) The Al element is contained in a range wider than 110 nm
which is a targeted thickness of the whole buffer layer, and the
range also includes part of the GaN substrate.
[0208] (6) Since the Al element is hardly detected in a region
where the concentration of the C element reaches a maximum in the
buffer layer, it is deemed that the buffer layer includes the GaN
layer which is significantly doped with C and the AlGaN layer which
is slightly doped with C.
[0209] The value R of the HEMT element described above was
calculated to be 0.90. That is to say, it is determined that the
current collapse is preferably suppressed also in the HEMT element
according to the present Example.
Example 9
[0210] The HEMT element 20 was manufactured under the condition
similar to that of the Example 8 except that the growth condition
of the buffer layer 2 and the channel layer 3 was as follows,
differing from the Example 8. That is to say, also in the present
Example, in the formation of the buffer layer 2, the formation
condition is set in two stages of a first condition and a second
condition, and is switched from the first condition to the second
condition halfway through the formation. A total thickness of the
buffer layer 2 was set to 350 nm.
[0211] Buffer layer (first condition):
[0212] Formation temperature=1050.degree. C.;
[0213] Reactor pressure=5 kPa;
[0214] Group 13 source gas=Al source and Ga source;
[0215] Gas ratio of group 15 to group 13=2000;
[0216] Gas ratio of Al source gas to group 13 source gas=0.01;
[0217] Growth rate=1 nm/sec.;
[0218] Growth time=50 seconds.
[0219] Buffer layer (second condition):
[0220] Formation temperature=1050.degree. C.;
[0221] Reactor pressure=10 kPa;
[0222] Gas ratio of group 15 to group 13=500;
[0223] Growth rate=1 nm/sec.;
[0224] Growth time=300 seconds.
[0225] GaN channel layer:
[0226] Formation temperature=1050.degree. C.;
[0227] Reactor pressure=100 kPa;
[0228] Gas ratio of group 15 to group 13=2000;
[0229] Thickness=1700 nm.
[0230] A concentration profile of the Zn element and the C element
from the surface (upper surface) of the barrier layer 4 in the
depth direction obtained by performing the SIMS measurement on the
HEMT element, which has been obtained, under the condition similar
to that of the Example 1 and a secondary ion signal profile of the
Al element in the depth direction show the following matters.
[0231] (1) The GaN substrate is doped with the Zn element at a high
concentration (1.times.10.sup.19 cm.sup.-3).
[0232] (2) The buffer layer includes a region which contains the C
element at a concentration equal to or higher than
1.times.10.sup.18 cm.sup.-3, 6.times.10.sup.18 cm.sup.-3 at a
maximum, and the concentration of the C element is equal to or
lower than approximately 1.times.10.sup.16 cm.sup.-3 in the channel
layer. The concentration of the C element is sharply changed at the
interface between the buffer layer and the channel layer, but is
gradually changed in the portion from the buffer layer toward the
GaN substrate.
[0233] (3) The concentration of the Zn element, which is high in a
portion from the interface between the buffer layer and the GaN
substrate toward the side of the substrate, sharply decreases in
the buffer layer, further decreases in the channel layer, and
reaches to 5.times.10.sup.14 cm.sup.-3, which is the lower
detection limit value of Zn in the SIMS measurement, at a
neighborhood of the interface (hetero interface) between the
barrier layer and the channel layer in the channel layer. That is
to say, the diffusion of the Zn element is suppressed.
[0234] (4) A logarithm change ratio of the Zn concentration per
.mu.m (a change ratio of a common logarithm value of the
concentration) in a portion where the Zn concentration is
1.times.10.sup.17 cm.sup.-3 is -58.3.
[0235] (5) The Al element is contained in a range wider than 350 nm
which is a targeted thickness of the whole buffer layer, and the
range also includes part of the GaN substrate.
[0236] (6) Since the Al element is hardly detected in a region
where the concentration of the C element reaches a maximum in the
buffer layer, it is deemed that the buffer layer includes the GaN
layer which is significantly doped with C and the AlGaN layer which
is slightly doped with C.
[0237] The value R of the HEMT element described above was
calculated to be 0.92. That is to say, it is determined that the
current collapse is preferably suppressed also in the HEMT element
according to the present Example.
* * * * *