United States Patent [191 [1 l] Patent Number: 4,614,961

Khan et a1. [45] Date of Patent: Sep. 30, 1986

[54] TUNABLE CUT-OFF UV DETECTOR BASED sure Metal Organic Deposition”, Applied Physics Letters,
ON THE ALUMINUM GALLIUM NITRIDE Sep., 1983, pp. 1-3.
MATERIAL SYSTEM A. R. Annoeva et al., “Photoelectric Effect in Varia
[75] Inventors: M. Asif Khan, Burnsville; Richard G. ble-Gap Ga1_xAlxP Surface-Barrier Structures”, Sov.
Schulze, Hopkins; Richard A. Phys. Semicond. l5 (1), Jan. 1981, pp. 64-66.
Skogman, Plymouth, all of Minn. A. R. Annoeva et al., “Ultraviolet Photodetector Based
on a Variable Gap Ga‘1_xAlxP Surface Barrier Struc
[73] Assignee: Honeywell Inc., Minneapolis, Minn. ture” Sov. Phys. Semicond. 15 (6), Jun. 1981, pp.
[21] Appl. No.: 658,961 646-647.
D. L. Smith et al., “Growth of AlGaN Films for Elec
[22] Filed: Oct. 9, 1984 trooptic Device Applns.”, Report to ONR N00014-7
[51] Int. Cl.‘ .................... .. H01L 27/14; H01L 31/00 7-C-0942.
[52] US. Cl. ...................................... .. 357/30; 357/15;
Primary Examiner—-James W. Davie
357/61
Field of Search ........................... .. 357/30, 15, 61; Assistant Examiner-Georgia Y. Epps
340/577, 578, 579 Attorney, Agent, or Firm—-Omund R. Dahle

[56] References Cited [57] ABSTRACT

U.S. PATENT DOCUMENTS A method of preparing a UV detector of AlxGa1_xN.
4,095,331 6/1978 Rutz .................................... .. 357/61
Metal organic chemical vapor deposition (MOCVD) is
4,300,149 11/1981 Howard et al. ..................... .. 357/15
utilized to grow AlN and then AlXGa1_xN on a sap
phire substrate. A photodetector structure is fabricated
OTHER PUBLICATIONS on the AlGaN.
Khan et al., “Properties of Ion Implantation of AlGaN
Epitaxial Single Crystal Films Prepared by Low Pres 6 Claims, 1 Drawing Figure

10

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BATTERY
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Au/TiW/Au METER
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+9.?‘ "E"
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U.S. Patent Sep. 30, 1986 4,614,961

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 4,614,961 2
1
BRIEF DESCRIPTION OF THE DRAWINGS
TUNABLE CUT-OFF UV DETECTOR BASED ON
THE ALUMINUM GALLIUM NITRIDE The single FIGURE of the drawing is a diagram
MATERIAL SYSTEM matic view of the UV detector made according to the
method of the invention.
The US. Government has certain rights in this inven DESCRIPTION
tion pursuant to the terms of a contract F33615-82-C
1722.
The present invention describes a solid-state Alumi
num Gallium Nitride (AlxGa1_xN) UV detector and
BACKGROUND AND SUMMARY OF THE the process of fabricating the device. In order to have a
INVENTION sharp wavelength cut-off feature the active laser mate
rial should be a single crystal semiconductor in which
This invention is directed to a MOCVD process of
direct intrinsic bandgap absorption sets in very
fabricating a solid-state UV detector whose long wave
abruptly. The AlxGa1_xN system is the preferred
length cut-off can be set between 220 and 360 nm for
15 choice because it has wide bandgaps which lie in the
?ame sensing and other applications. The detector is ultra violet range of energies and because the spectral
base on the aluminum gallium nitride (AlGaN) material response can be tuned or tailored to the application by
system. varying the aluminum to gallium ratio. Thus AlGaN
In the prior art it is known to have photocathodes and has been grown by MOCVD in the compositional range
photomultiplier-tubes (PMT’s) which sense ultraviolet required to produce detectors having peak sensitivities
(UV) radiation. The PMT’s are costly, large size and between 3.53 eV(35O nm) and 4.64 eV(267 nm). The
fragile, and they require high voltage. In addition the MOCVD process is well adapted (unlike halide trans
long wavelength cut-off of these detectors is not adjust port vapor phase epitaxy) to the growth of aluminum
able and they respond to wavelengths longer than 300 gallium alloy systems because the ratio of aluminum to
nm. Filters can be used to reject wavelengths longer 25 gallium can be easily controlled.
than 300 nm but this adds mass and cost. The solid-state For the absorbed photons to be detected electrically,
AlGaN detector of this invention is an ideal replace the electrons and holes produced must be separated
ment for the PMT’s having low mass, reliability, low before they recombine. This is conveniently accom
cost and has a sharp cutoff wavelength for UV detec plished by drift in an electric ?eld such as that provided
tion. 30 by a Schottky barrier or photoconductor approach. The
In the prior art certain UV detectors of AlxGa1_xP Schottky barrier metal-semiconductor junction results
have appeared in the literature. Two of these articles in a depletion region in the AlGaN semiconductor in
are by the same authors A. R. Annoeva et al, “Photoe which the photogenerated electrons and holes are sepa
lectric Effect in Variable-Gap Ga1_xAlxP Surface-Bar rated by the built-in electric ?led which may be aug
rier Structures”, Sov. Phys. Semicond. 15(1) January 35 mented if desired by an applied bias. In the forming of
1981, P64-66 and “Ultra- violet Photodetector Based this function the doping of the semiconductor is impor
on a Variable-Gap Ga1_ xAlxPx (x,=0.5 +0.1) Surface tant. If the AlGaN material is too heavily doped n-type
Barrier Structure”, Sov. Phys. Semicond. 15(6) June (~1018 crn—3), the depletion layer will be very narrow,
1981, P646-7. These prior art AlGaP devices were and tunneling of electrons to the semiconductor
grown by liquid phase epitaxy (LPE). A third article 40 through the Schottky barrier will lead to leakage cur
data Feb. 81 is by Donald L. Smith and Richard H. rent or to a‘ ohmic contact instead of a good Schottky
Bruce, entitled “Growth of Aluminum Gallium Nitride barrier contact. If the doping is too low, that is if the
Films for Electro-optic Device Applications” and is an Fermi level lies greater than several kT below the con
unrestricted report to the Of?ce of Naval Research duction band, the bulk material will be higly resistive.
In the AlGaN system, to form a good Schottky barrier
under a Contract No. NOO0l4-77-C-0492. In the prior
requires a net shallow donor concentration on the order
art an article by Khan et al, “Properties of Ion Implanta
of 1016 cm-3.
tion of AlxGa1_xN Epitaxial Single Crystal Films Pre Referring now to the ?gure there is shown a solid
pared by Low Pressure Metal Organic Chemical Vapor state solar blind UV detector 10 having a basal plane
Deposition”, Appl. Physics Letters, September 1983 50 sapphire (A1203) substrate 11. In preparing the device
teaches one method by which AlxGa1_XN has been the substrate is loaded into a metalorganic chemical
grown on a sapphire substrate for use as an optical vapor deposition (MOCVD) reactor and heated such as
device in the UV region of the spectrum. by rf induction to l0OO° C. Then NH3 and (CH3)3A1
The present invention provides an improved method (trimethylaluminum) or (C2H5)3Al (triethylaluminum)
of growing a AlGaN sensor for ultraviolet which solves 55 are introduced into the growth chamber and epitaxial
a problem of detecting UV radiation against a hot re growth continues for about 10 minutes resulting in a
fractory background or solar radiation. Thus this detec single crystalline aluminum nitride (AlN) layer 12 about
tor can sense UV radiation of a ?ame in a furnace with 0.5 pm thick on the surface 13 of the substrate. The
a hot refractory background, for example, responding buffer layer 12 of AlN results in a higher electron mo
only to the UV and not to radiation of other wavelength 60 bility of the epitaxial AlxGa1_xN layer to be next
emanating from the hot furnace interior. This UV grown thereon. Then triethylgallium (C2H5)3Ga is also
detector is based on interband absorptions of incoming introduced into the growth chamber and the epitaxial
radiation in the AlGaN material system. The detector growth of the aluminum gallium nitride (AlxGa1_xN) is
does not require any additional ?lter as the intrinsic carried out for about 2 hours. This results in a single
absorption cutoff in the semiconductor acts as a ?lter. 65 crystalline aluminum gallium nitride (AlxGa1_xN)
The method includes ?rst growing a layer of AlN on layer 14 on the order of 2 pm thick. The x value se
the sapphire substrate and then the AlGaN layer upon lected can be controlled as desired by adjusting the gas
which a photodetector structure is fabricated. flow rates of the several gases. The temperature during
 4,614,961
3 4
AlxGa1_xN growth is lowered from the lOOO“ C. and is determined by the bandgap of the active AlxGa1_xN
selected depending upon the x value selected. In one layer.
embodiment we grow the active AlXGa1_xN layer with While the apparatus has been shown and described as
an x value of about 0.35 which puts the cutoff wave being negatively biased for operation, it can also be
length at 290 nm. The AlXGa1_xN layer as grown is 11 operated in a zero-bias photovoltaic mode which makes
type with Nd~5>< l016/cc. it fail-safe as no signal is possible except under UV
A metal Schottky barrier 15 is fabricated on the illumination.
AlGaN layer. For fabrication of the Schottky barrier 15 The electron-hole pairs and hence the signal current
and the ohmic contact 16 onto the surface 17 of the is only produced if the wavelength of incident light is
AlxGa1_xAs layer 14, the surface 17 is masked to delin less than or equal to g where g=hc/Eg where “h” is the
eate contact 16 and a layer of 3000 A of gold or other Planck’s constant, “c” the velocity of light and “Eg” is
suitable metal is ?rst deposited for contact 16 and is then the bandgap of the semiconductor AlxGa1_xN. An
annealed at 700° C. under ?owing NH3 for 5 min. The other kind of photodetector structure, a photoconduc
surface 17 is again masked with photoresist to delineate tor can also be used. In this both metal contacts 15 and
the Schottky barrier location. Then for barrier 1§ there 15 16 are ohmic contacts and a source of electric ?eld bias
is applied onto surface 17 Au/TiW/Au (100 A/ 1000 is required.
A/5000 A) using for instance an rf-sputtering system. In The embodiments of the invention in which an exclu
this particular Schottky metalliazation, the TiW acts as a sive property or right is claimed are de?ned as follows:
diffusion barrier for the 5000 A layer of gold. 1. In a solid state UV detector comprising:
Attached to the device 10 at Schottky barrier 15 and 20 a. a basal plane sapphire (A1203) substrate;
ohmic contact 16 is a series circuit including conductors b. an epitaxial single-crystalline aluminum nitride
18 and 19, do source such as battery 20 and a current (AlN) layer grown on the surface of the substrate;
meter 21 for measurement of the resulting photocur 0. An epitaxial single-crystalline aluminum gallium
rent. nitride (AlXGa1_xN) layer grown over said AlN
In operation the Schottky barrier is kept under re 25 layer; and,
verse bias (e.g. 2 to 3 V) so that only a leakage current d. a photodetector fabricated on said AlxGa1_xN
?ows in the external circuit. When a photon (UV light layer surface.
from the flame) enters the depletion region under the 2. The detector according to claim 1 in which the
Schottky barrier through the transparent A1203 sub AlN layer is on the order of 0.5 um thick.
strate (typically 1 mm thick) an electron-hole pair is 30 3. The detector according to claim 1 in which the
created. That is, when a UV photon with an energy AlXGa1_xN layer is on the oder of 2 pm thick.
E<Eg (Eg is the bandgap energy for AlxGa1_xN) is 4. The detector according to claim 1 wherein said
incident on the active layer it creates electron-hole pairs photodetector is a Schottky barrier.
which are swept out by the electric ?eld and hence a 5. The detector according to claim 4 wherein said
signal current is detected in the external circuit. The 35 Schottky barrier comprises layers of Au, TiW and Au.
signal current is only produced when the UV-photon is 6. The detector according to claim 1, wherein said
absorbed in the active layer, and thus the device shows photodetector is of the photoconductor.
a response which turns on very sharply at a wavelength * * * * *

45

55

65.
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT N0. ; 4,614,961
DATED : September 30, 1986 _
INVENTOR(S) : M. Asif Khan; Richard G. Schulze; Richard’ A. Skogman'
It is certified that errbr appears in the above-identified patent and that said Letters'Patent is hereby
corrected asshown below: '

In Column 4, vli'ne 37, afteri"p“hotoconductor" insert

—-type--.

Signed and Sealed this

Seventh Day 0f May, 1991

Arrest:

HARRY F. MANBECK. .IR.

_AII€Sfmg O?‘icer Cmnmissioner of Parent: and Trademark: