U.S. patent application number 14/979899 was filed with the patent office on 2016-04-21 for lattice matchable alloy for solar cells.
The applicant listed for this patent is SOLAR JUNCTION CORPORATION. Invention is credited to REBECCA ELIZABETH JONES-ALBERTUS, TING LIU, PRANOB MISRA, HOMAN BERNARD YUEN.
Application Number | 20160111569 14/979899 |
Document ID | / |
Family ID | 44654966 |
Filed Date | 2016-04-21 |
United States Patent
Application |
20160111569 |
Kind Code |
A1 |
JONES-ALBERTUS; REBECCA ELIZABETH ;
et al. |
April 21, 2016 |
LATTICE MATCHABLE ALLOY FOR SOLAR CELLS
Abstract
An alloy composition for a subcell of a solar cell is provided
that has a bandgap of at least 0.9 eV, namely,
Ga.sub.1-xIn.sub.xN.sub.yAs.sub.1-y-zSb.sub.z with a low antimony
(Sb) content and with enhanced indium (In) content and enhanced
nitrogen (N) content, achieving substantial lattice matching to
GaAs and Ge substrates and providing both high short circuit
currents and high open circuit voltages in GaInNAsSb subcells for
multijunction solar cells. The composition ranges for
Ga.sub.1-xIn.sub.xN.sub.yAs.sub.1-y-zSb.sub.z are
0.07.ltoreq.x.ltoreq.0.18, 0.025.ltoreq.y.ltoreq.0.04 and
0.001.ltoreq.z.ltoreq.0.03.
Inventors: |
JONES-ALBERTUS; REBECCA
ELIZABETH; (WASHINGTON, DC) ; YUEN; HOMAN
BERNARD; (SANTA CLARA, CA) ; LIU; TING; (SAN
JOSE, CA) ; MISRA; PRANOB; (SANTA CLARA, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SOLAR JUNCTION CORPORATION |
SAN JOSE |
CA |
US |
|
|
Family ID: |
44654966 |
Appl. No.: |
14/979899 |
Filed: |
December 28, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14678737 |
Apr 3, 2015 |
9252315 |
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14979899 |
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14597621 |
Jan 15, 2015 |
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14678737 |
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14512224 |
Oct 10, 2014 |
9018522 |
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14597621 |
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13739989 |
Jan 11, 2013 |
8912433 |
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14512224 |
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12749076 |
Mar 29, 2010 |
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13739989 |
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Current U.S.
Class: |
428/544 ;
420/580 |
Current CPC
Class: |
H01L 31/03048 20130101;
C30B 33/02 20130101; H01L 31/0725 20130101; H01L 31/1848 20130101;
H01L 31/03046 20130101; H01L 31/0304 20130101; Y02E 10/544
20130101; Y10T 428/12 20150115; Y02P 70/521 20151101; C30B 23/025
20130101; C30B 29/40 20130101; C30B 23/066 20130101; Y02P 70/50
20151101; H01L 31/1844 20130101; H01L 31/0735 20130101; C22C 28/00
20130101; C22C 30/00 20130101; H01L 31/078 20130101; H01L 31/1852
20130101; H01L 31/036 20130101 |
International
Class: |
H01L 31/0304 20060101
H01L031/0304; C22C 30/00 20060101 C22C030/00; H01L 31/036 20060101
H01L031/036 |
Claims
1. An electron generating junction comprising a semiconductor alloy
composition, wherein the semiconductor alloy composition is
Ga.sub.1-xIn.sub.xN.sub.yAs.sub.1-y-zSb.sub.z wherein, the content
values for x, y, and z are within composition ranges as follows:
0.07.ltoreq.x.ltoreq.0.18, 0.025.ltoreq.y.ltoreq.0.04 and
0.001.ltoreq.z.ltoreq.0.03; the content levels are selected such
that the semiconductor alloy composition exhibits a bandgap from
0.9 eV to 1.1 eV; and a short circuit current density Jsc greater
than 13 mA/cm.sup.2 and an open circuit voltage Voc greater than
0.3 V when illuminated with a filtered 1 sun AM1.5D spectrum in
which all light having an energy greater than the bandgap of GaAs
is blocked.
2. The electron generating junction of claim 1, wherein the
semiconductor alloy composition is characterized by a thickness
from 1 .mu.m to 2 .mu.m.
3. The electron generating junction of claim 1, wherein the
semiconductor alloy composition is characterized by a thickness
greater than 1 .mu.m.
4. The electron generating junction of claim 1, wherein the
semiconductor alloy composition is substantially lattice matched to
GaAs.
5. The electron generating junction of claim 1, wherein the
semiconductor alloy composition is substantially lattice matched to
Ge.
6. The electron generating junction of claim 1, wherein the
semiconductor alloy composition is n-doped.
7. The electron generating junction of claim 1, wherein the
semiconductor alloy composition is p-doped.
8. The electron generating junction of claim 1, wherein the
semiconductor alloy composition is in the form of a layer of
semiconductor material.
9. The electron generating junction of claim 1, wherein the content
values are selected such that the semiconductor alloy composition
is lattice matched to GaAs or Ge.
10. A diode comprising the electron generating junction of claim
1.
11. A photodiode comprising the electron generating junction of
claim 1.
12. A photodetector comprising the electron generating junction of
claim 1.
Description
[0001] This application is a continuation of U.S. application Ser.
No. 14/678,737, filed on Apr. 3, 2015, now allowed, which is a
continuation of U.S. application Ser. No. 14/597,621, filed on Jan.
15, 2015, which is a continuation of U.S. application Ser. No.
14/512,224, filed on Oct. 10, 2014, issued as U.S. Pat. No.
9,018,522, which is a continuation of 13/739,989, filed on Jan. 11,
2013, issued as U.S. Pat. No. 8,912,433, which is a divisional of
U.S. application Ser. No. 12/749,076, filed on Mar. 29, 2010, each
of which is incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to multijunction solar cells,
and in particular to high efficiency solar cells comprised of III-V
semiconductor alloys.
[0003] Multijunction solar cells made primarily of III-V
semiconductor alloys are known to produce solar cell efficiencies
exceeding efficiencies of other types of photovoltaic materials.
Such alloys are combinations of elements drawn from columns III and
V of the standard Periodic Table, identified hereinafter by their
standard chemical symbols, names and abbreviation. (Those of skill
in the art can identify their class of semiconductor properties by
class without specific reference to their column.) The high
efficiencies of these solar cells make them attractive for
terrestrial concentrating photovoltaic systems and systems designed
to operate in outer space. Multijunction solar cells with
efficiencies above 40% under concentrations equivalent to several
hundred suns have been reported. The known highest efficiency
devices have three subcells with each subcell consisting of a
functional p-n junction and other layers, such as front and back
surface field layers. These subcells are connected through tunnel
junctions, and the dominant layers are either lattice matched to
the underlying substrate or are grown over metamorphic layers.
Lattice-matched devices and designs are desirable because they have
proven reliability and because they use less semiconductor material
than metamorphic solar cells, which require relatively thick buffer
layers to accommodate differences in the lattice constants of the
various materials. As set forth more fully in U.S. patent
application Ser. No. 12/217,818, entitled "GaInNAsSb Solar Cells
Grown by Molecular Beam Epitaxy," which application is incorporated
herein by reference, a layer made of GaInNAsSb material to create a
third junction having a band gap of approximately 1.0 eV offers a
promising approach to improving the efficiency of multijunction
cells. Improvements are nevertheless to be considered on the cell
described in that application.
[0004] The known highest efficiency, lattice-matched solar cells
typically include a monolithic stack of three functional p-n
junctions, or subcells, grown epitaxially on a germanium (Ge)
substrate. The top subcell has been made of (Al)GaInP, the middle
one of (In)GaAs, and the bottom junction included the Ge substrate.
(The foregoing nomenclature for a III-V alloy, wherein a
constituent element is shown parenthetically, denotes a condition
of variability in which that particular element can be zero.) This
structure is not optimal for efficiency, in that the bottom
junction can generate roughly twice the short circuit current of
the upper two junctions, as reported by J. F. Geisz et al.,
"Inverted GaInP/(In)GaAs/InGaAs triple junction solar cells with
low-stress metamorphic bottom junctions," Proceedings of the
33.sup.rd IEEE PVSC Photovoltaics Specialists Conference, 2008.
This extra current capability is wasted, since the net current must
be uniform through the entire stack, a design feature known as
current matching.
[0005] In the disclosure of above noted U.S. patent application
Ser. No. 12/217,818, it was shown that a material that is
substantially lattice matched to Ge or GaAs with a band gap near
1.0 eV might be used to create a triple junction solar cell with
efficiencies higher than the structure described above by replacing
the bottom Ge junction with a junction made of a different material
that produces a higher voltage.
[0006] In addition, it has been suggested that the use of this 1 eV
material might be considered as a fourth junction to take advantage
of the entire portion of the spectrum lying between 0.7 eV (the
band gap for germanium) and 1.1 eV (the upper end of the range of
bandgaps for the .about.1 eV layer). See for example, S. R. Kurtz,
D. Myers, and J. M. Olson, "Projected Performance of Three and
Four-Junction Devices Using GaAs and GaInP," 26th IEEE
Photovoltaics Specialists Conference, 1997, pp. 875-878.
Ga.sub.1-xIn.sub.xN.sub.yAs.sub.1-y has been identified as such a 1
eV material, but currents high enough to match the other subcells
have not been achieved, see, e.g., A. J. Ptak et al., Journal of
Applied Physics 98 (2005) 094501. This has been attributed to low
minority carrier diffusion lengths that prevent effective
photocarrier collection. Solar subcell design composed of gallium,
indium, nitrogen, arsenic and various concentrations of antimony
(GaInNAsSb) has been investigated with the reported outcome that
antimony is helpful in decreasing surface roughness and allowing
growth at higher substrate temperatures where annealing is not
necessary, but the investigators reported that antimony, even in
small concentrations is critical to be avoided as detrimental to
adequate device performance. See Ptak et al., "Effects of
temperature, nitrogen ion, and antimony on wide depletion width
GaInNAs," Journal of Vacuum Science Technology B 25(3) May/June
2007 pp. 955-959. Devices reported in that paper have short circuit
currents far too low for integration into multijunction solar
cells. Nevertheless, it is known that
Ga.sub.1-xIn.sub.xN.sub.yAs.sub.1-y-zSb.sub.z with
0.05.ltoreq.x.ltoreq.0.07, 0.01.ltoreq.y.ltoreq.0.02 and
0.02.ltoreq.z.ltoreq.0.06 can be used to produce a lattice-matched
material with a band gap of approximately 1 eV that can provide
sufficient current for integration into a multijunction solar cell.
However, the voltages generated by subcells containing this
material have not exceeded 0.30 V under 1 sun of illumination. See
D. B. Jackrel et al., Journal of Applied Physics 101 (114916) 2007.
Thus, a triple-junction solar cell with this material as the bottom
subcell has been expected to be only a small improvement upon an
analogous triple junction solar cell with a bottom subcell of Ge,
which produces an open circuit voltage of approximately 0.25 V. See
H. Cotal et al., Energy and Environmental Science 2 (174) 2009.
What is needed is a material that is lattice-matched to Ge and GaAs
with a band gap near 1 eV that produces an open circuit voltage
greater than 0.30 V and sufficient current to match (AI)InGaP and
(In)GaAs subcells. Such a material would also be advantageous as a
subcell in high efficiency solar cells with 4 or more
junctions.
SUMMARY OF THE INVENTION
[0007] According to the invention, an alloy composition is provided
that has a bandgap of at least 0.9 eV, namely,
Ga.sub.1-xIn.sub.xN.sub.yAs.sub.1-y-zSb.sub.z with a low antimony
(Sb) content and with enhanced indium (In) content and enhanced
nitrogen (N) content as compared with known alloys of GaInNAsSb,
achieving substantial lattice matching to GaAs and Ge substrates
and providing both high short circuit currents and high open
circuit voltages in GaInNAsSb subcells suitable for use in
multijunction solar cells. The composition ranges for
Ga.sub.1-xIn.sub.xN.sub.yAs.sub.1-y-zSb.sub.z are
0.07.ltoreq.x.ltoreq.0.18, 0.025.ltoreq.y.ltoreq.0.04 and
0.001.ltoreq.z.ltoreq.0.03. These composition ranges employ greater
fractions of In and N in GaInNAsSb than previously taught and allow
the creation of subcells with bandgaps that are design-tunable in
the range of 0.9-1.1 eV, which is the range of interest for
GaInNAsSb subcells. This composition range alloy will hereinafter
be denoted "low-antimony, enhanced indium-and-nitrogen GaInNAsSb"
alloy. Subcells of such an alloy can be grown by molecular beam
epitaxy (MBE) and should be able to be grown by metallorganic
chemical vapor deposition (MOCVD), using techniques known to one
skilled in the art.
[0008] The invention described herein reflects a further refinement
of work described in U.S. patent application Ser. No. 12/217,818,
including the discovery and identification of specific ranges of
elements, i.e., a specific alloy mix of the various elements in
GaInNAsSb that improve significantly the performance of the
disclosed solar cells.
[0009] The invention will be better understood by reference to the
following detailed description in connection with the accompanying
drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1A is a schematic cross-section of a three junction
solar cell incorporating the invention.
[0011] FIG. 1B is a schematic cross-section of a four junction
solar cell incorporating the invention.
[0012] FIG. 2A is a schematic cross-section of a GaInNAsSb subcell
according to the invention.
[0013] FIG. 2B is a detailed schematic cross-section illustrating
an example GaInNAsSb subcell.
[0014] FIG. 3 is a graph showing the efficiency versus band gap
energy of subcells formed from different alloy materials, for
comparison.
[0015] FIG. 4 is a plot showing the short circuit current
(J.sub.sc) and open circuit voltage (V.sub.oc) of subcells formed
from different alloy materials, for comparison.
[0016] FIG. 5 is a graph showing the photocurrent as a function of
voltage for a triple junction solar cell incorporating a subcell
according to the invention, under 1-sun AM1.5D illumination.
[0017] FIG. 6 is a graph showing the photocurrent as a function of
voltage for a triple junction solar cell incorporating a subcell
according to the invention, under AM1.5D illumination equivalent to
523 suns.
[0018] FIG. 7 is a graph of the short circuit current (J.sub.sc)
and open circuit voltage (V.sub.oc) of low Sb, enhanced In and N
GaInNAsSb subcells distinguished by the strain imparted to the film
by the substrate.
DETAILED DESCRIPTION OF THE INVENTION
[0019] FIG. 1A is a schematic cross-section showing an example of a
triple junction solar cell 10 according to the invention consisting
essentially of a low Sb, enhanced In and N GaInNAsSb subcell 12
adjacent the Ge, GaAs or otherwise compatible substrate 14 with a
top subcell 16 of (Al)InGaP and a middle subcell 18 using (In)GaAs.
Tunnel junction 20 is between subcells 16 and 18, while tunnel
junction 22 is between subcells 18 and 12. Each of the subcells 12,
16, 18 comprises several associated layers, including front and
back surface fields, an emitter and a base. The named subcell
material (e.g., (In)GaAs) forms the base layer, and may or may not
form the other layers.
[0020] Low Sb, enhanced In and N GaInNAsSb subcells may also be
incorporated into multijunction solar cells with four or more
junctions without departing from the spirit and scope of the
invention. FIG. 1B shows one such four-junction solar cell 100 with
a specific low Sb, enhanced In and N GaInNAsSb subcell 12 as the
third junction, and with a top subcell 16 of (Al)InGaP, a second
subcell 18 of (In)GaAs and a bottom subcell 140 of Ge, which is
also incorporated into a germanium (Ge) substrate. Each of the
subcells 16, 18, 12, 140 is separated by respective tunnel
junctions 20, 22, 24, and each of the subcells 16, 18, 12, 140 may
comprise several associated layers, including optional front and
back surface fields, an emitter and a base. The named subcell
material (e.g., (In)GaAs) forms the base layer, and may or may not
form the other layers.
[0021] By way of further illustration, FIG. 2A is a schematic
cross-section in greater detail of a GaInNAsSb subcell 12,
according to the invention. The low Sb, enhanced In and N GaInNAsSb
subcell 12 is therefore characterized by its use of low Sb,
enhanced In and N GaInNAsSb as the base layer 220 in the subcell
12. Other components of the GaInNAsSb subcell 12, including an
emitter 26, an optional front surface field 28 and back surface
field 30, are preferably III-V alloys, including by way of example
GaInNAs(Sb), (In)(Al)GaAs, (Al)InGaP or Ge. The low Sb, enhanced In
and N GaInNAsSb base 220 may either be p-type or n-type, with an
emitter 26 of the opposite type.
[0022] To determine the effect of Sb on enhanced In and N GaInNAsSb
subcell performance, various subcells of the type (12) of the
structure shown in FIG. 2B were investigated. FIG. 2B is a
representative example of the more general structure 12 in FIG. 2A.
Base layers 220 with no Sb, low Sb (0.001.ltoreq.z.ltoreq.0.03) and
high Sb (0.03<z<0.06) were grown by molecular beam epitaxy
and were substantially lattice-matched to a GaAs substrate (not
shown). These alloy compositions were verified by secondary ion
mass spectroscopy. The subcells 12 were subjected to a thermal
anneal, processed with generally known solar cell processing, and
then measured under the AM1.5D spectrum (1 sun) below a filter that
blocked all light above the GaAs band gap. This filter was
appropriate because a GaInNAsSb subcell 12 is typically beneath an
(In)GaAs subcell in a multijunction stack (e.g., FIGS. 1A and 1B),
and thus light of higher energies will not reach the subcell
12.
[0023] FIG. 3 shows the efficiencies produced by the subcells 12
grown with different fractions of Sb as a function of their band
gaps. The indium and nitrogen concentrations were each in the 0.07
to 0.18 and 0.025 to 0.04 ranges, respectively. It can be seen that
the low Sb, enhanced In and N GaInNAsSb subcells (represented by
triangles) have consistently higher subcell efficiencies than the
other two candidates (represented by diamonds and squares). This is
due to the combination of high voltage and high current
capabilities in the low Sb, enhanced In and N GaInNAsSb devices.
(See FIG. 4). As can be seen in FIG. 4, both the low and high
concentration Sb devices have sufficient short-circuit current to
match high efficiency (Al)InGaP subcells and (In)GaAs subcells
(>13 mA/cm.sup.2under the filtered AM1.5D spectrum), and thus
they may be used in typical three junction or four-junction solar
cells 10, 100 without reducing the total current through the entire
cell. This current-matching is essential for high efficiency. The
devices without Sb have relatively high subcell efficiencies due to
their high open circuit voltages, but their short circuit currents
are too low for high efficiency multijunction solar cells, as is
shown in FIG. 4.
[0024] FIG. 4 also confirms that Sb has a deleterious effect on
voltage, as previously reported for other alloy compositions.
However, in contrast to what has been previously reported for other
alloy compositions, the addition of antimony does NOT decrease the
short circuit current. The low Sb-type subcells have roughly 100 mV
higher open-circuit voltages than the high Sb-type subcells. To
illustrate the effect of this improvement, a triple-junction solar
cell 10 with an open circuit voltage of 3.1 V is found to have 3.3%
higher relative efficiency compared to an otherwise identical cell
with an open circuit voltage of 3.0 V. Thus, the inclusion of Sb in
GaInNAs(Sb) solar cells is necessary to produce sufficient current
for a high efficiency solar cell, but only by using low Sb (0.1-3%)
can both high voltages and high currents be achieved.
[0025] Compressive strain improves the open circuit voltage of low
Sb, enhanced In and N GaInNAsSb subcells 10, 100. More
specifically, low Sb, enhanced In and N GaInNAsSb layers 220 that
have a lattice constant larger than that of a GaAs or Ge substrate
when fully relaxed (.ltoreq.0.5% larger), and are thus under
compressive strain when grown pseudomorphically on those
substrates. They also give better device performance than layers
with a smaller, fully relaxed lattice constant (under tensile
strain).
[0026] FIG. 7 shows the short circuit current and open circuit
voltage of low Sb, enhanced In and N GaInNAsSb subcells grown on
GaAs substrates under compressive strain (triangles) and tensile
strain (diamonds). It can be seen that the subcells under
compressive strain have consistently higher open circuit voltages
than those under tensile strain.
[0027] Low Sb, enhanced In and N, compressively-strained GaInNAsSb
subcells have been successfully integrated into high efficiency
multijunction solar cells. FIG. 5 shows a current-voltage curve of
a triple junction solar cell of the structure in FIG. 1A under
AM1.5D illumination equivalent to 1 sun. The efficiency of this
device is 30.5%. FIG. 6 shows the current-voltage curve of the
triple junction solar cell operated under a concentration
equivalent to 523 suns, with an efficiency of 39.2%.
[0028] The invention has been explained with reference to specific
embodiments. Other embodiments will be evident to those of ordinary
skill in the art. It is therefore not intended for the invention to
be limited, except as indicated by the appended claims.
* * * * *