IEE/CEEM Seminar: Richard King and Novel Semiconductor Materials For High-Efficiency Multijunction Photovoltaics

Novel Semiconductor Materials for High-Efficiency Multijunction Photovoltaics
Richard R. King Spectrolab, Inc.

Sylmar, CA
R. R. King, University Seminar, 2014
Novel Semiconductor Materials for High-Efficiency Multijunction Photovoltaics

Richard R. King Spectrolab, Inc.
Sylmar, CA
Seminar University of California, Santa Barbara

Jan. 24, 2014
Acknowledgments
Manuel Romero, Sarah Kurtz, Dan Friedman, Daryl Myers, Tom Moriarty, Keith Emery NREL Angus Rockett Univ. of Illinois Gerald Siefer CalLab, Fraunhofer ISE Geoff Kinsey Fraunhofer CSE Rosina Bierbaum Univ. of Michigan Russ Jones, Jim Ermer, Chris Fetzer, Abdallah Zakaria, Xing-Quan Liu, Daniel Law, Philip Chiu, Shoghig Mesropian, Xiaogang Bai, Dimitri Krut, Kent Barbour, Mark Takahashi, Andrey Masalykin, John Frost, Nasser Karam ...and the entire multijunction solar cell team at Spectrolab
R. R. King, UCSB Seminar, Jan. 24, 2014
Outline
700
Intensity per Unit Photon Energy (W/m 2 . eV)
600 500 400 300 200 100 0 0 0.5 1
0.8 0.6 0.4 0.2 0 1.5 2 2.5 Photon Energy (eV) 3 3.5 4
Solar cell efficiency limits
Unifying behavior in semiconductor energy levels Electronic activity of defects in different semiconductor families Multijunction solar cells and concentrator photovoltaics (CPV)
Photon utilization efficiency
Big Picture
AM1.5D, ASTM G173-03, 1000 W/m2 1.4 Utilization efficiency of photon energy 1-junction cell 3-junction cell 1.2 6-junction cell
Big Picture
Climate Change Temperature Anomaly by Year

1000 years of Earth temperature history and 100 years of projection
IPCC (2001) scenarios to 2100
Rosina Bierbaum, Univ. of Michigan Intergovernmental Panel on Climate Change (IPCC)
Fossil fuels are contributing to global climate change at alarming rate Further, dependence on imported fuels has a high toll in terms of political stability and national security
R. R. King, UCSB Seminar, Jan. 24, 2014 6
Concentrator Photovoltaics (CPV) using high-efficiency III-V 3-junction solar cells
Courtesy Amonix Cogentrix, Alamosa, CO 30 MW, III-V multijunction cells
Photovoltaic solar electricity combined with... power storage in plug-in hybrid vehicles long-distance power transmission from sunny locales to high-demand areas offer a major part of a solution to these problems
Solar cell efficiency limits
Shockley and Queisser (1961)
Detailed Balance Limit of Solar Cell Efficiency
Singlejunction solar cell
30% efficient single-gap solar cell at one sun, for 1 e-/photon 44% ultimate efficiency for device with single cutoff energy
Photon Utilization Efficiency 1-Junction Solar Cells

700
AM1.5D, ASTM G173-03, 1000 W/m2 1.4 Utilization efficiency of photon energy to bandgap Eg to Voc at 1000 suns 1.2 to Voc at 1 sun
600 500 400 300 200 100 0 0 0.5 1
0.8 0.6 0.4 0.2 0 1.5 2 2.5 Photon Energy (eV) 3 3.5 4

10
Assumptions Opportunities
Assumptions in Shockley and Quiesser (1961) Viewed from a different angle, these limitations represent opportunities for higher efficiency devices
Assumption limiting solar cell efficiency Single band gap energy One e--h+ pair per photon Device principle overcoming this limitation Multijunction solar cells Quantum well, quantum dot solar cells Down conversion Multiple exciton generation Avalanche multiplication Up conversion Hot carrier solar cells Intermediate-band solar cells Quantum well, quantum dot solar cells Concentrator solar cells
Non-use of sub-band-gap photons Single population of each charge carrier type
One-sun incident intensity
11
C. H. Henry (1980) Theoretical Efficiency of Multijunction Solar Cells
3-junction solar cell
Theo. efficiency at 1000 suns 1J: 37% 2J: 50% 3J: 56% 36J: 72%

700
AM1.5D, ASTM G173-03, 1000 W/m2 1.4 Utilization efficiency of photon energy 1-junction cell 3-junction cell 1.2
600 500 400 300 200 100 0 0 0.5 1
0.8 0.6 0.4 0.2 0 1.5 2 2.5 Photon Energy (eV) 3 3.5 4

13
Unifying behavior in semiconductor energy levels
14
Unifying trends of defect energy levels in different semiconductors

A number of phenomena have been observed indicating the tendency for some defect levels to form at a nearly constant energy in different semiconductors with respect to the vacuum level
Universal alignment of hydrogen levels in semiconductors Van de Walle and Neugebauer, Nature (2003) Bulk reference level in Cu(GaxIn1-x)(SySe1-y)2 semiconductors Turcu, Ktschau, and Rau,, J. Appl. Phys. (2002) Fermi-level stabilization energy Walukiewicz, Phys. Rev. B (1988) These observations indicate a common defect configuration at the atomic scale may be responsible for the near constancy of energy level in different semiconductors The position of common defect energies has the power to explain and predict doping properties and defect recombination activity in the same semiconductor family ( e.g., CuInSe2 and Cu(GaIn)(SSe)2 ) and in different families ( e.g., Cu(GaIn)(SSe)2 and GaInN )
15
Hydrogen energy levels in different host semiconductors
Hydrogen energy level (red bars) is at nearly constant level with respect to vacuum level when incorporated into a wide variety of semiconductors Applies to group-IV, III-V, and II-VI semiconductors, and even to electrolytes Van de Walle and Neugebauer, Nature, 2003
Unifying trends of defect energy levels in different semiconductors Questions:

To what extent and in what circumstances do the energy levels
of certain defects mirror the constancy of hydrogen atom states in different semiconductors?
Does this behavior establish the tendency for some types of

defects to form near a specified energy from the vacuum level?
17
Admittance Spectroscopy
Changes in capacitance with frequency and temperature extraction of defect energies and densities through admittance spectroscopy Leads to a clear picture of the evolution of spontaneously forming defect energies in Cu(GaxIn1-x)(SySe1-y)2 chalcopyrites with changing S and Ga composition Turcu, Ktschau, Rau, JAP, 2002
Similarity of defect energy levels in different chalcopyrites
Trap energies due to native defects in Cu(GaxIn1-x)(SySe1-y)2 are approximately constant with respect to group-VI composition in semiconductor Trap energies are closer to midgap for higher bandgap compositions leads to higher recombination at higher Eg challenge for finding high Eg top cell material for chalcopyrite-based multijunction cell Turcu, Ktschau, Rau, JAP, 2002
Unifying trends of defect energy levels in different semiconductors Questions:

To what extent and in what circumstances do the energy levels
of certain defects mirror the constancy of hydrogen atom states in different semiconductors?
Does this behavior establish the tendency for some types of

defects to form near a specified energy from the vacuum level?
To what degree does the reference bulk defect energy level

observed in I-III-VI chalcopyrites extend to other semiconductor families?
What does this behavior say about the recombination at

defects in different host semiconductors, especially the low recombination activity observed in materials such as CuInSe2 and GaInN?
Fermi-level stabilization energy
Fermi level stabilizes at nearly constant level with respect to vacuum level in a wide variety of semiconductors and semiconductor families Both for damage induced by radiation and at semiconductor surfaces Close to energy of hydrogen incorporated in semiconductors Fermi-level stabilization energy EFS is near midgap in GaAs and GaInP, but near conduction band in GaInN reduces recombination activity of states at EFS as In content goes up Walukiewicz, PRB, 1988; Li et al., PRB, 2005
Experimental and Theoretical Bandgap-Voltage Offset Woc

2.0
Voc and band gap-voltage offset Woc = (Eg/q) - Voc of solar cells with wide range of band gaps
measured Voc
Eg/q, Voc, and (Eg/q) - Voc (V)
meas. Eg from EQE Woc = (Eg/q) - Voc
1.5
radiative recomb. only detailed balance model
Ge (indirect gap)
1.0
0.79-eV GaInAs
0.97-eV GaInAs
Si (indirect gap)
1.10-eV GaInAs
1.24-eV GaInAs
1.30-eV GaInAs
GaInNAs
1.4 - eV GaInAs GaAs
AlGaInAs
AlGaInAs
Ref.: R. R. King et al., Prog. in PV, doi: 10.1002/pip.1044 (2010)
0.5
0.0 0.6 1 1.4 Band Gap Eg (eV) 1.8 2.2
Difference between bandgap and steady-state quasi-Fermi level splitting (opencircuit voltage) in solar cells is strikingly similar across wide range of III-V and groupIV semiconductors (as well as II-VI, I-III-VI, and other classes of semiconductors)
o-GaInP
d-AlGaInP
d-GaInP
d-AlGaInP
d-AlGaInP
Semiconductor Eqns. Formulated in Terms of Band Gap-Voltage Offset W W (E g q ) V
pn = n e
2 qV / kT i
pn = N C NV e qW / kT
kT N C N V W= ln q pn
kT pn ln V = 2 q ni
J o = J ph e qVoc / kT
J ph qWoc / kT Jo Ko 2 = e ni N C NV
Woc formulation has more physical basis, related to NC , NV rather than ni2 Far more invariant with respect to Eg , good for multiple subcells in MJ cells Makes Woc a convenient indicator of solar cell quality amount of SRH recombination vs. radiative recombination for wide range of Eg Ko Jo / ni2 has nearly all band gap dependence taken out
Unifying trends of defect energy levels in different semiconductors Each of these observations reveals a profound, unifying aspect of the fundamental nature of these materials Connections between defect energies in very different semiconductor systems may help identify fundamental principles behind the remarkably low defect recombination activity in some types of semiconductors, such as CuInSe2 and GaInN Finding answers to these questions will help us understand at a deeper level why we observe the semiconductor properties that we do
Electronic activity of defects in different semiconductor families
25
Electronic activity of defects in different semiconductor families Semiconductor growth and characterization Some interesting materials systems
Metamorphic III-Vs Dilute nitride GaInNAs(Sb) Polycrystalline I-III-VIs and related materials Chalcopyrites (CuvAg1-v)(AlxGayIn1-x-y)(SzSe1-z)2 e.g., CIGS Kesterite Perovskites Cu2ZnSn(S,Se)4 CH3NH3Pb(X)3 where X = Cl, Br, I
26
Organometallic Vapor-Phase Epitaxy (OMVPE)

H2
AsH3/Ph3
Chemical Reactor Chamber Low Pressure & High Temperature H2 + TMGa Scrubbed Hydrogen
H2
Sealed Bubbler containing MO source precursor
Crystal growth on substrates on heated rotating graphite Exhaust Gasses
Point Of Use Gas Scrubber
Typical Precursor Chemicals:

Ga H As P
In Te
Hydrogen, H2
Arsine, AsH3
Phosphine, PH3
Trimethylgallium or TMGa, Ga(CH3)3
Trimethylindium TMIn, In(CH3)3
Diethyltelluride DETe, Te(C2H5)2
27
Molecular Beam Epitaxy
28
Selenization and Sulfidation CIGS and CZTS
www.unk.edu/nss/chemistry.aspx?id=41606
auo.com/print.php?sn=192&lang=en-US onlinelibrary.wiley.com/doi/10.1002/cphc.v14.9/issuetoc
www.beltfurnaces.com/efficiency_of_CIGS.html
www.prweb.com/releases/Smit_ovens/CIGS/prweb2039344.htm
29
Recombination activity at defects

Characterization of energy levels, capture cross sections, density, and recombination activity of defects:
deep-level transient spectroscopy (DLTS) admittance spectroscopy, both in the dark and with photoexcitation time-resolved photoluminescence (TRPL) among others
Atomic reconstruction and bonding configuration of defects:

transmission electron microscopy (TEM) atom probe tomography (APT) atomic force microscopy (AFM) Fourier transform infrared spectroscopy (FTIR) other imaging and characterization tools
30
Metamorphic III-Vs
31
Terrestrial Conc. Cell Designs from 40% to 50%

2.0
C1 Eg
52%
C2 Eg C3 Eg C4 Eg C5 Eg
1.8
50% 48% 46% 44% 42% 40%
Subcell Band Gaps (eV)
1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2
C6 Eg MJ Cell Efficiency
metal gridline
38% 36% 34%
1.83-eV GaInP cell 1

(a)
3J LatticeMatched (LM) C3MJ+
(b)
3J Metamorphic (MM) low mismatch C4MJ
(c)
3J Metamorphic (MM) high mismatch
(d)
3J Inverted Metamorphic (IMM)
4J Meta4J Double1.35-eV GaInAs cell 2
(e)
(f)
(g)
5J LatticeMatched (LM) w. epitaxial Ge subcell
(h)
5J LatticeMatched (LM) w. GaInNAsSb subcell
(i)
5J LatticeMatched (LM) Semiconductor Bonded (SBT)
(j)
6J Triple-Grade Inverted Metamorphic (MMX3)
transparent buffer
morphic (MM) high mismatch
Grade Inverted Metamorphic (MMX2)
MJ Cell 39.42% Efficiency Change 0.0% in Power from C3MJ+
40.00% 1.5%
40.54% 2.8%
43.26% 9.7%
0.67-eV Ge cell 3 44.44% 47.87% and substrate

12.7% 21.4%
43.25% 9.7%
47.43% 20.3%
47.64% 20.9%
50.91% 29.2%
Efficiencies for AM1.5D, ASTM G173-03 spectrum, 50.0 W/cm2 (500 suns), 25C
Modeled production avg. efficiency of 40.0% at 500 suns (50.0 W/cm2)

MJ Cell Efficiency (%)
Cross sectional TEM Ga0.44In0.56P/ Ga0.92In0.08As/ Ge Cell
Low dislocation density in active cell layers in top portion of epilayer stack: ~2x from EBIC and CL meas. 105 cm-2
GaInAs cap
GaInP TC
Tunnel junction GaInAs MC
0.2 m
GaInAs graded buffer to 8%-In
Dislocations confined to graded buffer layers in bottom portion of epilayer stack
Misfit dislocations Pre-grade buffer
Ge substrate
0.2 m
High-Resolution XRD Reciprocal Space Map (RSM)

GaInP/ 8%-In GaInAs/ Ge metamorphic (MM) cell structure Nearly 100% relaxed stepgraded buffer removes driving force for dislocations to propagate into active cell layers 56%-In GaInP top cell pseudomorphic with respect to GaInAs middle cell
Line of 100% relaxation
Ge
Qy (Strain) -1
Graded Buffer
Ga0.92In0.08As MC GaInP TC
(115) glancing exit XRD

Qx (Tilt) -1 Line of 0% relaxation
34
Internal QE of Metamorphic GaInAs Cells on Ge

1.40 1.38 1.30 1.26
Metamorphic = "changed form"

100
Internal Quantum Efficiency (%)
90 80 70 60 50 40 30 20 10 0 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 Wavelength (nm)
35
GaInAs single-junction solar cells
1.6% lattice mismatch 2.4% lattice mismatch
1.08
0.96 eV
Dislocation Imaging in 23%-In GaInAs

23%-In GaInAs double heterostructure on Ge
20 m 1 m
Cathodoluminescence (CL) disloc. density = 4.4 x 106 cm-2
Plan-View Transmission Electron Microscopy (TEM) disloc. density = 3.1 x 106 cm-2
36
Dislocations in Inverted Metamorphic Cells EBIC
50 m
GaInAs comp. Latt. mismatch Disloc. density
8e-9766-1
50 m
8e-9756-1
50 m
8e-9760-1
50 m
8e-9783-11
1.39-eV ILM subcell

2% In 0.1% 2.5 x 105 cm-2
1.10-eV IMM subcell

23% In 1.6% 3.9 x 106 cm-2
0.97-eV IMM subcell

33% In 2.3% 5.0 x 106 cm-2
0.84-eV IMM subcell

44% In 3.1% 6.3 x 106 cm-2
metal contact
metal contact
metal contact
metal contact
1.39-eV GaInAs inverted LM subcell

base emitter
1.39-eV GaInAs
buffer layer
nucleation
1.10-eV GaInAs inverted MM subcell

base emitter
1.10-eV GaInAs
0.970.97-eV GaInAs inverted MM subcell

base emitter
0.97-eV GaInAs
0.840.84-eV GaInAs inverted MM subcell

base emitter
0.84-eV GaInAs
transparent MM graded buffer layers

nucleation and pre-grade buffer


Ge or GaAs substrate
Ge substrate
Ge substrate
Ge substrate
EBIC images and dislocation density of inverted metamorphic cell test structures
Dislocations in Inverted Metamorphic Cells

Lattice Mismatch Relative to Ge (%)
-0.07 0.64 1.36 2.07 2.79 3.51
9
Dislocation Density from EBIC (10 cm ) and Photon Intensity from CL (10 cps)
50
8 7
Inverted metamorphic (MM) GaxIn1-xAs solar cells

Dislocation density from EBIC Overall % photon intensity from CL % carrier loss at each dislocation from CL
-2
45 40 35 30 25
Carrier Loss (%)
Ref.: R. R. King et al., 23rd European Photovoltaic Solar Energy Conf., Valencia, Spain, Sep. 2008. 38
6 5 4
20 3 2 1 0 0 10 20 30 In Composition for Gax In1-x As (%)

15 10 5 0 40 50
Time-Resolved Photoluminescence: GaInP- and GaInAs-base DHs

AlGaInP/ GaInP/ AlGaInP double heterostructure
1000
Photoluminescence Intensity (arb. units)
Photoluminescence Intensity (arb. units)
10000
1000
eff = 47 ns
100
100
GaInP/ GaInAs/ GaInP double heterostructure

10
10
eff = 2450 ns
1
1 0 100 200 300 400 500
2000
4000
6000
8000
10000
Time (ns)
Time (ns)
Double heterostructures grown with AlGaInP/GaInP and GaInP/GaInAs interfaces, in stack similar to MJ cells TRPL measurements at NREL Minority-carrier lifetime up to 2450 ns in 1%-In GaInAs on Ge substrate
Time-Resolved PL of LM & MM Double Heterostructures

10000
Eg = 1.407 eV Base Material Recent data nid-GaInAs, recent data p-GaInP (disordered) Previous data nid-GaInAs nid-GaInP (ordered) nid-GaInP (disordered)
eff Measured by TRPL (ns)
1000
100
1.813 eV 1.887 eV 1.311 eV 1.114 eV 0.994 eV
10
1.736 eV 1.619 eV 1.807 eV 1.529 eV
0.1 0 5 10 15 20 25 30 35
Indium Mole Fraction of GaInAs Lattice-Matched to Base (%)
40
Sublattice ordering
41
Group-III Sublattice Ordering

all In all Ga
[001] (111) planes
Ga0.5In0.5P
fully ordered (order parameter = 1) CuPtB ordering on [111] or [111] planes
all In
In practice: = 0.4-0.5 , Eg 1.8 eV for GaInP lattice matched to GaAs Eg() = Eg(0) - (0.471 eV)2
[100] P Ga In
[010]
Group-III Sublattice Ordering

random Ga & In
random Ga & In
[001] (111) planes
Ga0.5In0.5P
fully disordered (order parameter = 0) No CuPtB ordering
random Ga & In
In practice: = 0.0-0.1 , Eg 1.9 eV for GaInP lattice matched to GaAs Bandgap difference with respect to ordered GaInP occurs in conduction band Ec
[100] P Ga In
[010]
43
Surface Reconstruction of GaInP
[110] cross-section of disordered GaInP epilayer showing [110]-oriented P dimers of the (2 x 4) reconstruction.
The stresses caused in in the growing crystal by surface phosphorus atoms provide the thermodynamic driving force for ordering.
44
Direct Meas. of GaInP Ordering from (115) XRD Peak

160
1.813 eV
(115) XRD Intensity Due to Group-III 1/2(115) XRD Intensity due to Group-III Sublattice Ordering in GaInP (counts/s) Ordering in GaInP (counts/s)
140 120 100 80 60 40 20 0

-2 0 0 2 2 4 -2 6 0
GaInP Ordering State and Lattice Match to GaInAs ordered, GaInP LM to 1%-In GaInAs partially disordered, " disordered, " ordered, GaInP LM to 8%-In GaInAs disordered, "
1.736 eV 1.867 eV 1.807 1.887 eV
-2 10
0 12
2 14
Relative Omega, referenced to 1%-In GaInAs Peak (degrees)
45
Dilute nitride GaInNAs(Sb)
46

2.0
C1 Eg
52%
1.8
50% 48% 46% 44%
1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2
metal gridline
42% 40% 38%
2.00-eV AlGaInP cell 1 1.71-eV AlGaInAs cell 2 1.40-eV GaInAs cell 3

(a)
36% 34%
(b)
(c)
(d)
(e)
(f)
4J DoubleGrade Inverted Metamorphic (MMX2)
1.12-eV GaInNAsSb cell 4 5J Lattice5J Lattice5J LatticeMatched (LM) Matched (LM) Matched (LM) 0.67-eV cell Semiconductor 5 w. epitaxial Ge w.Ge GaInNAsSb subcell subcell Bonded (SBT) and substrate
43.25% 9.7% 47.43% 20.3% 47.64% 20.9%
(g)
(h)
(i)
(j)
40.00% 1.5%
40.54% 2.8%
43.26% 9.7%
44.44% 12.7%
47.87% 21.4%
50.91% 29.2%


Two defect levels consistently seen in GaInNAs by DLTS Electron trap stays at 0.9-1.0 eV above valence band as N is added and Eg decreases Electron trap becomes quite shallow for N compositions near 1 eV 2nd defect level follows lowering of conduction band as N is added stays near midgap and acts as effective recombination center
Ptak et al., NREL PRM, 2003

Presence of H greatly decreases formation energy of (N-H-VGa)2defect complex Acts as acceptor May be one of the main fundamental defects in GaInNAs(Sb) Positron annihilation spectroscopy shows increased VGa in MBEgrown nitride in the presence of H
Ptak et al., NREL PRM, 2003
Quantum efficiencies well above 90% and comparable to those for GaAs can be achieved for a range of N compositions and bandgaps in GaInNAs(Sb) grown by MBE These current densities are high enough to contribute usefully to high-efficiency multijunction solar cells
Ptak et al., JAP, 2005

Dilute nitride GaInNAs grown by MOVPE can have high measured quantum efficiencies Annealing and thermal history have a strong influence on the quality of dilute nitride GaInNAs(Sb)
Volz et al., JCG, 2008

0.2% N 2.5% In
FTIR spectra of Ga0.975In0.025N0.002As0.998 (2.5% In) N primarily bound to Ga in Ga4N configuration before anneal (467 cm-1) Higher fraction of N bound to In in Ga3InN configuration after anneal greater mass of In causes lower vibrational frequency signal (457 cm-1) Evidence for H forming bonds with N in GaInNAs change upon annealing may be due to change from NH to NH2 defect complex Kurtz et al., APL, 2001
Probability of N finding In-N nearest neighbor environment much higher for greater In compositions in GaInNAs Change in N bonding environment also thought to be cause of blueshift in fundamental bandgap of GaInNAs upon annealing ~20 mV per additional indium atom in bonding configuration Volz et al., JCG, 2008

Chain-like columnar nitrogen ordering in the [001] direction causes local strain fluctuations as seen in strain sensitive (202) dark field TEM images Nitrogen chains are broken up resulting in more homogeneous strain in GaInNAs with increasing anneal schedule in images (a), (b), (c)
Volz et al., JCG, 2008
Chalcopyrites
Cu(In,Ga)Se2 (CIGS) and more

The CIGS Device

Light absorbing layer: a Cu(In,Ga)Se2 alloy Remarkably low recombination at extended defects Alternate window (emitter) layers available Back contact: nearly always Mo for stability
Angus Rockett U. Illinois

The Real Device

Devices are thought to be limited by recombination in the depletion region, not by heterojunction recombination.
What is the major recombination center? What do grain boundaries do? Why does CuGaSe2 not work well? Why do some growth processes work better than others?
TEM image
Schematic
Chalcopyrite CIGS
Disordering energy is low so there are many point defects A polar compound so charged surfaces could be a problem
In
Yet:
Se
Extended defects inactive Polar surfaces most stable Hole mobility phonon limited for p to >1019 cm-3 Polycrystalline devices work better than single crystals Angus Rockett U. Illinois
(220)/(204) Oriented CIGS

Layers facet spontaneously into polar (112) type planes Smooth facets alternate with rough facets Indexing surface planes shows smooth planes are metal terminated
(220)/(204) epitaxial layer AFM image
Conclusion: Somehow the polar surfaces are stabilized, giving a very strong preference for these.
Red: metal terminated Blue: Se terminated

59
(112)A
(112)B
Conclusions of all of this
CIGS solar cells

Are heterojunction devices with a very strongly inverted junction (Cd doping overwhelms Fermi level pinning). Do not mind grain boundaries because they are highly faceted to extremely passive (112) surfaces. Heterojunction is made to these surfaces regardless of grain orientation. Point defects control doping in the bulk and are very consistent. Edge dislocations do not matter because they turn into (112) surfaces.
Perovskites
61
Perovskite solar cells
Present perovskite-based solar cells evolved from dye-sensitized solar cell (DSSC) technology Perovskite CH3NH3PbClxI3-x absorbers have very high absorption coefficients allowing thin, practical layers to be used Very simple processing
Much of electron and hole transport can take place through the perovskite light absorber material itself, rather than through the porous TiO2 scaffold used in DSSCs Perovskite cells work even better with insulating porous Al2O3 scaffold, avoiding voltage loss of 0.2-0.3 V from lower conduction band of TiO2 External quantum efficiency (incident photon-to-electron conversion efficiency, or IPCE) of two types of perovskite absorbers, with bandgaps of ~2.2 and 1.55 eV >12% 1-sun eff. using porous Al2O3 scaffold, 15% with vapor-deposited perovskite
Snaith, JPCL, 2013

High Eg of perovskites (2.2 eV for CH3NH3PbBr3 to 1.55 eV for CH3NH3PbI3 ) a good match for top cell of flat-plate, one-sun multijunction with silicon, Cu(GaxIn1-x)(SySe1-y)2 or kesterite Cu2ZnSn(S,Se)4 bottom cell Snaith, JPCL, 2013
Multijunction solar cells and concentrator photovoltaics (CPV)
65
Lattice-Matched and Metamorphic Cell Structure
66
Record efficiency III-V multijunction solar cells
67
Record 40.7%-Efficient Concentrator Solar Cell

First solar cell of any type to reach over 40% efficiency
Spectrolab Metamorphic GaInP/ GaInAs/ Ge Cell
Voc Jsc FF Vmp = = = = 2.911 V 3.832 A/cm2 87.50% 2.589 V
Efficiency = 40.7% 2.4%

240 suns (24.0 W/cm2) intensity 0.2669 cm2 designated area 25 1C, AM1.5D, low-AOD spectrum
Efficiencies have now reached 41.6% for both metamorphic and lattice-matched 3-junction cells
Ref.: R. R. King et al., "40% efficient metamorphic GaInP / GaInAs / Ge multijunction solar cells," Appl. Phys. Lett., 90, 183516, 4 May 2007.
Concentrator cell light I-V and efficiency independently verified by J. Kiehl, T. Moriarty, K. Emery NREL
External QE of LM and MM 3-Junction Cells
69

Solar Junction 3-junction cell with dilute nitride bottom cell
70
3-junction record efficiency cell with dilute nitride bottom cell
metal gridline
Solar Junction 44.0% eff.

AM1.5D under concentration NREL confirmed
1.89-eV GaInP cell 1 1.42-eV GaAs cell 2 ~1-eV GaInNAs(Sb) cell 3
www.semiconductor-today.com/news_items/2012/OCT/SOLARJUNCTION_151012.html R. R. King, UCSB Seminar, Jan. 24, 2014 71

Soitec/Fraunhofer ISE 4-junction semiconductor bonded cell
72
4-junction record efficiency semiconductor bonded cell

bonded interface
metal gridline
Fraunhofer ISE/ Soitec 44.7% eff.

AM1.5D under concentration Fraunhofer ISE confirmed
(Al)GaInP cell 1 GaAs cell 2 GaInPAs cell 3 GaInAs cell 4
www.ise.fraunhofer.de/en/press-and-media/press-releases/presseinformationen-2013/world-record-solar-cell-with-44.7-efficiency R. R. King, UCSB Seminar, Jan. 24, 2014 73
Record Efficiency One-Sun SBT 5-Junction Cell

Spectrolab 5-junction semiconductor bonded cell, 1-sun, AM1.5G
38.8%
D. Law, P. Chiu et al., to be published

5-junction record 1-sun efficiency semiconductor bonded cell

semiconductor bonded interface
metal gridline
Spectrolab 38.8% eff.

AM1.5G, 1-sun cell NREL confirmed
2.0-eV AlGaInP cell 1 1.7-eV AlGaInAs cell 2 1.4-eV GaInAs cell 3 1.1-eV GaInPAs cell 4 0.75-eV GaInAs cell 5
75
Semiconductor-Bonded Technology (SBT) Terrestrial Concentrator Cell
Direct semiconductor bonding for multijunction solar cells semi Both high-bandgap and low-bandgap cell sets use high-quality, lattice-matched materials Atomically abrupt semiconductor bonded 1.4-eV GaInAs cell 3 interface Both small-lattice 2.0-eV AlGaInP cell 1 (GaAs) and large-lattice (InP) growth substrates GaAs or Ge can be growth reused after substrate substrate removal
1.7-eV AlGaInAs cell 2 conductor bonded interface
GaAs or Ge metal gridline growth substrate GaAs or Ge growth substrate 2.0-eV AlGaInP cell 1 2.0-eV AlGaInP cell 1 1.7-eV AlGaInAs cell 2 1.7-eV AlGaInAs cell 2 1.4-eV GaInAs cell 3 1.4-eV GaInAs cell 3 1.1-eV GaInPAs cell 4 0.75-eV GaInAs cell 5
InP growth substrate
76
Record Efficiency One-Sun SBT 5-Junction Cell

Fabricated preliminary SBT AM1.5G cell under IR&D leveraging knowledge from SBT space cells. Record Efficiency = 38.83% Spectrolabs SBT terrestrial cell achieved efficiency of 37.8%, 1-sun, AM1.5G (then world record) in April 2013.
Recently achieved new world record efficiency of 38.8%, 1-sun, AM1.5G in August 2013
Highest efficiency 1-sun terrestrial solar cell of any type. Expect Eff. > 47% at moderate concentrations
Chiu et al., PVSC, 2013


2.0
C1 Eg
52%
1.8
50% 48% 46% 44%
1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2
metal gridline
42% 40% 38%
2.00-eV AlGaInP cell 1 1.71-eV AlGaInAs cell 2 1.40-eV GaInAs cell 3

(a)
36% 34%
(b)
(c)
(d)
(e)
(f)
1.12-eV GaInNAsSb cell 4 5J Lattice5J Lattice5J LatticeMatched (LM) Matched (LM) Matched (LM) 0.67-eV cell Semiconductor 5 w. epitaxial Ge w.Ge GaInNAsSb subcell subcell Bonded (SBT) and substrate
43.25% 9.7% 47.43% 20.3% 47.64% 20.9%
(g)
(h)
(i)
(j)
40.00% 1.5%
40.54% 2.8%
43.26% 9.7%
44.44% 12.7%
47.87% 21.4%
50.91% 29.2%

5-junction nitride solar cell measured light I-V

14 12
Current Density (mA/cm )
10 8 6 4 2 0 0 1 2 3 4 5
4J, no nitride, EQE Jsc, no AR 20.2% 4J, no nitride, IQE Jsc 5J nitride, EQE Jsc, no AR 5J nitride, IQE Jsc 29.8% eff. 22.2% 32.4% eff.
AM0 efficiency projected from QP cells, no AR
Voltage (V)
Addition of dilute nitride GaInNAs cell to 5-junction stack adds ~400 mV open-circuit voltage to cell at one sun
5-junction nitride solar cell measured quantum efficiency

100 90
Quantum Efficiency (%)
80 70 60 50 40 30 20 10 0 300
IQE 12.0 12.3 12.1 13.3 17.6

mA/cm 2
500
700
900
Wavelength (nm)
1100
1300
1500
1700
1900
80

2.0
C1 Eg
52%
1.8
50% 48%
1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2
gr Ge o ow th r Ga su As bs t ra te metal
gridline
46% 44% 42% 40% 38%
2.00-eV AlGaInP cell 1 1.77-eV AlGaAs cell 2 1.465-eV AlGaAs cell 3

(a)
36% 34%
(b)
(c)
(d)
(e)
(f)
(g) (h) transparent buffer
(i)
5J LatticeMatched (LM) Semiconductor Bonded (SBT)
(j)
1.20-eV GaInAs cell 4

transparent buffer
5J LatticeMatched (LM) w. epitaxial Ge subcell
5J LatticeMatched (LM) w. GaInNAsSb subcell
40.00% 1.5%
40.54% 2.8%
43.26% 9.7%
44.44% 12.7%
47.87% 21.4%
0.97-eV cell 547.64% 43.25% GaInAs 47.43%

transparent buffer
50.91% 29.2%
9.7% GaInAs 20.3% 0.70-eV cell 6 20.9%


700
AM1.5D, ASTM G173-03, 1000 W/m2 1.4 Utilization efficiency of photon energy 1-junction cell 3-junction cell 1.2
600 500 400 300 200 100 0 0 0.5 1
0.8 0.6 0.4 0.2 0 1.5 2 2.5 Photon Energy (eV) 3 3.5 4

82

700
AM1.5D, ASTM G173-03, 1000 W/m2 1.4 Utilization efficiency of photon energy 1-junction cell 3-junction cell 1.2 6-junction cell
600 500 400 300 200 100 0 0 0.5 1
0.8 0.6 0.4 0.2 0 1.5 2 2.5 Photon Energy (eV) 3 3.5 4

83
Quantum efficiency of subcells in 6-junction cell

100
1.91-eV GaInP Cell 1 EQE
80
60
40
20
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 Photon Energy (eV)

100
1.91-eV GaInP Cell 1 EQE 1.81-eV GaInP Cell 2 EQE
80
60
40
20
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 Photon Energy (eV)

100
1.91-eV GaInP Cell 1 EQE 1.81-eV GaInP Cell 2 EQE 1.57-eV AlGaInAs Cell 3 EQE
80
60
40
20
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 Photon Energy (eV)

100
1.91-eV GaInP Cell 1 EQE 1.81-eV GaInP Cell 2 EQE 1.57-eV AlGaInAs Cell 3 EQE 1.39-eV GaInAs Cell 4 EQE
80
60
40
20
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 Photon Energy (eV)

100
1.91-eV GaInP Cell 1 EQE 1.81-eV GaInP Cell 2 EQE 1.57-eV AlGaInAs Cell 3 EQE 1.39-eV GaInAs Cell 4 EQE 1.05-eV GaInNAs Cell 5 EQE
80
60
40
20
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 Photon Energy (eV)

100
1.91-eV GaInP Cell 1 EQE 1.81-eV GaInP Cell 2 EQE 1.57-eV AlGaInAs Cell 3 EQE 1.39-eV GaInAs Cell 4 EQE 1.05-eV GaInNAs Cell 5 EQE 0.67-eV Ge Cell 6 EQE 6J, cumulative EQE
80
60
40
20
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 Photon Energy (eV)
Concentrator Cell Receivers
MJ Solar Cell
Bypass Diode
Metallized Substrate
Individual cells mounted on individual substrates, each with a bypass diode Suitable for point focus modules
Case Study 1: Soitec Concentrix Technology
Courtesy Soitec
Soitec Concentrix Technology
Concentration ratio ~500 High efficiency cells based on III-V materials Fresnel lens as primary optics
Courtesy Soitec
Case Study 2: Solar Systems
Dense array, active cooling
Courtesy Solar Systems Pty Ltd, Australia

Solar Systems
Courtesy Solar Systems Pty Ltd, Australia, Photo: Pierre Verlinden

Summary and Future Prospects

Fossil fuels contributing to global climate change at alarming rate Multijunction cells break Shockley-Queisser single-junction efficiency limits Wide range of semiconductor bandgaps needed with low recombination Unifying behavior in semiconductor energy levels offers deeper experimental and theoretical understanding of universal patterns in formation of defect energy levels across broad classes of semiconductors Will provide framework to understand and better use inherently low defect recombination activity in certain polar covalent semiconductors, in families represented by CuInSe2, GaInN, and Cu2ZnSn(S,Se)4 Novel semiconductor materials enable a zoo of new multijunction solar cells with efficiencies ranging over
50%
for cost-effective
Path to 50% efficiency promises to open wide geographic regions photovoltaics
Efficiency advantage of 4, 5, and 6J cells outweighs the effect of variable spectrum on current balance New understanding of defect structure in semiconductor families such as chalcopyrite, kesterite, and perovskite materials will enable advances in wide-bandgap top cells for flat-plate multijunction cells, bringing together the high efficiency of multijunctions with thin-film technology for low-cost solar electricity
96

IEE/CEEM Seminar: Richard King and Novel Semiconductor Materials For High-Efficiency Multijunction Photovoltaics

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IEE/CEEM Seminar: Richard King and Novel Semiconductor Materials For High-Efficiency Multijunction Photovoltaics

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Novel Semiconductor Materials for High-Efficiency Multijunction Photovoltaics

Richard R. King Spectrolab, Inc.

R. R. King, University Seminar, 2014

Novel Semiconductor Materials for High-Efficiency Multijunction Photovoltaics

Seminar University of California, Santa Barbara

R. R. King, University Seminar, 2014

R. R. King, UCSB Seminar, Jan. 24, 2014

600 500 400 300 200 100 0 0 0.5 1

Solar cell efficiency limits

Photon utilization efficiency

R. R. King, UCSB Seminar, Jan. 24, 2014

R. R. King, UCSB Seminar, Jan. 24, 2014

Climate Change Temperature Anomaly by Year

IPCC (2001) scenarios to 2100

Rosina Bierbaum, Univ. of Michigan Intergovernmental Panel on Climate Change (IPCC)

Concentrator Photovoltaics (CPV) using high-efficiency III-V 3-junction solar cells

Courtesy Amonix Cogentrix, Alamosa, CO 30 MW, III-V multijunction cells

Solar cell efficiency limits

R. R. King, UCSB Seminar, Jan. 24, 2014

Shockley and Queisser (1961)

Detailed Balance Limit of Solar Cell Efficiency

Singlejunction solar cell

Photon Utilization Efficiency 1-Junction Solar Cells

600 500 400 300 200 100 0 0 0.5 1

Photon utilization efficiency

R. R. King, UCSB Seminar, Jan. 24, 2014

Non-use of sub-band-gap photons Single population of each charge carrier type

One-sun incident intensity

R. R. King, UCSB Seminar, Jan. 24, 2014

C. H. Henry (1980) Theoretical Efficiency of Multijunction Solar Cells

3-junction solar cell

Photon Utilization Efficiency 3-Junction Solar Cells

600 500 400 300 200 100 0 0 0.5 1

Photon utilization efficiency

R. R. King, UCSB Seminar, Jan. 24, 2014

Unifying behavior in semiconductor energy levels

R. R. King, UCSB Seminar, Jan. 24, 2014

Unifying trends of defect energy levels in different semiconductors

R. R. King, UCSB Seminar, Jan. 24, 2014

Hydrogen energy levels in different host semiconductors

Unifying trends of defect energy levels in different semiconductors Questions:

Does this behavior establish the tendency for some types of

R. R. King, UCSB Seminar, Jan. 24, 2014

Similarity of defect energy levels in different chalcopyrites

Unifying trends of defect energy levels in different semiconductors Questions:

Does this behavior establish the tendency for some types of

To what degree does the reference bulk defect energy level

What does this behavior say about the recombination at

Fermi-level stabilization energy

Experimental and Theoretical Bandgap-Voltage Offset Woc

Eg/q, Voc, and (Eg/q) - Voc (V)

meas. Eg from EQE Woc = (Eg/q) - Voc

radiative recomb. only detailed balance model

1.4 - eV GaInAs GaAs

Ref.: R. R. King et al., Prog. in PV, doi: 10.1002/pip.1044 (2010)

0.0 0.6 1 1.4 Band Gap Eg (eV) 1.8 2.2

Semiconductor Eqns. Formulated in Terms of Band Gap-Voltage Offset W W (E g q ) V

Electronic activity of defects in different semiconductor families

R. R. King, UCSB Seminar, Jan. 24, 2014

R. R. King, UCSB Seminar, Jan. 24, 2014

Organometallic Vapor-Phase Epitaxy (OMVPE)

Sealed Bubbler containing MO source precursor

Crystal growth on substrates on heated rotating graphite Exhaust Gasses