Photonics for High-efficiency Crystalline Silicon Solar Cells Stefan Glunz Fraunhofer Institute for Solar Energy Systems ISE Workshop “Nanophotonics essential ingredient for efficient and cost-effective solar cells?” EU-PVSEC, Paris, Sept. 2013 © Fraunhofer ISE AGENDA Crystalline Silicon: How to handle an indirect semiconductor? Theoretical efficiency limit Light absorption Increasing light absorption: Classical approaches Pyramids Internal reflection layers Increasing light absorption: New concepts Plasmonic structure Diffractive optics Using the full spectrum Up-conversion 2 © Fraunhofer ISE, S. W.Glunz, September 2013 AGENDA Crystalline Silicon: How to handle an indirect semiconductor? Theoretical efficiency limit Light absorption Increasing light absorption: Classical approaches Pyramids Internal reflection layers Increasing light absorption: New concepts Plasmonic structure Diffractive optics Using the full spectrum Up-conversion 3 © Fraunhofer ISE, S. W.Glunz, September 2013 Shockley-Queisser-Limit Maximum efficiency as function of bandgap Detailed balance between sun (temp. T1) and solar cells (temp. T2) 0.35 Maximum efficiency ~ 33% 0.30 High non-absorption for high band gap energy Efficiency High thermalization for low band gap energy GaAs 0.20 mc-Si InP CdTe 0.15 Actual record efficiency of GaAs closer to limit than Silicon 0.00 0.5 © Fraunhofer ISE, S. W.Glunz, September 2013 Record Efficiencies c-Si 0.10 4 Shockley-Queisser 0.25 Silicon and GaAs are close to the optimum band gap Why? Non-absorption Thermalization 0.05 a-Si GaSb AlGaAs Ge 1.0 1.5 EG [eV] 2.0 2.5 Shockley-Queisser-Limit Other recombination channels Ideal solar cell has only radiative recombination (Shockley and Queisser, J. Appl. Phys. 1961) But silicon is an indirect semiconductor therefore direct recombination has no high probability (three particle process) Radiative recombination in an indirect semiconductor 5 © Fraunhofer ISE, S. W.Glunz, September 2013 Shockley-Queisser-Limit Other recombination channels Ideal solar cell has only radiative recombination (Shockley and Queisser, J. Appl. Phys. 1961) But silicon is an indirect semiconductor therefore direct recombination has no high probability (three particle process) In silicon solar cells Auger recombination (non-radiative) is limiting loss mechanism. 6 © Fraunhofer ISE, S. W.Glunz, September 2013 Auger recombination process in an indirect semiconductor What is the maximum efficiency? Including Auger recombination Shockley, Queisser (1961): Efficiency limit of solar cell made of one material = 33% (AM1.5) Theoretical efficiency for silicon = 29.4%1 Best silicon cell = 25% 85% of theoretical efficiency! 1Richter, 7 © Fraunhofer ISE, S. W.Glunz, September 2013 Hermle, Glunz et al., IEEE J. Photovolt. (2013) What is the maximum efficiency? Including Auger recombination Theoretical efficiency for silicon = 29.4%1 Best silicon cell = 25% 85% of theoretical efficiency! Shockley-Queisser 0.35 Record Efficiencies 0.30 Efficiency Shockley, Queisser (1961): Efficiency limit of solar cell made of one material = 33% (AM1.5) GaAs 0.25 c-Si 0.20 mc-Si InP CdTe 0.15 0.10 0.05 0.00 0.5 a-Si GaSb Ge 1.0 1.5 EG [eV] 8 © Fraunhofer ISE, S. W.Glunz, September 2013 AlGaAs 2.0 2.5 AGENDA Crystalline Silicon: How to handle an indirect semiconductor? Theoretical efficiency limit Light absorption Increasing light absorption: Classical approaches Pyramids Internal reflection layers Increasing light absorption: New concepts Plasmonic structure Diffractive optics Using the full spectrum Up-conversion 9 © Fraunhofer ISE, S. W.Glunz, September 2013 Light absorption Indirect semiconductors as silicon exhibit a low absorption for photons with energies around the band gap energy IR P. Würfel, Physik der Solarzellen 10 © Fraunhofer ISE, S. W.Glunz, September 2013 UV AGENDA Crystalline Silicon: How to handle an indirect semiconductor? Theoretical efficiency limit Light absorption Increasing light absorption: Classical approaches Pyramids Internal reflection layers Increasing light absorption: New concepts Plasmonic structure Diffractive optics Using the full spectrum Up-conversion 11 © Fraunhofer ISE, S. W.Glunz, September 2013 Light trapping in thin silicon solar cells Reduction of direct reflection due to multiple chances to enter the cell Oblique path of light increases optical thickness D. Kray, M. Hermle, and S. W. Glunz, Progress in Photovoltaics 16 (2008) 12 © Fraunhofer ISE, S. W.Glunz, September 2013 Light trapping in thin silicon solar cells Perfect scattering Goetzberger, IEEE-PVSC 1981: Perfect rear scatterer (Lambertian) Yablonovitch, J. Opt. Soc. 1982: Absorption enhancement limit 4n2 J. Eisenlohr, Diploma Thesis, Uni Freiburg (2012) 13 © Fraunhofer ISE, S. W.Glunz, September 2013 High-efficiency cells with dielectrically passivated rear Rear reflector Optimized Cell with improved optical and electrical performance Rear passivation layer serves as internal reflector (low n) - + Passivation Layer (SiO2, Al2O3/SiNX) Reduced Contact Area 14 © Fraunhofer ISE, S. W.Glunz, September 2013 - + Cell parameters as a function of thickness 21.5 21.0 Diffusion length (Material quality) High (L>> 250 μm) Medium (L 250 μm) Low (L<< 250 μm) [%] 20.5 20.0 19.5 19.0 18.5 18.0 0 50 100 150 200 250 Thickness [µm] Thin cells can improve electrical characteristics (carrier confinement) But: Light trapping has to be excellent! 15 © Fraunhofer ISE, S. W.Glunz, September 2013 Cell parameters as a function of thickness Measurement can be described by parameters extracted from test structures 2 Short-circuit current Jsc [mA/cm ] Short-circuit current as a function of cell thickness of a PERC cell on high-quality material 40 39 38 37 Measurement Simulation 36 0 50 100 150 200 250 Cell Thickness W [µm] Thin cells can improve electrical characteristics (carrier confinement) But: Light trapping has to be excellent! 16 © Fraunhofer ISE, S. W.Glunz, September 2013 Ultra-thin high-efficiency cells 20.2% on 37 μm thin wafer using LFC technology 750 mV with HIT cell structure by Sanyo/Panasonic on 98 μm thickness S.W. Glunz, Sol. Energy and Solar Cells 90 (2006) 17 © Fraunhofer ISE, S. W.Glunz, September 2013 AGENDA Crystalline Silicon: How to handle an indirect semiconductor? Theoretical efficiency limit Light absorption Increasing light absorption: Classical approaches Pyramids Internal reflection layers Increasing light absorption: New concepts Plasmonic structure Diffractive optics Using the full spectrum Up-conversion 18 © Fraunhofer ISE, S. W.Glunz, September 2013 Improving light absorption Plasmonics Scattering at metal nanoparticles at front longer effective path length Metal nanoparticles Corrugated embedded in semiconductor/metal semiconductor back surface Near–field longer effective excitation of carriers path length Atwater and Polman, Nature Materials 9 (2010) 19 © Fraunhofer ISE, S. W.Glunz, September 2013 Improving light absorption Plasmonics Plasmonic on rear side: Only small wavelength range has to be considered Less parasitic absorption in Ag particles possible Separation of Ag particles from semiconductor by thin passivation layer (e.g. Al2O3) Better electrical performance Uniform size distribution crucial Jüchter et al., EUPVSEC (2013) 20 © Fraunhofer ISE, S. W.Glunz, September 2013 Fabrication of Nanoparticles Interference Lithography, Imprint, Metallization, Lift-off Interference lithography masters up to m2 possible Uniform distribution of particle size achieved Proof of concept at cell level under investigation ~31 nm ~150 nm Jüchter et al., EUPVSEC (2013) 21 © Fraunhofer ISE, S. W.Glunz, September 2013 AGENDA Crystalline Silicon: How to handle an indirect semiconductor? Theoretical efficiency limit Light absorption Increasing light absorption: Classical approaches Pyramids Internal reflection layers Increasing light absorption: New concepts Plasmonic structures Diffractive optics Using the full spectrum Up-conversion 22 © Fraunhofer ISE, S. W.Glunz, September 2013 Increasing light absorption Diffractive rear surfaces Heine and Morf, Applied Optics 34 (1995) Diffractive optics But: Structuring of silicon can increase surface recombination Heine and Morf, Applied Optics 34 (1995) 23 © Fraunhofer ISE, S. W.Glunz, September 2013 Increasing light absorption Diffractive rear surfaces Diffractive allows longwavelength light to be redirect in very shallow angles incoming light emitter Optical properties decoupled from rear surface passivation diffracted light Optically rough, Electrically flat passivation Important especially for very thin cells diffractive rear side structure © Fraunhofer ISE, S. W.Glunz, September 2013 base rear side metal Janz et al., EU-PVSEC 2009 Voisin et al., EU-PVSEC 2009 24 antireflection layer Increasing light absorption Diffractive rear surfaces Optimization using rigorous coupled wave analysis (RCWA1) simulation Simulated photo current densities 2 photo current density [mA/cm ] 45 40 AM1.5g (280-1200nm) 35 front: planar (no ARC) - rear: mirror front: planar (DARC) - rear: mirror 30 25 front: planar (no ARC) - rear: perfect scatterer front: planar (DARC) - rear: perfect scatterer 20 15 10 front: inverted pyramids with SARC - rear: mirror front: planar (DARC) - rear: sphere grating 1 10 cell thickness [m] 1RCWA P. Lalanne, Reticolo 2D 25 © Fraunhofer ISE, S. W.Glunz, September 2013 100 Increasing light absorption Diffractive rear surfaces Realization by self-organized opaline structures Hexagonal photonic structure Deposition of ALD Al2O3 layer (surface passivation) Spin Coating of spherical nanoparticles (SiO2) Eisenlohr et al., EU-PVSEC 2011 26 © Fraunhofer ISE, S. W.Glunz, September 2013 Increasing light absorption Diffractive rear surfaces Realization by self-organized opaline structures Hexagonal photonic structure Deposition of ALD Al2O3 layer (surface passivation) Spin Coating of spherical nanoparticles (SiO2) Structure filled up using ALD of TiO2 (alternative SolGel) Eisenlohr et al., EUPVSEC (2013) 27 © Fraunhofer ISE, S. W.Glunz, September 2013 Realization by self-organized opaline structures Hexagonal photonic structure Deposition of ALD Al2O3 layer (surface passivation) Spin Coating of spherical nanoparticles (SiO2) Structure filled up using ALD of TiO2 (alternative SolGel) absorption enhancement A-Aref[%] Increasing light absorption Diffractive rear surfaces 20 15 10 5 0 -5 700 wafer thickness 100 m, measured wafer thickness 250 m, measured 800 900 1000 wavelength [nm] Current gain 1.5 mA/cm2 Surface passivation < 10 cm/s 28 © Fraunhofer ISE, S. W.Glunz, September 2013 1100 Eisenlohr et al., EUPVSEC (2013) 1200 1300 AGENDA Crystalline Silicon: How to handle an indirect semiconductor? Theoretical efficiency limit Light absorption Increasing light absorption: Classical approaches Pyramids Internal reflection layers Increasing light absorption: New concepts Plasmonic structures Diffractive optics Using the full spectrum Up-conversion 29 © Fraunhofer ISE, S. W.Glunz, September 2013 Specifications for solar cell upconverter devices Bifacial solar cell Large transmittance of subband-gap photons Large EQE of UC photons from the rear Upconverter Large absorptance Large upconversion quantum yield (UCQY) Broad absorption range Er3+ based upconverter Shockley-Queisser limit enhanced from 30% to 40%1 1T. Trupke, et al., Sol. Energy Mater. Sol. Cells 90, 3327 (2006) 30 © Fraunhofer ISE, S. W.Glunz, September 2013 Symbolic example Upconversion (UC) Er3+ based upconverter Laser 1523 nm Energy transfer most efficient UC process (ETU) Subsequent absorption of photons (GSA, ESA) UC luminescence due to spontaneous emission (SPE) Multi-phonon relaxation (MPR) F. Auzel, Chemical Review 104, 139-73 (2004) K. W. Krämer, et al., Chemistry of Materials 16(7), 1244-51 (2004) 31 © Fraunhofer ISE, S. W.Glunz, September 2013 Solar cell upconverter device Short-circuit current density Monochromatic laser excitation 1.79% at 1000 W/m2 (0.179 cm2/W) Broad-band excitation 0.77% at 1063 W/m2 (0.072 cm2/W) 2.2 mA/cm2 under 78 suns Solar concentrator 13.3 mA/cm2 under 207 suns Efficiency increase of 0.19% 1S. Fischer et al., submitted to SOLMAT (2013) 32 © Fraunhofer ISE, S. W.Glunz, September 2013 Conclusion Q: “Nanophotonics - essential ingredient for efficient and cost-effective solar cells?” A: Yes, but … Don´t deteriorate the surfaces electrically! Structures should be applicable and not only scientifically sexy! 33 © Fraunhofer ISE, S. W.Glunz, September 2013 Acknowledgements My sincere thanks to my all my coworkers at Fraunhofer ISE especially to Johannes Eisenlohr, Stefan Fischer, Benedikt Bläsi, Jan-Christoph Goldschmidt for the fruitful and pleasant national and international cooperation for the budget from industry, German Government and European Commission 34 © Fraunhofer ISE, S. W.Glunz, September 2013 AGENDA Crystalline Silicon: How to handle an indirect semiconductor? Theoretical efficiency limit Light absorption Increasing light absorption: Classical approaches Pyramids Internal reflection layers Increasing light absorption: New concepts Diffractive optics Plasmonic structure Using the full spectrum Up-conversion Spectral splitting 35 © Fraunhofer ISE, S. W.Glunz, September 2013 Using the full spectrum Spectral splitting Spectral splitting of the spectrum using beam splitters Different cells adapted to each part of the spectrum Realized system: Efficiency 32.1% B. Mitchell et al., Progress in Photovoltaics 19 (2011) 36 © Fraunhofer ISE, S. W.Glunz, September 2013