High-temperature Selective Emitter for Thermophotovoltaic Energy Conversion

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1 Physical Sciences Inc. VG High-temperature Selective Emitter for Thermophotovoltaic Energy Conversion David Woolf and Joel Hensley, Andover, MA Jeff Cederberg and Eric A. Shaner Sandia National Laboratories OSA Incubator on the Fundamental Limits of Optical Energy Conversion November 2014 Acknowledgement of Support and Disclaimer This material is based upon work supported by the Office of Naval Research under Contract Number_N P Any opinions, findings and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the Office of Naval Research. 20 New England Business Center Andover, MA

2 Who we are A growing 41 year-old company of 180 talented scientists, engineers and administrative personnel PSI is headquartered in Andover, MA, with operations in Bedford, MA; Dayton, OH; Lanham, MD; Princeton, NJ and Pleasanton, CA PSI companies FY2014 revenues of >$40M Q-Peak manufactures lasers and optical devices Research Support Instruments supports space ops Faraday Technology develops industrial processes Multiple commercial spin-outs PSI is a 100% employee owned company VG Significant efforts in developing photonicsbased technologies and devices Sensors: RMLD, TLDAS, QCL systems AIRIS, LIDAR Thermophotovoltaics

3 Filter Thermophotovoltaics Overview VG Heat in Emitter Radiation PV Cell Electrical Power OUT Concentrated solar energy, combustion source Blackbody, greybody, modified emissive surface Dielectric filters, Plasma (TCO filters) Silicon Germanium, III-Vs 1980s Very high temperature emitters Rare earth oxides, SiC, etc 1990s Low bandgap materials Ge InGaAs, Sb-based materials 2000s Breakthrough in spectrally selective materials Plasmonics Metamaterials Now Can we make a selective emitter that: Survives T > 1300 K Survives repeated thermal cycling Operates in ambient atmosphere Has non-directional (Lambertian) emission Matches well with PV EQE

4 TPV Energy Conversion: Model Assume InGaAs 0.6 ev TPV cell, 1300K blackbody VG Black Body Power Spectrum P = 2hc2 1 λ 5 hc eλk BT 1 Black Body Photon Density Spectrum n Bb = 2c 1 λ 4 hc eλk BT 1 PV Cell Fill Factor Most power, photons are below band-gap useless if transmitted, increases TPV heating if absorbed Predicts h TPV = 8.25%, P out = 1.28 W/cm 2 Can see h TPV as P PV /P rad I SC I m FF = I mv m I SC V OC V m V OC

5 Model with Ideal Selective Emitter Only emits where EQE of TPV cell is near unity VG P rad = emitter spectrum x blackbody power spectrum P out = emitter spectrum x blackbody photon density (norm) x EQE h TPV = magenta area / cyan area Model predicts h TPV = 39.2% at 1300 K 475% increase in efficiency compared to black-body radiation Want actual emitter to approximate this ideal emitter

6 Selective Emitter Design VG Metamaterial emitter consists of a thin-film Pt cross above a Pt backplane Sapphire substrate, Al 2 O 3 spacer Al 2 O 3 and Pt: t Stable in atmosphere Matched CTE up to ~ 1500 K Al Pt h Used Lumerical FDTD to determine geometric parameters: p w Spacer (h 90 nm) Pt cross (t 45 nm) l h p 550 nm, w 275 nm, l 200 nm Fabricated via e-beam lithography + e-beam evaporation Woolf et al., APL105,

7 Fabrication procedure Fabricated Structures Sapphire Wafer E-beam evaporate Pt and Al 2 O 3 Spin lift-off resist and e-beam resist Write pattern Develop e-beam resist Undercut lift-off resist Deposit Pt Remove resists Optical image of Fabricated Structure Higher order absorption resonances give each array distinct color VG nm l 250 nm 400 nm p 600 nm 500 μm 250 nm w 300 nm Woolf et al., APL105,

8 Fabrication procedure Fabricated Structures Sapphire Wafer E-beam evaporate Pt and Al 2 O 3 Spin lift-off resist and e-beam resist SEM image of Fabricated Structure VG Write pattern Develop e-beam resist Undercut lift-off resist Deposit Pt SEM has resolution of ~ 20 nm Remove resists Woolf et al., APL105,

9 Thermal Testing at 1300 K SEM Images Heat sample in RTA in 1 atm of Argon, hold for 2 min VG Before Heating After Heating Pt/AlO thin films survive (no delamination) Metal pattern on surface deforms Due to interfacial stress Woolf et al., APL105,

10 Thermal Testing at 1300 K Optical Images Heat sample in RTA in 1 atm of Argon, hold for 2 min VG Before Heating After Heating Visible frequency color change indicates morphological pattern change Woolf et al., APL105,

11 Spectral Emission after Heating at 1300K VG Heat cycle at 1300 K 2 min cycle 10 min cycle Pre-heat cycle Spectral shift happens in first 2 minutes then remains static through additional heating cycles Could redesign emitter to optimize post-anneal geometry Lose some tuning parameters (cross to square shape) Absorption feature narrows (not good for matching TPV EQE) Woolf et al., APL105,

12 Use encapsulation to stabilize cross pattern Emitter Stabilization Deposit ~150 nm of Al 2 O 3 using Atomic Layer Deposition (ALD) on top of structure ALD chosen because it is more conformal than sputtering Encapsulating material same as dielectric spacer more thermally stable configuration for micro-structures Pre-thermal cycling Post-thermal cycling VG nm Woolf et al., APL105,

13 Emitter Encapsulation Optical Images VG Before heating After 2 min at 1000 C After min heating cycles After min heating cycles Woolf et al., APL105,

14 Encapsulated Emitter Thermal testing at 1300 K VG Minimal spectral effect due to heating Slight shift in spectrum in first heating cycle Densification of Al 2 O 3 Remains constant through 2, 5, 5 minute thermal cycles Heat cycle at 1300 K min cycles 2 min cycle Pre-heat cycle Encapsulation layer broadens resonance What is the expected TPV power and efficiency using this emitter? Woolf et al., APL105,

15 Selective Emitter Predicted Performance VG Selective emitter boosts TPV conversion efficiency to 22% at 1300 K from 8.5% with no selective emitter 1.2 W/cm 2 out 27% at 1500 K 3 W/cm 2 out With cold side filter, efficiency can be improved to ~40% Woolf et al., APL105,

16 Selective Emitter Predicted Performance VG Selective emitter boosts TPV conversion efficiency to 22% at 1300 K from 8.5% with no selective emitter 1.2 W/cm 2 out 27% at 1500 K 3 W/cm 2 out With cold side filter, efficiency can be improved to ~40% Minimal benefit from using more exotic TPV materials due to worsening dark current, EQE Woolf et al., APL105,

17 Large-area Emitter Fabrication E-beam lithography is not scalable Nano-imprint, interference lithography Not mature Stepper projection lithography Commercially viable VG Fabrication steps using deep UV stepper photolithography Mask Prepared Substrate Spin on Antireflection + Photoresist UV expose Resolution limit ~ 200nm compared to ~20nm resolution for e-beam used in P1 base Lift Off Deposit Metal Develop Need to verify that performance still okay with 10x resolution

18 Large-area Fabrication via Stepper Lithography Preliminary demonstration of large-area fabrication using conventional lithography methods Puck geometry can produce spectra equivalent to cross geometry spectra 330nm VG Pt Al nm

19 Conclusions and Outlook Fabricated a heterogeneous metasurface capable of surviving repeated temperature cycling to 1300 K VG Measured metasurface reflectivity, used to estimate thermal-toelectrical energy conversion efficiency Demonstrated large scale fabrication using conventional lithography Suitable for TPV or Solar TPV applications TPV is rapidly maturing due to innovations in high-temperature emitters Applications in remote energy generation and combined heat and power

20 Physical Sciences Inc. VG Thank you. Questions? 20 New England Business Center Andover, MA

21 Physical Sciences Inc. VG Backup Slides 20 New England Business Center Andover, MA

22 What We Do Applied research and development for all major agencies of the U.S. government ~ 60% FY 10 revenue Technology transition and product development for government and industrial customers ~ 15% FY 10 revenue Pre-production manufacturing process development ~ 5% FY 10 revenue Components, systems, and instrumentation for industry and government sales ~20% FY 10 revenue Technology and product licensing to strategic partners and spin-outs for high-volume commercial markets ~ 2% FY 10 revenue from royalties VG

23 TPV Converter Cell Model Concept VG Reflected power TPV cell >BG Generated power P out Heat Source Radiated power from combustion P rad Reradiated power <BG Below bandgap absorption Electrical Losses Selective Emitter Goal of TPV model is to calculate: Electrical output power: P out TPV efficiency: η TPV = P out P rad TPV spectral efficiency: η spec = N abs N rad Reradiated power Not included in model: Temperature rise of TPV (assume perfect heatsinking) Above bandgap thermalization Below bandgap absorption Electrical losses

24 Experimental Results - Fabrication Fabrication process SEM Image Sapphire Wafer E-beam evaporate Pt and Al 2 O 3 Spin lift-off resist and e-beam photoresist Write pattern Develop e-beam photoresist Undercut lift-off resist Deposit Pt Remove resists using acetone

25 Motivation Need a higher energy-density source for remote energy generation Energy Density (MJ/kg) VG Combined heat and power (CHP) potential. 10% total efficiency TPV beats battery by factor

26 VG

27 VG

28 VG

29 VG

30 VG

31 Experiments vs Theory Measurements taken using FTIR Unity absorption on resonance FWHM ~ 1um Tunable Matches simulations

32 Team PSI Dr. David Woolf Dr. Joel Hensley Acknowledgements Funding ONR N P-1190 VG Sandia Dr. Eric Shaner Dr. Jeff Cederberg Albert Grine Don Bethke

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