Printed Thermoelectric, Piezoelectric and Pyroelectric Energy Harvesters

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1 Printed Thermoelectric, Piezoelectric and Pyroelectric Energy Harvesters Professor Robert Dorey, Chair of Nanomaterials Thursday, 09 April

2 Introduction Harvesting using films Creating film harvesters Performances Based on: Integrated Powder-based Thick Films for Thermoelectric, Pyroelectric and Piezoelectric Energy Harvesting Devices Robert A. Dorey IEEE Sensors Journal, vol 14, no 7, pp , 2014 Thursday, 09 April

3 Introduction Thursday, 09 April

4 Introduction typical architecture Functional Conducting Structural Thursday, 09 April

5 Processing Temperature Processing Temperature Co-processing Ceramics Ceramics Metals Metals Glass & Si Polymers Glass & Si Polymers Thursday, 09 April

6 Powder based films Power Larger volumes thick films powder based manufacturing PZT film before sintering Thursday, 09 April

7 Co-processing Temperature induced degradation: Interdiffusion Evaporation Degradation Solutions: Low temperature e.g. < 750 C for PZT/Si Diffusion barrier e.g. ZrO 2 R.A. Dorey, S.B. Stringfellow, R.W. Whatmore, Effect of sintering aid and repeated sol infiltrations on the dielectric and piezoelectric properties of a PZT composite thick film, J.Euro.Ceram.Soc., 22, , Thursday, 09 April

8 Manufacturing techniques Thursday, 09 April

9 Deposition screen printing Thursday, 09 April

10 Deposition tape casting & spray coating 50 mm Tape casting Spray coating Thursday, 09 April

11 Powder sol gel Sol infiltration & spinning PZT sol Dry Pyrolyse Sinter & Crystallise Spinning of composite slurry PZT powder Thursday, 09 April

12 Future manufacturing techniques Thursday, 09 April

13 Structuring direct writing PZT features created by ink jet printing Thursday, 09 April

14 Structuring pad printing Silver NPs deposited by pad printing Thursday, 09 April

15 Structuring micromoulding PZT features created by micro moulding D. Wang, S.A. Rocks, R.A. Dorey, Micromoulding of PZT film structures using electrohydrodynamic atomization mould filling, J.Euro.Ceram.Soc., 29, , Thursday, 09 April

16 Structuring micromoulding Thursday, 09 April

17 Structuring micromoulding PZT Spreading region Thursday, 09 April

18 Structuring additive vs subtractive DRIE Powder blast Wet etch Micromould Thursday, 09 April

19 Powders, inks & processing temperatures Powder Powder Carrier Binder Thickness Temperature ( C) Synthesis (µm) Drying Burnout Sinter Screen Mech 76 wt% Bi-Te 22 wt% 2 wt% (hours) 250/10 m - Toluene Polystyrene Screen In situ 75 wt% Bi-Te 20.3 wt% /15 m 200/5 m 400/30 m (N 2 ) 550 (N 2 ) Screen In situ 79.6% ZnSb 18% None /10 m 330 C/20 m 380/20 m (N 2 ) Screen Mech vol% 64-36vol% n/a (Ar) Bi-Te epoxy resin Screen Calcination 80 wt% PZT 19.2 wt% 0.8 wt% Screen Calcination PZT Terpineol Ethyl /30 m 550/1 h 900/60 m cellulose 700/30 m Screen Calcination PZT /10 m - 925/30 m Screen Calcination PZT Terpineol & PVB-PVAc /10 m ethyl acetate Screen Calcination Complex Terpineol Ethyl /2 h perovkites cellulose Tape Calcination PZT - PVB 30 vacuum 600/3 h PSG Calcination 98 wt% PZT 4 wt% sol None 4 450/3 m 700/10 m 700/15 m PSG Calcination 60 wt% PZT 40 wt% sol None /60 s 450/15 s 720/20 m EPD Calcination PZT Acetic acid None (low O 2 ) EPD Calcination 30 wt% Al 2 O 3 ethanol PVB/PVAc Thursday, 09 April

20 Powders, inks & processing temperatures Powder Powder Carrier Binder Thickness Temperature ( C) Synthesis (µm) Drying Burnout Sinter Screen Mech 76 wt% Bi-Te 22 wt% 2 wt% (hours) 250/10 m - Toluene Polystyrene Screen In situ 75 wt% Bi-Te 20.3 wt% /15 m 200/5 m 400/30 m (N 2 ) 550 (N 2 ) Screen In situ 79.6% ZnSb 18% None /10 m 330 C/20 m 380/20 m (N 2 ) Screen Mech vol% 64-36vol% n/a (Ar) Bi-Te epoxy resin Screen Calcination 80 wt% PZT 19.2 wt% 0.8 wt% Screen Calcination PZT Terpineol Ethyl /30 m 550/1 h 900/60 m cellulose 700/30 m Screen Calcination PZT /10 m - 925/30 m Screen Calcination PZT Terpineol & PVB-PVAc /10 m ethyl acetate Screen Calcination Complex Terpineol Ethyl /2 h perovkites cellulose Tape Calcination PZT - PVB 30 vacuum 600/3 h PSG Calcination 98 wt% PZT 4 wt% sol None 4 450/3 m 700/10 m 700/15 m PSG Calcination 60 wt% PZT 40 wt% sol None /60 s 450/15 s 720/20 m EPD Calcination PZT Acetic acid None (low O 2 ) EPD Calcination 30 wt% Al 2 O 3 ethanol PVB/PVAc Thursday, 09 April

21 Powders, inks & processing temperatures Powder Powder Carrier Binder Thickness Temperature ( C) Synthesis (µm) Drying Burnout Sinter Screen Mech 76 wt% Bi-Te 22 wt% 2 wt% (hours) 250/10 m - Toluene Polystyrene Screen In situ 75 wt% Bi-Te 20.3 wt% /15 m 200/5 m 400/30 m (N 2 ) 550 (N 2 ) Screen In situ 79.6% ZnSb 18% None /10 m 330 C/20 m 380/20 m (N 2 ) Screen Mech vol% 64-36vol% n/a (Ar) Bi-Te epoxy resin Screen Calcination 80 wt% PZT 19.2 wt% 0.8 wt% Screen Calcination PZT Terpineol Ethyl /30 m 550/1 h 900/60 m cellulose 700/30 m Screen Calcination PZT /10 m - 925/30 m Screen Calcination PZT Terpineol & PVB-PVAc /10 m ethyl acetate Screen Calcination Complex Terpineol Ethyl /2 h perovkites cellulose Tape Calcination PZT - PVB 30 vacuum 600/3 h PSG Calcination 98 wt% PZT 4 wt% sol None 4 450/3 m 700/10 m 700/15 m PSG Calcination 60 wt% PZT 40 wt% sol None /60 s 450/15 s 720/20 m EPD Calcination PZT Acetic acid None (low O 2 ) EPD Calcination 30 wt% Al 2 O 3 ethanol PVB/PVAc Thursday, 09 April

22 Powders, inks & processing temperatures Powder Powder Carrier Binder Thickness Temperature ( C) Synthesis (µm) Drying Burnout Sinter Screen Mech 76 wt% Bi-Te 22 wt% 2 wt% (hours) 250/10 m - Toluene Polystyrene Screen In situ 75 wt% Bi-Te 20.3 wt% /15 m 200/5 m 400/30 m (N 2 ) 550 (N 2 ) Screen In situ 79.6% ZnSb 18% None /10 m 330 C/20 m 380/20 m (N 2 ) Screen Mech vol% 64-36vol% n/a (Ar) Bi-Te epoxy resin Screen Calcination 80 wt% PZT 19.2 wt% 0.8 wt% Screen Calcination PZT Terpineol Ethyl /30 m 550/1 h 900/60 m cellulose 700/30 m Screen Calcination PZT /10 m - 925/30 m Screen Calcination PZT Terpineol & PVB-PVAc /10 m ethyl acetate Screen Calcination Complex Terpineol Ethyl /2 h perovkites cellulose Tape Calcination PZT - PVB 30 vacuum 600/3 h PSG Calcination 98 wt% PZT 4 wt% sol None 4 450/3 m 700/10 m 700/15 m PSG Calcination 60 wt% PZT 40 wt% sol None /60 s 450/15 s 720/20 m EPD Calcination PZT Acetic acid None (low O 2 ) EPD Calcination 30 wt% Al 2 O 3 ethanol PVB/PVAc Thursday, 09 April

23 Powders, inks & processing temperatures Powder Powder Carrier Binder Thickness Temperature ( C) Synthesis (µm) Drying Burnout Sinter Screen Mech 76 wt% Bi-Te 22 wt% 2 wt% (hours) 250/10 m - Toluene Polystyrene Screen In situ 75 wt% Bi-Te 20.3 wt% /15 m 200/5 m 400/30 m (N 2 ) 550 (N 2 ) Screen In situ 79.6% ZnSb 18% None /10 m 330 C/20 m 380/20 m (N 2 ) Screen Mech vol% 64-36vol% n/a (Ar) Bi-Te epoxy resin Screen Calcination 80 wt% PZT 19.2 wt% 0.8 wt% Screen Calcination PZT Terpineol Ethyl /30 m 550/1 h 900/60 m cellulose 700/30 m Screen Calcination PZT /10 m - 925/30 m Screen Calcination PZT Terpineol & PVB-PVAc /10 m ethyl acetate Screen Calcination Complex Terpineol Ethyl /2 h perovkites cellulose Tape Calcination PZT - PVB 30 vacuum 600/3 h PSG Calcination 98 wt% PZT 4 wt% sol None 4 450/3 m 700/10 m 700/15 m PSG Calcination 60 wt% PZT 40 wt% sol None /60 s 450/15 s 720/20 m EPD Calcination PZT Acetic acid None (low O 2 ) EPD Calcination 30 wt% Al 2 O 3 ethanol PVB/PVAc Thursday, 09 April

24 Powders, inks & processing temperatures Powder Powder Carrier Binder Thickness Temperature ( C) Synthesis (µm) Drying Burnout Sinter Screen Mech 76 wt% Bi-Te 22 wt% 2 wt% (hours) 250/10 m - Toluene Polystyrene Screen In situ 75 wt% Bi-Te 20.3 wt% /15 m 200/5 m 400/30 m (N 2 ) 550 (N 2 ) Screen In situ 79.6% ZnSb 18% None /10 m 330 C/20 m 380/20 m (N 2 ) Screen Mech vol% 64-36vol% n/a (Ar) Bi-Te epoxy resin Screen Calcination 80 wt% PZT 19.2 wt% 0.8 wt% Screen Calcination PZT Terpineol Ethyl /30 m 550/1 h 900/60 m cellulose 700/30 m Screen Calcination PZT /10 m - 925/30 m Screen Calcination PZT Terpineol & PVB-PVAc /10 m ethyl acetate Screen Calcination Complex Terpineol Ethyl /2 h perovkites cellulose Tape Calcination PZT - PVB 30 vacuum 600/3 h PSG Calcination 98 wt% PZT 4 wt% sol None 4 450/3 m 700/10 m 700/15 m PSG Calcination 60 wt% PZT 40 wt% sol None /60 s 450/15 s 720/20 m EPD Calcination PZT Acetic acid None (low O 2 ) EPD Calcination 30 wt% Al 2 O 3 ethanol PVB/PVAc Thursday, 09 April

25 Piezoelectric energy harvesters PZT micro energy harvesting cantilever Thursday, 09 April

26 Performance Thursday, 09 April

27 Printed piezoelectrics & pyroelectrics Architecture Process Active material thickness (µm) Substrate thickness (µm) Dimensions L x W (mm) Power (µw) Power density (µw/cm 3 ) Operational frequency (Hz) Bimorph Screen 20 (x2) n/a 6.5 x g Bimorph Screen 55 none 18 x @0.5 g 227 Unimorph Screen 65 (x2) x Unimorph Screen ( ) x x Unimoph PSG/spin x 17 1 g 1 g 89 Unimorph Aerosol x g 1.5 g 112 Unimorph Tape cast x Pyroelectric Screen ~ 10-3 Thursday, 09 April

28 Printed piezoelectrics & pyroelectrics Architecture Process Active material thickness (µm) Substrate thickness (µm) Dimensions L x W (mm) Power (µw) Power density (µw/cm 3 ) Operational frequency (Hz) Bimorph Screen 20 (x2) n/a 6.5 x g Bimorph Screen 55 none 18 x @0.5 g 227 Unimorph Screen 65 (x2) x Unimorph Screen ( ) x x Unimoph PSG/spin x 17 1 g 1 g 89 Unimorph Aerosol x g 1.5 g 112 Unimorph Tape cast x Pyroelectric Screen ~ 10-3 Likely to be pw level Thursday, 09 April

29 Printed thermoelectrics Architecture Processing Active material thickness (µm) In-plane (n) (Bi,Sb) 2 Te) 3 (p) Bi 2 (Se,Te) 3 In-plane Elements Seebeck coef. (µv/k) ZT Power factor (α 2 σ) mw/m 2 K Screen Power density (µw/cm 3 ) (unimat) Bi 2 Te 3 (20 K ΔT) Dispenser RT Film only Screen (@RT) Bi 2 Te 3 Film only Ca 3 Co 4 O 9 Aerosol (@ C) Film only ZnSb Screen (@ K) Bi 0.85 Sb 0.15 /epoxy Screen 97 Ag-Ni Screen ~RT 30 Multilayer (n) LaSrTiO 3 (p) Ni-Mo In-plane (n) Bi 2 Te 3 (p) Sb 2 Te 3 Π Cu/Ni Multilayer (n) 100 (p) 25 Coevaporation Electroplate 50 (n) RT (p) RT - 8 (n) 248 (p) 188 (n) (p) (n) 300K (p) 300K (n) 300K (p) 300K (200 K ΔT) 450 (360 K ΔT) (0.12 K ΔT) - Thursday, 09 April

30 Summary Film based harvesters can be fabricated Thick films are reliant on consolidation of powders i.e. heat required Film forming techniques are continually improving Cheaper & quicker to fabricate than bulk systems Based on: Integrated Powder-based Thick Films for Thermoelectric, Pyroelectric and Piezoelectric Energy Harvesting Devices Robert A. Dorey IEEE Sensors Journal, vol 14, no 7, pp , 2014 Thursday, 09 April

31 Contact details Professor Robert Dorey Chair in Nanomaterials Department of Mechanical Engineering Sciences, Faculty of Engineering and Physical Sciences, University of Surrey Guildford Surrey UK GU2 7XH Ceramic Thick Films for MEMS and Microdevices ISBN: Thursday, 09 April

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