Nanotechnology in Photovoltaics

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1 Nanotechnology in Photovoltaics ECSAC10 Losinj, August 25 th, 2009 Vanni Lughi Dipartimento dei Materiali e delle Risorse Naturali University of Trieste

2 Our laboratory Two lines of research on photovoltaic materials: Thin film PV (CdS/CdTe-based) Novel nanostructured materials low-cost and high efficiency Part of MEL, Laboratory for Energy Materials research and services in the field of energy materials, including photovoltaic installations (e.g. 20 kw installation on DMRN s building roof, 20 kw installation on the City Hall s Roof in Trieste, )

3 Doctoral student: Luca Cozzarini Our laboratory Students: Michele Pianigiani Matteo Barbone Alice Orzan Alice Furlan Emanuele Slejko Giulio Pipan Stefania Cacovich Luca Pavan MaXun-Genefinity personnel: Dr. Francesca Antoniolli, Ph.D Andrea Radivo Mauro Del Ben Facilties: Dept. Materials and Natural Resources (DMRN) Spectroscopy Lab DMRN

4 Introduction Why photovoltaics (PV)? Evolution of PV (economical technical social) Current PV technologies Basic physics Si-based technology Thin films Contents Emerging technologies High efficiency approaches (Tandem) Low-cost approaches (Biomimetics) Third generation technologies Nanostructured materials colloidal solids

5 Photovoltaics Direct conversion of solar energy to electrical energy (for free!)

6 Why Photovoltaics?

7 Growth of the Energy Demand - Particularly in the developing countries-

8 Growth of the Energy Demand - Particularly in the developing countries-

9 Need for carbon-free energy sources Temperature rising (?)

10 Need for carbon-free energy sources Temperature rising (?) Old Data New Data

11 Need for carbon-free energy sources Ice Melting

12 Need for carbon-free energy sources Climate change

13 Need for carbon-free energy sources Economic sanctions

14 Need for carbon-free energy sources Hoffert, Nature 1998

15 Photovoltaics vs. other Renewable Resources Allen Barnett

16 Evolution of Photovoltaics Economical Technical Social acceptance and integration

17 Economical Evolution: Photovoltaic Market

18 New Markets Off-grid Rural Applications Off-grid Telecommunications On-grid Residential and commercial Allen Barnett

19 Market size and growth World Market: 15B Demand and supply growth: 35%/year Demand exceeds supply Annual Installation (GWp) Trends in photovoltaic applications, Survey report of selected IEA countries between 1992 and 2005, report IEA- PVPS T1-15:2006 DOE Solar Energy Technologies Program, Multi-Year Program Plan , U.S. Department of Energy, Energy Efficiency and Renewable Energy

20 Average price ($/Wp) Price Learning curve: 80% Silicon technology Thin film technology 2 Apr-01 Jan-04 Oct-06

21 Technological evolution

22 Technology evolution: Efficiency increase NREL - US Dept.of Energy

23 Efficeincy Technology evolution: Efficiency increase 24.7% 30% (theoretical limit) Silicon CdTe Thin film 16.5% 2009 Time

24 Efficiency (%) Tecno-Economical Evolution - Cost and Efficiency PV Figures of Merit - Economical convenience 0.1 $/W 0.2 $/W Grid parity 0.5 $/W Ultimate thermodynamic limit $/W SQ limit for single junction 3.5 $/W Cost ($/m 2 )

25 Integration of PV

26 Traditional Photovoltaic Installations

27 Integration: Aesthetics

28 Integration: Aesthetics

29 Integration: Aesthetics & Function

30 Integration: Aesthetics & Function

31 Current PV Technologies

32

33 Photovoltaic Effect

34 Photovoltaic Effect

35 Energiy p-n junction p n E p Conduction band Valence band n Spatial coordinate

36 Photovoltaic Effect Energy 1. Absorption of solar radiation Conduction Band Creation of free carriers Free carrier transport and extraction Valence Band Electrical energy

37 Photovoltaic Effect Choice of materials 1. Absorption of solar radiation Creation of free carriers Materials with good absorption of the solar radiation 2. Free carrier extraction Electrical energy Perfect materials (large mean free paths for the carriers) Short carrier paths

38 Silicon technology

39 Silicon technology Record performance Single crystal silicon Polycrystalline Cell Record 24.7% 20.3% Module record 22.7% 15.3% Commercial modules 15-18% 12-15

40 Efficeincy Silicon Technology 24.7% 30% (theoretical limit) Silicon 2009 Time

41 Silicon Technology - Summary Efficeincy Mature Technology (max efficiency > 80% thermodynamic limit) Silicon 24.7% 30% (theoretical limit) 2009 Time Large quantities of pure silicon are needed high cost of raw material Limitation in raw material supply Kazmersky, 2006

42 Efficiency (%) Tecno-Economical Evolution - Cost and Efficiency PV Figures of Merit - Economical convenience 0.1 $/W 0.2 $/W Grid parity 0.5 $/W Ultimate thermodynamic limit Silicon technology 1 $/W SQ limit for single junction 3.5 $/W Cost ($/m 2 )

43 Thin Film Solar Cells Materials with: high absorption coefficient good match with the solar spectrum (1.5 ev) Less active material is needed (thin films: um) Lower cost Less problems with supply of raw materials Short carrier paths (perfection requirements are relaxed)

44 Thin Film Solar Cells Medium efficiency Low Cost CdTe CIGSS Amorphous Si Cell Record 16.5% 19.5% 9.5% Module record 10.7% 13.4% -- Commercial modules 8-10% %

45 Efficeincy Technology evolution: Efficiency increase 24.7% 30% (theoretical limit) Silicon CdTe Thin film 16.5% 2009 Time

46 Efficiency (%) Tecno-Economical Evolution - Cost and Efficiency PV Figures of Merit - Economical convenience 0.1 $/W 0.2 $/W Grid parity 0.5 $/W Ultimate thermodynamic limit 40 1 $/W SQ limit for single junction 20 Thin film technology Silicon technology 3.5 $/W Cost ($/m 2 )

47 Thin Film Solar Cells Young Technology(max efficiency is 30-40% of thermodynamic limit) Films can be deposited on various substrates (flexible, architectural elements for building integration, etc.) Low Cost Thermodynamic limit is still 30% Nanotechnology-based films are currently reaching the market

48 PV efficiency: Thermodynamic limit Energy Conduction Band + - Valence Band

49 Energy PV efficiency: Thermodynamic limit Conduction Band Valence Band Max efficiency: 30%

50 Beyond The Single Junction Limit: Tandem cells More efficient use of the solar spectrum

51 Tandem Cells Current efficiency record > 40% Multijunction cells very expensive Aerospace applications or terrestrial concentration

52 Efficiency (%) Tecno-Economical Evolution - Cost and Efficiency PV Figures of Merit - Economical convenience 0.1 $/W 0.2 $/W Grid parity 0.5 $/W Ultimate thermodynamic limit 40 1 $/W Multijunctions SQ limit for single junction 20 Thin film technology Silicon technology 3.5 $/W Cost ($/m 2 )

53 Why nanotechnology? Morphological advantages (surface area) Phenomena that govern optoelectronic properties of materials occur at the nanoscale Phenomena at the nanoscale are governed by the laws of quantum mechanics new opportunities for controlling material properties

54 Dye Sensitized Solar Cell (DSSC) Graetzel Cell

55 Dye-sensitized solar cell (DSSC) Grätzel cell Efficiency ~ 5-10% Liquid electrolyte DSSC c-si

56 Photosynthesis Energy is absorbed by the antenna complexes Cascade of energy transfer between donors and acceptors embedded in antennas (FRET) Energy is funneled to the reaction center Subsequent multistep electron transfer This creates a charge-separated state which lasts for 10s of s or more, with a ~100% QE Limitations Absorption is only efficient at specific wavelenghts To reach the charge-separated state the electron needs to spend energy Energy converted in chemical energy ~ 9%

57 Artificial Photosynthesis: Basic Example Porphyrin-fullerene couples self-assembled on surfaces Donors and acceptors are bonded covalently Thiol Porphyrin C 60 Methil Viologen (MV 2+ ) Quantum yield: 0.5% Lifetime 0.77 s Loose packing on the surface

58 Artificial Photosynthesis Requirements Appropriate redox potentials and excitation energy for donors and acceptors (quantum yield) Small reorganization energy (- G cs ~ and - G CR >> ) to favor forward electron transfer (charge separation time) Distance between donors and acceptors Solvent characteristics Vibrational modes of the molecules

59 Artificial Photosynthesis: A more efficient scheme Ferrocene Porphyrin C 60 Quantum yield > 25% Lifetime ~ 16 s Dense packing on the surface Pentads do even better H. Imahori et al., Adv. Func. Materials 14, 525 (2004)

60 Artificial Photosynthesis: Mimicking energy transfer Boron Dipyrrin Thiol Ferrocene Porphyrin Quantum yield: up to 50% Enhanced spectral absorption Dense packing on the surface H. Imahori et al., Adv. Func. Materials 14, 525 (2004)

61 Artificial Photosynthesis on Transparent Conductive Oxide (ITO) Avoids quenching by electrode Transparent substrate H. Imahori et al., Adv. Func. Materials 14, 525 (2004)

62 Artificial Photosynthesis: Hierarchical assembly for enhancing absorption C 60 Porphirine H. Imahori et al., Adv. Func. Materials 14, 525 (2004)

63 Artificial Photosynthesis: Hierarchical assembly for enhancing absorption Gold nanoparticle H. Imahori et al., Adv. Func. Materials 14, 525 (2004)

64 Stealing from Nature Photoactive reaction centers on metal substrates e - L. Forlov et al., Adv. Materials 17, 2434 (2005)

65 Beyond The Single Junction Limit: Tandem cells More efficient use of the solar spectrum

66 Intermediate Band Materials Beyond single junction limits (at low cost!)

67 Making an Intermediate Band Material Quantum dots embedded in a semiconductor Nanotechnology at the service of PV Conduction band Valence Band Intermediate Band

68 Photovoltaic Devices Based on Intermediate Band Materials Max efficiency 47% Current record for single-junction cell: 28.3% Scalable, low-cost production approaches Diversity of substrates excellent integration (nanoinks and photovoltaic paints )

69 Efficiency (%) Tecno-Economical Evolution - Cost and Efficiency PV Figures of Merit - Economical convenience 0.1 $/W 0.2 $/W Grid parity 0.5 $/W Ultimate thermodynamic limit 40 IB Materials 1 $/W Multijunctions SQ limit for single junction 20 Thin film technology Silicon technology 3.5 $/W Cost ($/m 2 )

70 Efficiency 47% (IB material limit) 24.7% 30% (single junction limit) Silicio 16.5% CdTe 2010 Time

71 Beyond The Single Junction Limit: Other approaches Multiple carrier generation using high energy photons to extract more than one electron per photon Hot electron extraction extracting high energy photogenerated electrons before they thermalize Thermodynamic limiting efficiency (both cases): 86.8%

72 Properties of nanomaterials Phenomena at the nanoscale are governed by the laws of quantum mechanics. new opportunities for controlling material properties Phenomena that govern optoelectronic properties of materials occur at the nanoscale

73 Properties of nanomaterials What does nano mean? A material is nano when a selected property starts to differ from its bulk behavior

74 EnergiY Electrons in a (spherical) box E 2 2 2m R e 2 n 2 n = 1, 2, 3, Electrons can be described by waves Confined waves can only have a discrete set of wavelengths In confined systems, electrons can only assume discrete values of energy Position of energy levels depends upon confinement (size of the box)

75 Quantum Dots Artificial atoms nanocrystal atom As for atoms, quantum dots have discrete electron energy levels

76 Nanocrystals 2.5 nm Typical size: nm ( atoms) Most atoms are at the surface (75% for 1 nm nanocrystals) Essentially free of lattice defects

77 Nanocrystals

78 Semiconductor nanocrystals (quantum dots): Optical properties

79 Energia Quantum dot absorption and emission Dependence on size E g ( Q. D.) E g m R eh 2

80

81 Semiconductor Nanocrystals: Synthesis

82 Semiconductor Nanocrystals: Synthesis Colloidal synthesis of cadmium selenide Cd-oleate + Se-TOP CdSe + products Cadmium precursor: Cd-oleate Selenium precursor: Se-TOP (trioctylphosphine-selenium) mixing Precipitation of CdSe

83 Semiconductor Nanocrystals: Colloidal Synthesis Key role of NUCLEATION and GROWTH TIME, TEMPERATURE and CONCENTRATION control reaction kinetics Surfactant are needed to avoid cluster formation

84 Nucleation

85 Nanocrystal shapes Paul Alivisatos, UC Berkeley

86 Nanostructured materials Colloidal solids A chance to design novel materials with entirely new properties 8 nm

87 Methods for assembling colloidal solids

88 Bio-templated nanomaterials E. Hu, UCSB A. Belcher, MIT

89 C.B. Murray et al., Annu. Rev. Mater. Sci 30, 545 (2000) Assembly and structural control D.J. Norris, Adv. Mater. 16, 1394 (2004) 8 nm diameter CdSe Glass Sticking coefficient Particle arrival speed Crystalline (ordered)

90 QD-solid assembly: QD Distance Engineering Curve Capping agent Atoms per chain Interparticle distance (Å) 50 nm h Trihexadecylphosphate i Trioctylphosphine calchogenide 8 11 j Tributylphosphine oxide 4 7 Y. Yin, A.P. Alivisatos, Nature 437, 664 (2005) C.B. Murray et al., Science 270, 1335 (1995)

91 Electronic properties of colloidal solids

92 QD-solid assembly: Bi-component QD-Solid PbSe Fe 2 O 3 {110} SL F.X. Redl et al., Nature 423, 968 (2003)

93 xxx Materials engineering CB IB VB

94 Energiy Our approach for sinthesizing an IB material Matrice di ZnSe matrix CdSe QDs Electron affinity Bandgap ZnSe CdSe ZnSe

95 Absorption Peak Position [nm] NCs Growth Kinetics Control of Size Cd:OA 1: Cd:OA 1: Temperature [ C]

96 Assembly: Control of interparticle forces

97 Intensity [a.u.] Peak Intensity [a.u.] Assembly: Ordering Time (s) q-spacing (A -1 )

98 Uniform Thin Films of NC assemblies

99 Counts Densification of NC assemblies Core/shell ITO ZnO ITO ZnO ZnO Core/shell ITO CdSe CdSe CdSe theta [ ] As deposited Core/shell Sintered

100 Optical properties of NC assemblies PL of the nanocrystals PL of the matrix

101 Concluding Remarks PV is at a tipping point breakthrough technology is just around the corner Bio- and Nanotechnology will likely be the key to high performance, low cost PV devices Colloidal routes to fabricate PV materials are extremely promising: The structure can be finely engineered at the nanoscale Cost can be reduced (ambient process conditions)

102 Doctoral student: Luca Cozzarini Aknowledgements Students: Michele Pianigiani Matteo Barbone Alice Orzan Alice Furlan Emanuele Slejko Giulio Pipan Stefania Cacovich Luca Pavan MaXun-Genefinity personnel: Dr. Francesca Antoniolli, Ph.D Andrea Radivo Mauro Del Ben Facilties: Dept. Materials and Natural Resources (DMRN) Spectroscopy Lab DMRN

103

104 State of the art

105 Stato dell arte

106 Moduli basati su film sottile Materiali con eccellente assorbimento della radiazione solare Piccoli spessori Stabilità dei costi Sostenibilità degli approvvigionamenti Flessibilità nella scelta del substrato Moduli integrati Esempi: Silicio amorfo; CIGS; CdTe

107 Moduli basati su film sottili di CdTe Proprietà elettroniche ideali (bandgap 1.5 ev massimo utilizzo della radiazione solare) Disponibilità delle materie prime Robustezza e varietà di processi produttivi disponibili Provata fattibilità industriale (First Solar; Antec)

108 Economia dell industria fotovoltaica 1200 PV Cell/Module Production (MW) Rest of World Europe Japan U.S World Watch Institute Fatturato complessivo ~ 10 Mld. /anno Crescita media ~ 35%/anno Installazione annuale (GW)

109 Vendite First Solar MW x

110 Costo dell energia fotovoltaica

111 Altre applicazioni

112 Schermi piatti Basso consumo Alta efficienza Un solo materiale per vari colori

113 QD-LED Quantum Dot-Based Light-Emitting Diodes La selezione della dimensione dei nanocristalli consente la scelta del colore da uno spettro continuo Applicazioni: Display più luminosi, con miglior riproduzione del colore, a basso consumo

114 Dyes biocompatibili Studio del comportamento di cellule, ed in generale degli esseri v

115 Diagnosi e cura dei tumori Le nanoparticelle vengono funzionalizzate in modo da venir accumulate presso il tumore Le proprietà di emissione vengono utilizzate per individuare il tumore Le proprietà di assorbimento vengono

116 Diagnosi e cura dei tumori

117 Inchiostri a fluorescenza Sicurezza e tecnologie anti-contraffazione

118 Main Losses in PV Devices Metal contact Metal contact

119 Sommario Tecnologia Rendimento Costo /Wp Tempo di ritorno dell energia [anni] Ritorno investimento energetico (EROI) Silicio monocristallo Silicio policristallo 15-22% % Film sottili 5-13% Celle tandem 30-42% alto?? DSSC 5-10% (2-3) Materiali organici 3-6% (1-2) <1 >50 Nanomateriali? (<1)

120 The bandgap dilemma

121 Absorption coefficients

122 Minimum thickness for full absorption Legge di Lambert Beer I = I0 exp (- z) z I0 g d N d N d d f ph ph 0 0 ) ( ) ( ) ) ( exp( (1 ) (

123 Minimum thickness for full absorption Legge di Lambert Beer I = I0 exp (- z) z I0 g d N d N d d f ph ph 0 0 ) ( ) ( ) ) ( exp( (1 ) (

124 Sintesi per test di reversibilità Temperatura Dimensione Temperatura [ C] Diametro NC [nm] Tempo [s] 3.4

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