Optical Hyperdoping: Transforming Semiconductor Band Structure for Solar Energy Harvesting
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1 Optical Hyperdoping: Transforming Semiconductor Band Structure for Solar Energy Harvesting 3G Solar Technologies Multidisciplinary Workshop MRS Spring Meeting San Francisco, CA, 5 April 2010
2 Michael P. Brenner Michael Brenner Alan Aspuru-Guzik Alán Aspuru-Guzik Cynthia Friend Cynthia M. Friend Eric Mazur Eric Mazur
3
4 Harvard NSF SOLAR team Aspuru group: Jacob Krich (PD) Justin Song (GS) Man Hong Yung (PD) Brenner group: Tobias Schneider (PD) Scott Norris (PD) Niall Mangan (GS) Friend group: Anne Co (PD) Stephen Jensen (GS) Mazur group: Meng-Ju Sher (GS) Yuting Lin (GS) Kasey Phillips (GS)
5 Introduction SF 6 Si irradiate with 100-fs 10 kj/m 2 pulses
6 Introduction black silicon
7 3 µm Introduction
8 Introduction absorptance (1 R int T int ) absorptance crystalline silicon wavelength (µm)
9 Introduction absorptance (1 R int T int ) black silicon absorptance crystalline silicon wavelength (µm)
10 Introduction
11 Introduction absorptance (1 R int T int ) absorptance multiple relections black silicon crystalline silicon wavelength (µm)
12 Introduction band structure changes: defects and/or impurities
13 Introduction optical hyperdoping puts 2% of sulfur in 200-nm surface layer
14 Introduction
15 Introduction open questions how do the impurities get incorporated? can we use optical hyperdoping for solar cells?
16 Outline goals optimizing dopant profile intermediate band
17 Goals interesting properties due to intermediate band CB impurity band VB
18 Goals generalize CB Si impurity band TiO 2 ZnO VB
19 Goals process CB Si impurity band TiO 2 ZnO properties VB structure
20 Goals process dopant incorporation modeling laser doping electrospray dopant delivery CB Si impurity band ZnO TiO 2 atomistic modeling XPS, STM, SIMS properties VB carrier life-time modeling band structure calculations T-dependent Hall IR spectroscopy structure
21 Goals Mathematics process dopant incorporation modeling laser doping electrospray dopant delivery CB Si impurity band ZnO TiO 2 atomistic modeling XPS, STM, SIMS properties VB carrier life-time modeling band structure calculations T-dependent Hall IR spectroscopy structure
22 Goals Chemistry process dopant incorporation modeling laser doping electrospray dopant delivery CB Si impurity band ZnO TiO 2 atomistic modeling XPS, STM, SIMS properties VB carrier life-time modeling band structure calculations T-dependent Hall IR spectroscopy structure
23 Goals Materials Science process dopant incorporation modeling laser doping electrospray dopant delivery CB Si impurity band ZnO TiO 2 atomistic modeling XPS, STM, SIMS properties VB carrier life-time modeling band structure calculations T-dependent Hall IR spectroscopy structure
24 Outline goals optimizing dopant profile intermediate band
25 Optimizing dopant profile Theoretical agenda explain enhanced doping optimize dopant profile for device design design process for optimal dopant profile
26 Optimizing dopant profile why does enhanced doping occur? Laser pulse Sulfur x Liquid Solid h(t) physical mechanisms: melting and resolidification of thin layer sulfur diffusion into liquid silicon incorporation into solid during resolidification
27 Optimizing dopant profile why does enhanced doping occur? Laser pulse Sulfur x Liquid Solid h(t) mathematical model: calculate dynamics of two fields temperature T(x,t) sulfur concentration c(x,t)
28 Optimizing dopant profile calculation step 1: temperature profile set up by laser
29 Optimizing dopant profile calculation step 1: temperature profile set up by laser Superheated!
30 Optimizing dopant profile calculation step 2: solid melts, solute incorporated
31 Optimizing dopant profile calculation step 2: solid melts, solute incorporated melting: heat diffusion energy balance
32 Optimizing dopant profile calculation step 2: solid melts, solute incorporated melting: heat diffusion energy balance incorporation: solute diffusion mass balance
33 Optimizing dopant profile calculation step 2: solid melts, solute incorporated melting: heat diffusion energy balance incorporation: solute diffusion mass balance
34 Optimizing dopant profile boundary condition critically affects dopant profile Laser pulse Sulfur x Liquid Solid h(t)
35 Optimizing dopant profile two scenarios
36
37
38 Optimizing dopant profile two scenarios constant concentration constant sulfur flux
39 10 µm Optimizing dopant profile
40 10 µm Optimizing dopant profile
41 Optimizing dopant profile
42 Optimizing dopant profile
43 Optimizing dopant profile
44 Optimizing dopant profile
45 Optimizing dopant profile cross-sectional Transmission Electron Microscopy
46 M. Wall, F. Génin (LLNL) Optimizing dopant profile 1 µm
47 Optimizing dopant profile decouple ablation from melting
48 Optimizing dopant profile decouple ablation from melting
49 Optimizing dopant profile decouple ablation from melting undoped doped
50 Optimizing dopant profile decouple ablation from melting
51 Optimizing dopant profile secondary ion mass spectrometry 1.0 concentration (10 21 cm 3 ) depth (nm)
52 Optimizing dopant profile 1.0 concentration (10 21 cm 3 ) depth (nm)
53 Optimizing dopant profile appears to be closer to constant flux
54 Outline goals optimizing dopant profile intermediate band
55 Intermediate band what dopant states/bands cause IR absorption?
56 Intermediate band 1 part in 10 6 sulfur introduces donor states in gap CB ev ev ev 0.11 ev 0.09 ev 0.08 ev ev ev VB Janzén et al., Phys. Rev. B 29, 1907 (1984)
57 Intermediate band absorptance (1 R int T int ) wavelength (µm) 2 1 absorptance 0.5 crystalline Si energy (ev) 1.5
58 Intermediate band 10 6 sulfur doping wavelength (µm) 2 1 absorptance 0.5 sulfur impurity states Si band edge crystalline Si energy (ev) 1.5
59 Intermediate band laser-doped S:Si wavelength (µm) 2 1 laser-doped Si absorptance 0.5 sulfur impurity states Si band edge crystalline Si energy (ev) 1.5
60 Intermediate band laser-doped S:Si wavelength (µm) 2 1 laser-doped Si multiple relections absorptance 0.5 sulfur impurity states Si band edge crystalline Si energy (ev) 1.5
61 Intermediate band laser-doped S:Si wavelength (µm) 2 1 laser-doped Si absorptance 0.5 sulfur impurity band Si band edge crystalline Si energy (ev) 1.5
62 Intermediate band isolate surface layer for Hall measurements device layer buried oxide silicon substrate
63 Intermediate band isolate surface layer for Hall measurements device layer buried oxide silicon substrate
64 Intermediate band isolate surface layer for Hall measurements laser device doped layer region buried oxide silicon substrate
65 Intermediate band isolate surface layer for Hall measurements buried oxide silicon substrate
66 Intermediate band isolate surface layer for Hall measurements buried oxide silicon substrate
67 Intermediate band
68 Intermediate band Hall measurements 100 temperature (K) E d = 310 mev 10 n-doped cm N = cm 3 N/N room 1 p-doped 10 -cm 0.1 laser-doped /T (mk 1 )
69 Intermediate band transition to metallic behavior at high doping T (K) N s (cm 2 ) highly S doped Si Si substrate /T 1 (K 1 )
70 Intermediate band can we understand this intermediate band using atomistic modeling?
71 Intermediate band density of states
72 Intermediate band density of states unoccupied, localized: eats electrons occupied, localized: eats holes
73 Intermediate band recombination rate
74 What s next? change dopant/substrate combination
75 What s next? optimal dopant profile is flat 1.0 concentration (10 21 cm 3 ) depth (nm)
76 What s next? change incorporation process: electrospray pulse sequence design
77 Acknowledgments
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