Silicon hybrid solar cells using nanocrystalline

Si quantum dots and Si nanotips for energy

management

Miss Naraphorn Tunghathaithip

Department of Physics, Faculty of Science, Chulalongkorn University

 Outline
Introduction

Purpose of the study

Experimental Details

Results

Conclusion
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 Introduction
Hybrid solar combine the advantages of organic and inorganic semiconductor.
The organic semiconductor is used to absorb light and transports holes.
The inorganic semiconductor is used as an acceptor and electron transport.

Nanocrystalline silicon quantum dots (nc-Si QDs) are very small semiconductor particles
which use as the absorbing photovoltaic material.

Silicon nanotips is one of optically active nanostructure which use as inorganic layer of
the hybrid solar cell.

PEDOT:PSS or poly(3, 4-ethylenedioxythiophene):poly(styrene sulfonate) is a polymer

mixture of two ionomers which use as organic layer of the hybrid solar cell.

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 Purpose
The purpose of this research is to fabricate more efficiency hybrid solar cells by using
nc-Si QDs.
Use the metal – catalyzed electroless etching (MCEE) method to fabricate silicon nanoholes (SiNHs)
Use chemical polishing etching (CPE) method to modify SiNHs into silicon nanotips
Compare the efficiency of three types of cell

Silicon nanotips are coated Silicon nanotips are coated Silicon nanotips are coated
with PEDOT:PSS only. with nc-Si QDs mixed with with nc-Si QDs followed by
PEDOT:PSS. PEDOT:PSS.

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 Experimental Details

n-type Si (100) Substrate SiNH by wet etching Silicon nanotips by CPE nc-Si QDs spin on
Silicon nanotips

Deposition of the top and Spin coating of PEDOT:PSS

rear electrodes

*CPE is Chemical Polishing etching

Ref: T. Subramani, J. Chen, Y. Sun, W. Jevasuwan, N. Fukata, Nano Energy, 2017

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 Results
Tdiffuse
HT  100%
Ttotal

Tdiffuse  Ttotal  Tspecular

Ttotal is the total transmittance

H T  0.1% Tdiffuse is the diffused transmittance

Tspecular is the specular transmittance

Fig. 2. Haze spectrum of nc-Si QDs on glass substrates

Ref: T. Subramani, J. Chen, Y. Sun, W. Jevasuwan, N. Fukata, Nano Energy, 2017

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 Results
Silicon nanoholes was fabricated by Metal – Catalyzed Electroless Etching (MCEE) method

Fig. 3. (a) 15๐ tilted view and (b) top view of SEM images of high-density SiNH arrays before the CPE process.

These nanoholes have an average diameter of 30 – 50 nm and a high density of 1010/cm2

Ref: T. Subramani, J. Chen, Y. Sun, W. Jevasuwan, N. Fukata, Nano Energy, 2017

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 Results
Silicon nanotips was fabricated by Chemical Polishing etching (CPE) treatment

Fig. 3. (c) CPE-treated and –modified tapered silicon nanotips after 5 s treatment. (d) nc-Si QD and PEDOT:PSS coated silicon nanotips

Ref: T. Subramani, J. Chen, Y. Sun, W. Jevasuwan, N. Fukata, Nano Energy, 2017

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 Results

Fig. 4. (a) J-V characteristics of PEDOT:PSS/Si hybrid solar cell (a) without nc-Si QDs and with 5, 7 and 10 wt% of nc-Si QDs mixed with
PEDOT:PSS. (b) nc-Si QDs directly coated on silicon nanotip surfaces, followed by PEDOT:PSS coating.

Ref: T. Subramani, J. Chen, Y. Sun, W. Jevasuwan, N. Fukata, Nano Energy, 2017

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 Results
The nc-Si QDs absorb UV light and release non-
radiative energy transfer (NRET) and radiative
energy transfer (RET).

The NRET and RET from nc-Si QDs generates

excess electron-hole pairs in the Si nanostructure
layer.

Fig. 5. Energy band diagram of the hybrid solar cell

PEDOT:PSS is used as a hole – transporting path, a

passivation layer and antireflection coating.

Ref: T. Subramani, J. Chen, Y. Sun, W. Jevasuwan, N. Fukata, Nano Energy, 2017

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 Results
Table 1: Photovoltaic parameter of PEDOT: PSS/Si hybrid solar cell with various concentrations
of GQDs and direct coating of nc-Si QDs on silicon nanostructure.

Sample PCE (%) Jsc (mA/cm2) Voc (V) FF (%)

PEDOT:PSS without 10.39 34.07 0.539 56.51

nc-Si QDs 10.21 34.08 0.535 55.95
(  0.16) (  0.01) (  0.003) (  0.49)
PEDOT:PSS+5% nc-Si 10.83 35.21 0.544 56.48
QDs 10.71 35.19 0.541 56.18
(  0.13) (  0.03) (  0.003) (  0.58)
PEDOT:PSS+7% nc-Si 11.65 36.30 0.542 59.14
QDs 11.47 36.24 0.537 58.86
(  0.16) (  0.11) (  0.008) (  0.48)
PEDOT:PSS+10% nc-Si 11.17 34.92 0.541 59.07
QDs 10.89 34.47 0.539 58.59
(  0.36) (  0.40) (  0.005) (  0.85)
PEDOT:PSS/nc-Si QDs 13.73 37.85 0.595 60.91
/Silicon nanotips 13.54 37.75 0.593 60.42
(  0.31) (  0.16) (  0.003) (  0.74)
*Numbers in bold are the maximum record values.

Ref: T. Subramani, J. Chen, Y. Sun, W. Jevasuwan, N. Fukata, Nano Energy, 2017

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 Conclusions
Silicon nanotips

Nc-Si QDs

PEDOT:PSS

By making use of the energy effect of nc-Si QDs, PEDOT:PSS/Si hybrid solar cells are
successfully fabricated with 13.6% efficiency.

With this architecture, the operating range is expanded toward the UV region and also be
effective in exciton collection.

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 References
[1] T. Subramani, J. Chen, Y. Sun, W. Jevasuwan, N. Fukata, High-efficiency silicon hybrid solar cells employing
nanocrystalline Si quantum and Si nanotips for energy management, Nano Energy, 2017

[2] S.C. Shiu, J.J. Chao, S.C. Hung, C.L. Lin, Morphology dependence of silicon nanowire/poly(3,4-
ethylenedioxythiophene):poly(styrene sulfonate) heterojunction solar cells, Chem. Mater, 2010

[3] J. Zhang, T. Song, X. Shen, X. Yu, S.T. Lee, B. Sun, A 12%-efficient upgraded metallurgical grade silicon –
organic heterojunction solar cell achieved by a self-purifying process, ACS Nano, 2014

[4] S.A. Hussain, An introduction to fluorescence resonance energy transfer (FRET), Energy, 2009

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 Redox reaction of MCEE Method -1

Simple scheme diagram of the MCEE method with chemical reactions

Ag  eVB

 Ag0 (s)

 Electrons from the valence band of the Si are attracted by Ag ion.

 The solid Ag0 particle is formed on the Si surface.
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 Redox reaction of MCEE Method -2

Simple scheme diagram of the MCEE method with chemical reactions

2Si(s)  2H2O  2SiO2  4H  4eVB



 SiO2 is formed around the Ag/Si interface (under Ag particle).

 SiO2 is etched away by HF acid.
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 Redox reaction MCEE Method -3

Simple scheme diagram of the MCEE method with chemical reactions

SiO2 ( s )  6HF  H 2SiF6  2H 2 O

 SiO2 is rapidly etched by HF acid, especially under Ag particle.

 More SiO2 more etching reaction!!!
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 Fabrication process of modified silicon nanoholes

Cleaning processes Etching processes

Acetone 10 min HF : AgNO3 5s

DI water 10 min HF : H2O2 25 s

H2SO4 : H2O2 10 min

HNO3 Remove Ag particles

(piranha solution)
HF Remove Si oxide

isopropanol 10 min
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Haze spectrum

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