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InternationalJournalofEnergyScience(IJES)Volume3Issue6,December2013www.ijesci.

org
doi:10.14355/ijes.2013.0306.04

BlackSilicon:MicrofabricationTechniques
andCharacterizationforSolarCells
Applications
A.Deraoui1,2,A.Balhamri3,4,M.Rattal1,Y.Bahou1,A.Tabyaoui1,M.Harmouchi1,Az.Mouhsen1andE.M.
Oualim1
UnivHassan1,LaboratoireRayonnementetMatire,26000Settat,Maroc
InstituteofCondensedMatterandNanosciencesNanophysics(IMCN/NAPS),UniversitCatholiquedeLouvain,
CheminduCyclotron2,B1348LouvainlaNeuve,Belgium
3UnivHassan1,EcoleSuprieuredeTechnologie,218Berrechid,Maroc
4ResearchInstituteforMaterialsandEngineering,ChimiedesInteractionsPlasmaSurface(ChIPIS),CIRMAP,
UniversitdeMons,PlaceduParc20,B7000,Belgium
1
2

a.deraoui@gmail.com,adil.balhamri@gmail.com,mourad.rattal@gmail.com,ylouch2000@gmail.com,
ylouch2000@gmail.com,mharmouchi@hotmail.com,az.mouhsen@gmail.com,oualim.elmostafa@gmail.com

Abstract
The properties of black silicon are well suited for use in
photovoltaicapplications.Weplantousetheadvantagesof
blacksilicontobuildnewtypesofsolarcellsthatwillbeable
to capture solar energy across a wider range, thereby
realizing greater efficiency in future photovoltaic cells (J.S.
Yoo2006)(K.Nishioka2009)(Y.M.Song2010)(Y.Xia2011).
The method of production has brought the use of black
silicon in photovoltaic arrays closer to commercial
realisation, as it will reduce the cost of black silicon
production, minimize reflectivity and maximize the
absorbance (B.S. Kim 2011) (H. Sai 2006) (H. Sai 2007) (K.
Tsujino 2006) (K. Nishioka 2008). The basicobjective of this
paper is to create black silicon by chemical wet etching
techniques using Au nano particles directly formed on
siliconsubstrates.Wefurtherdecidedtotrytooptimizethis
materialusingnonheavilyphotolithographicmethods,such
asetching.ThemorphologyofBlackSiwascharacterizedby
Scanning Electron Microscopy (SEM) and the optical
propertiesweregiventhankstoCarySpectrometer.

more absorbed and less reflected (figure 2). This is


whatgivesblacksiliconitsname.

FIG.1SEMIMAGEOFAPYRAMIDTEXTUREDBLACKSILICON
SURFACE

Keywords
SolarCells;BlackSilicon;Photolithographic;Thinfilms

Introduction
Black silicon is a material that is chemically equal to
normalsilicon.Theonlydifferencebetweenthesetwo
isthesurfacetreatmentthatchangesthemorphology.
This special morphology has to represent a certain
roughnessofthesurfaceanditistypicallydoneby
creatingpyramidtextures(figure1)ortrencheswithin
the silicon. When these structures are in place, and
when they are small enough, incident light will be

FIG.2SCHEMATICREPRESENTATIONOFLIGHT
INTERACTIONWITHANORMALSILICONSURFACE(LEFT)
ANDABLACKSILICONSURFACE(RIGHT)

Due to its increased absorption this material shows a


lot of promising of applicability in photoelectric
devices, such as solar panels. The need for new
energetic sources has stimulated considerably the
drive for better renewable energy efficiency in which
solar is included. Since black silicon can absorb more

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light due to its structure, it has the potential to be a


major innovation in this domain. The biggest
challenge for the moment resides in the making of
black silicon, preferably using cheaper and simpler
techniques. The fact that it is based on a well known
material and that it shows real promise in enhancing
photoelectric devices has made black silicon an
interestingtopicforresearchers.

cleaning as follow: they were immersed in a sulfuric


acidhydrogen peroxide mixture (SPM) for 10 min,
rinsedwithultrapurewaterfor10minanddippedin
dilute hydrofluoric acid 2% HF for 15 seconds. Three
differentwafershavebeenpreparedandtheywereall
cleanedwiththeabovemethodasshowninthefigure
below. Since now, we will use notations sample 1 for
theonewhereoxidizedlayerwasdeposited,sample2
for the one siliconnitride layer was deposited and
sample 3 for the reference wafer where there was no
insulationlayeronit.

Thebasicobjectiveofthispaperistoexploitdifferent
techniques of micro fabrication to create black silicon
and then characterize it.; and further this material is
determined to be built using nonheavily
photolithographic methods, such as etching (J. Zhao
1998). In this paper the wet etching process was
developedtocreateblacksilicon.
Experimental Setup
Wetetchingmethodshavebeendevelopedtofabricate
highaspectratioholesinsilicon.Inthismethod,deep
straight holes or trenches can be produced by wet
chemical etching, which is suitable for mass
production, in solutions containing hydrofluoric acid
(HF). It is a simple and fast technique that creates
thesetexturesusingwetchemicalprocesses.
Thefollowingmechanismisproposed:

Cathodereaction(atmetal):

FIG.3BASICPROCESSFORCREATINGBLACKSILICON
SURFACEWITHGOLDNANOPARTICLES

H2O2+2H 2H2O+2h (21)

2H+2eH2
(22)
Anodereaction(Si):
+

On sample 1, 400 nm of oxide layer was deposited


using oxidation wet technique and on sample 2, 200
nm siliconnitride (Si3N4) was deposited using Low
pressure Chemical Vapor Deposition (LPCVD)
technique. The temperature of deposition for this
oxide layer is 1000C (1273.15 K). Oxidation wet was
used since it gives a better quality of oxide than the
dryoxidation.Onthethirdsample,noinsulatinglayer
was deposited since we want to study the effect of
insulatinglayersontheperformanceofblacksiliconin
relation with its optical and electrical properties by
using this sample as a reference one. Then about 300
nm polysilicon (PSi) was deposited on sample 1 and
sample2byLPCVDtechniqueat625C.Then1nm,3
nmand7nmofAumetalweredepositedonsamples
1, 2 and 3 by metal evaporation technique. This was
performed by lift off set up on the front side of our
samples.Thiscouldbeachievedbycontrollingtherate
of the evaporation. These samples were annealed at
500Cfor10minutes.Althoughannealingisthebasic
stepinmakingblacksiliconwithwetetching,wehave
made sample without annealing to see the effect. Of
course,thiswasdonesinceitwasnotpossibletomake

Si+4h++4HFSiF4+4H+(23)

SiF4+2HFH2SiF6(24)
Overallreaction:
Si+H2O2+6HF2H2O+H2SiF6+H2
(25)
Methodsusingthinmetalfilmsorparticlesloadedon
silicon wafersfor assisting wet chemical etching have
recently been developed. These methods utilize the
catalytic actions of metals for dissolution of silicon in
HFbased solutions. Since these methods do not need
electrochemical equipment, they seem to be suitable
formassproduction.Ithasbeenfoundthatcylindrical
holeswithdiametersoftensnanometerswereformed
insiliconinthe(100)directionbywetchemicaletching
in an aqueous solution containing HF and hydrogen
peroxide(H2O2)whengoldnanoparticleswereloaded
on the silicon surface before the etching process. As
the holes were generated,gold particles sankinto the
bulkofsilicon.
PolishedSi(100)waferswereusedinthefabricationof
blacksilicon.TheSisampleswerecleanedbystandard

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InternationalJournalofEnergyScience(IJES)Volume3Issue6,December2013

annealing on our samples even though they could be


helpful for comparison. The samples were etched in
aqueous solutions containing HF and H2O2 after the
sampleswerecleanedwithH2Ofordeionization.The
concentration of HF in solutions was 49%, and H2O2
was 30%. The importance of Gold in the wet etching
wastousethemasacatalyst.Unlessweusecatalysts
to speed up the reaction, the whole process will be
nothing except simple slow etching of the SiO2 layer,
which doesnt have technological importance. First
when the Si layer is exposed with H2O2, SiO2 and H2
gas will be removed from the product. Then the
samples were etched with 49% HF. In this process
there will be creation of SiF6 in the form of gas. As
soon as this gas is evaporated from the sample, the
gold metal particles will sink down, creating lots of
highaspectratioholeswhichwillbetheblacksilicon.

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4(b) shows the same sample but after it was etched


with HF and H2O2 for 120 seconds. From this figure
we can see black dots on the brighter background.
Theseblackspotsaresupposedlytheholeswherethe
metal particles sink down. This could be further
arguedbythefactthattheaveragesizeoftheseblack
spots(holes)is122nmwhichisinagoodcorrelation
with the average size of the Au particles. These two
pictures are very critical in explaining the whole
processofmakingtheblacksilicon.
The effect of the metal layer thickness on the
penetration depth of the particles has been studied
from their respective SEM images. The results are
presentedinthefiguresbelow:
a

Results and Discussion


Morphologies and Cross sectional views of the
samples were observed by scanning electron
microscopy (SEM). With Scanning microscope, it is
possible to compare the difference in morphology
betweenthereferencesampleandthosewithdifferent
structures and layers. Even with naked eye, it is
possibletoseethedifferencebetweenthem.

FIG.5SEMIMAGESOFSAMPLESAFTERANNEALING1nmAu
LAYER(a),3nmAuLAYER(b)AND7nmAuLAYER(c)

Figure below shows SEM images of black silicon


sample where the thickness of the Au metal is 7 nm.
The annealing temperature of these samples was
500C and the annealing time was 10 minutes as
explainedontheprocessingpart.
a

FIG.6SEMCROSSSECTIONALAREAIMAGESOFSAMPLES
AFTERANNEALING1nmAuLAYER(a),3nmAuLAYER(b)
AND7nmAuLAYER(c)

TheaveragesizeoftheAumetalparticlesincreasesas
thethicknessofthemetallayerincreases.Forthethree
images shown in figure 5, the average size of the
grains is found to be 20, 40 nm and 120 nm
respectively. This increase in the particle size is
associatedwiththefluxofparticlesdiffusingwhenthe
temperatureishighenough.Whenthereisonly1nm
layerofAuatoms,therewillbelessnumberofatoms
makingtheparticlesthanthe7nmlayereventhough
theannealingtemperatureandtheannealingtimeare
keptthesame.

FIG.4SEMIMAGEOFSAMPLEAFTERANNEALING(a)AND
AFTERETCHING(b)

From figure 4(a), we can see that when Au metal is


annealed at high temperature, the metal atoms will
diffuse and make gold particles. The temperature of
this annealing is made high so as to increase the
kinetics of diffusion, Au atoms will make nanosized
particles. From this figure we can see clearly spaced
gold particles with an average size of 131 nm. Figure

All the measurements were tested at the wavelength


from 250 to 1100 nm at room temperature with a
spectral resolution of 15 nm. The reflectance and the
absorbanceofeachofthefoursamplesweremeasured
usingapurposebuiltintegratingsphereattachmentof
ahighaccuracyspectrometer.

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Theabsorbanceofblacksiliconisgreaterthan85%,in
thewavelengthrangefrom250to1100nm,itreached
96%forthesampleofblackSiusing7nmAufilmand
theabsorbanceofuntreatedsiliconintheUVandNIR
was much lower than the black silicon one and the
absorbance bandwidth of black silicon was much
wider than the untreated silicon one. This is mainly
due to the microstructured surface of black silicon,
such as column and pores, giving rise to the multi
reflectionoftheincidentlightandincreasingthearea
of absorbing surface. The photon is reflected several
timesbythemicrocolumnandnanopores,whichwill
increase its absorbing probability. Due to no
introduction of impurity into the silicon, there is no
extraabsorbingenergylevelinthegapofblacksilicon.
Consequently, the photons with the energy below
band gap cannot be absorbed. Thus, the spectrum of
absorbance of the black silicon achieved by wet
etching is similar to the absorbing spectrum of the
common untreated silicon at the wavelength larger
than1100nm.

FIG.7NORMALINCIDENCESPECTRALREFLECTANCEFROM
BLACKSISURFACEETCHEDWITHVARIOUSAuFILM
THICKNESSES(1,3AND7nm)ANDFROMUNTREATED
SILICONSURFACE

Figure 7 shows a typical normal incidence spectral


reflectance of black Si surface. The reflectance of the
untreated silicon is also plotted for comparison. The
reflectanceoftheblackSisampleusing7nmAufilm
was the lowest. The reflectance was maintained at
almost0%forthevisibleregionaswellasthenearIR
region.ThesamplesofBlackSiusing1nmand3nm
Au film were also maintained at less than 3%. The
reflectiondecreaseddrasticallycomparedtountreated
siliconsurfaceasexpected.Thethicknessofdeposited
thin film of gold on the surface played an important
role and changed the value of the reflectance. It
decreased when the thickness of Au film increased.
We can conclude that our treatment changes
significantlytheopticalpropertiesofBlackSisamples.

Conclusions
Inthisstudy,experimentswereundertakeninorderto
determinetheoptimizedprocessusingvarioussizesof
Au nano particle. The Au nano particles were
fabricatedviathermalannealingofAuthinfilmswith
1, 3 and 7 nm thickness. It was found that the initial
Au film thickness can affect the particle size and
change the etching conditions and optimize optical
properties of the surface. The absorption was
significantly increased and the reflection decreased
drastically in the wavelength range from 250 to 1100
nm after the formation of the antireflection, and if
applied to a solar cell, it will greatly increase the
conversionefficiency.
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FIG.8NORMALINCIDENCESPECTRALABSORBANCEFROM
BLACKSISURFACEETCHEDWITHVARIOUSAuFILM
THICKNESSES(1,3AND7nm)ANDFROMUNTREATED
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InternationalJournalofEnergyScience(IJES)Volume3Issue6,December2013

developing and improving PV cells in several material


systems, Characterizing PV cells, modules, and systems to
improve performance and reliability and PV engineering.
His scientific interests include design of Micro and
Nanosystems, Microfacbrication techniques, biomimetic
transfer of reverse engineered mechanisms to material
scienceandvacuumphysicsandtechniques.

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K. Tsujino, M. Matsumura, Sol. Energy Mater. Sol. Cells 90
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AdilBALHAMRIwasborninMorocco
in1980.HereceivedhisPh.D.degreein
Physics in 2012 from the University of
Hassan 1er, Morocco. His scientific
interests include solar cells and
Renewable Energy, plasma diagnostics,
thin film growth during ionized PVD
processes in particular HPPMS. He is
the author of several lectures and
articles. After a Researcher as a PhD student at the
UniversityofMons,Belgium,hecurrentlyholdsaProfessor
position, at the High School of Technology, in particular at
the Department of Industrial Engineering and Renewable
Energy.

(2008):919922.
Y. Xia, B. Liu, J. Liu, Z. Shen, C. Li, Sol. Energy 85 (2011):
15741578.

Abdessitir DERAOUI was born in


MeknesMoroccoin1980.Heisateacher
assistant at Catholic University of
LouvainBelgium.HereceivedhisM.Sin
physics from Hassan 1st university of
Settat Morocco. He is currently PhD
student at the same University. His
thesis topic is solar energy, it including

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