EPJ Photovoltaics 3, 35004 (2012)

www.ep j- pv .org
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Abstract !%
the (ears
to co/e,
electricit(
pro&)ctio%
is 'o)%&
to i%crease,
a%& 6)
2
<%*%(*, *e)
4
(6<:*)
co/po)%&s,
&)e to their
s)ita'ilit(
to thi%- l/
solar cells,
co)l& 'e a
/ea%s to
=)l ll the
&e- /a%&.
;=ter
e>plai%i%g
the reaso%s
o= the
s)&&e%
i%terest o=
the 6!?*
scie%tic
co//)%it(
=or 6<:*
solar cells,
this paper
reviews
rece%t
papers
p)'lishe& o%
the s)'ject
o=
@1esterites-
'ase& solar
cells. ;=ter a
&escriptio%
o=
cr(stallograp
hic a%&
optoelectro%
ic
properties,
i%cl)&i%g
6<:*
cr(stalli%e
str)ct)re,
&e=ect
=or/atio%
a%& /etal
co/positio%,
this review
paper
=oc)ses o%
6<:*
s(%thesis
processes
a%& &evice
prop- erties.
*(%thesis
strategies,
i%cl)&i%g
o%e- or two-
step
processes,
&epositio%
te/perat)re,
'i%ar(
=or/atio%
co%trol via
at/osphere
co%trol a%&
their e ect
o% &evice
properties
are
&isc)sse&.
1
Sustainabil
ity of
photovoltai
c industry
!% the
(ears to co/e,
electricit(
pro&)ctio% is
'o)%& to
i%crease (=ro/
15 P4 h i%
200A to 2$B34
P4 h i%
2035 C1D) a%&
as a
co%se2)e%ce
the i%crease&
&e/a%& o%
=ossil =)els as
well as possi'le
reg)latio%s o%
6
2
e/issio%s
are 'o)%& to
i%crease the
wholesale
electricit(
costs. %
the other
ha%&, the
price-
e>perie%ce
=actor o= 22E
that
was o'serve&
=or the last 4
&eca&es
sho)l& sta( at
the
sa/e level or
slightl( 'elow
C2, 3D, lea&i%g
to a &ecrease
o= photovoltaic
(PF) electricit(
costs C2, 4D. ;
rst cha%ge
o= para&ig/ is
%ow
happe%i%g,
'eca)se i%
so/e places
li@e *o)th !tal(
a%& other
s)%%(#high
electricit(
price re-
gio%s C5D, the
price o= retail
electricit( is
higher tha%
the
cost o= PF
electricit(
(gri& parit(). ;
seco%& parit(,
the
G=)el
parit(H, will
happe% whe%
the cost o= PF
electricit(
is lower tha%
the /argi%al
costs o=
operati%g
=ossil =)el
'ase& power
pla%ts C3D.
;ccor&i%g to
&eplo(/e%t
sce%ar-
ios, this =)el
parit( co)l&
happe%
'etwee% 2020
a%
&
20
40.
:
h
e
/
a
s
s
i
v
e
&
e
p
l
o
(
/
e
%
t
o
=
P
F

=
o
r
e
s
e
e
%
i
%

(
e
a
r
s
20
20
2
04
0
co
)l
&
lea
&
to
1.5
to
2.5
:
4
p
o=
wo
rl&
-
wi
&e
i%s
tall
e&
PF
ca
pa
cit
(
i%
20
30,
wit
h
a
&e
/a
%&
o=
20
1
50
?
4
p#
(
a%
&
aro
)%
&
30
E
o=
the
/a
r@e
t
ta@
e%
'(
th
i%
l
/
s
C2,
4D.
:
h
e
2
)
e
s
ti
o
%
o
=
t
h
e
s
)
s
t
ai%a'il
it( o=
the
pro&)c
tio% o=
20150
?4p#( o=
PF was
raise& '(
a =ew
p)'licatio
%s,
a%& i%
partic)lar
the
worl&wi&e
/i%i%g
a%&
re %i%g
capac-
it( o= a
=ew
critical
ele/e%ts
co)l& 'e
the /ai%
pro'le/
o= the
photovolt
aic
i%&)str(
i% the
(ears to
co/e.
Each
a
e-/ail"
delbos.s
ebastien
!mail.
com
PF
tech%olog
( has o%e
or /ore
li/iti%g
ele/e%ts,
s)ch as
silver =or
cr(stalli%e
silico%,
i%&i)/
a%&
galli)/
=or 6!?*,
:ell)ri)/
=or 6&:e,
,)the%i)
/ =or
&(e-
se%sitiIe&
solar cells,
silver a%&
i%&i)/
=or thi%-
l/
silico%,
ger/a%i)
/, gol&,
i%&i)/
=or !!!-F
PF C5, $D.
:he
chalcoge%i
&e tech-
%ologies
are
partic)larl
(
v)l%era'le
to !%, ?a,
:e s)ppl(,
which has
'ee%
%ote&
critical or
%ear
critical '(
the 8*
De-
part/e%t
o= E%erg(
CAD or the
E)ropea%
6o//issi
o% C10D.
;ccor
&i%g to
vario)s
a)thors,
the
pro&)ctio
% o= PF
/o&)les
co)l& 'e
li/ite&
'elow the
&e/a%&
reporte&
ear- lier i%
this
paper, as
s)//ariIe
& i%
:a'le 1.
6r(stalli%
e silico%
PF see/s
s)ita'le
=or
s)ppl(i%g
the
&e/a%&,
')t o%e
sho)l&
@eep i%
/i%& that
the 'asic
ass)/ptio
% )se& =or
the thir&
a%&
=o)rth
col)/% o=
this ta'le
is that all
worl&wi&e
pro&)ctio
% o= silver
is )se& =or
cr(stalli%e
PF. :he
=th
col)/%
shows the
=orecast
2030
&e/a%&
=or ;g, :e,
!% with
respect to
the 200$
pro&)ctio
%. !t
appears
that the
&e/a%&
will grow
e%or/o)sl
(. != we
=oc)s o%
!%, i%
2030 the
total
&e/a%&
(i%cl)&i%g
PF a%&
other
)ses)
co)l& 'e 3
to 5 ti/es
the 200$
pro&)ctio
% C10,11D,
whereas,
as !% is a
'(pro&)ct
o= <%
e>tractio%,
the
elasticit(
o= the
pro&)ctio
% with
respect to
&e/a%&
is low.
%e
a)thor
s)ggests
that 6!?*
a%& 6&:e
tech%ologi
es will %ot
'e i/-
pe&e& '(
reso)rces
pro'le/s,
')t he
&oes %ot
ta@e the
i%crease
o= other
so)rces o=
&e/a%&
=or !%
a%& :e
i%to
acco)%t
C12D.
:he
s)stai%a'i
lit( o= PF
pro&)ctio
% is
there=ore
a real
2)estio%,
a%& the
&evelop/
e%t o= a
%ew PF
tech%ol-
og( 'ase&
o%
a')%&a%t
a%&
pre=era'l(
%o%-to>ic
ele/e%ts
wo)l&
alleviate
the
press)re
o% all PF
tech%ologi
es i% ter/
o=
reso)rces.
"his is an #pen Access
article distributed under
the terms of the $ r eat i v e
$o mm on s A tt r i but i on %
& onco m m e r c i a l ' i cen s e
3 . ( ) which permits
unrestricted use)
distribution) and
reproduction in any
noncommercial medium)
provided the ori!inal wor* is
properly cited.
35004-p4
EPJ Photovoltaics
12
10
8
6
4
2
0
1996 1998 2000 2002 2004 2006 2008 2010
2012 2014
+i!. 1. Evol)tio% o= the recor& e cie %c( =or 6<:* solar cells. *ee :a'le 2 =or the re=ere%ces.
"able 1. Pro&)ctio% li/itatio%s o= the PF tech%ologies C5, $, 10B12, 12AD.
PF tech%olog( Ji/iti%g
ele/e%t
9a> i%stalle& capacit(
'ase& o% the li/iti%g
ele/e%t reserves
(1.5B2.5 :4p &e/a%&)
9a> (earl( pro&)ctio% 'ase&
o% a%%)al pro&)ctio% o=
li/iti%g /aterial
(20B150 ?4p &e/a%&)
,atio (&e/a%&
2030#200$ pro&)ctio%)
o= li/iti%g ele/e%t
c-*i ;g 5B15 :4p 305 ?4p 20
6&:e :e 0.1B0.$ :4p 2.3B40 ?4p 50
6!?*
D(e-se%sitiIe&
solar cells
!%
,), !% (:6)
0.1B0.3 :4p
0.03B0.A :4p
13B23 ?4p
2.2 ?4p
3
%.a.
2 Advanta!es of $,"S
,ece%tl( the 6!?* scie%ti c co//)%it( starte& to
wor@ o% 6)
2
<%*%(*, *e)
4
, (6<:*), a%& the e%th)sias/
was @i%&le& '( the =ast i%crease o= recor& e cie%c( o=
6<:*-'ase& solar cells, =ro/ the 200A recor& o= 3.5E C13D to
2011 recor& o= 10.1E C14D, as show% i% +ig)re 1. 6<:* has
%)/ero)s a&va%tages that co)l& lea& to its /assive )se as
a% a')%&a%t, %o% to>ic, low cost a'sor'er =or thi%- l/
photovoltaic solar cells"
- it is a co/po)%& whose i%tri%sic poi%t &e=ects lea& to
p-t(pe se/ico%&)ctor 'ehaviorK
- it has a &irect 'a%&gap a%& a% a'sorptio% coe -
cie%t >10
4
c/
1
, which is s)ita'le =or thi% l/ photo-
voltaics applicatio%s C15B15DK
- its 'a%& gap has 'ee% pre&icte& C1$D to 'e 1.0 eF =or
6)
2
<%*%*e
4
a%& 1.5 eF =or 6)
2
<%*%*
4
a%& evi&e%ces
o= the 'a%&gap t)%a'ilit( have 'ee% =o)%& via the vari-
atio%s o= F
#$
C1AD, as well as &irect /eas)re/e%ts o=
the variatio% o= the 'a%&gap 'etwee% 1.0 eF =or 6)
2
<%*%*e
4
a%& 1.5 eF =or 6)
2
<%*%*
4
C20B24D. :he 'a%&
gap o= 6<:* ca% also 'e t)%e& '( i%corporatio% o= ?e,
?e-co%tai%i%g /aterials havi%g s/aller 'a%&gap
tha% their ?e-=ree co)%terparts C25D. :his t)%a'ilit( is
o= partic)lar i%terest =or the /a%)=act)ri%g o= a'-
sor'ers with a 'a%& gap 'etwee% 1.1 a%& 1.5 eF, which
allow theoretical e cie%cies higher tha% 30E C23DK
- its cr(stallographic str)ct)re ca% accept so/e shi=ts
=ro/ the stoichio/etric co/positio% C25DK
- it i%cl)&es <% a%& *% which are respectivel( pro&)ce& i%
2)a%tit( 20 000 a%& 500 ti/es 'igger tha% !% C2$DK
- it is possi'le to /a@e 6<:* solar cells j)st '( replaci%g
6!?* '( 6<:* i% 6!?* solar cells, a%& s)ch solar cells
(iel&e& ecie%cies )p to 10.1E C14, 2AD. :he @%owle&ge
gathere& o% 'ac@ co%tact, ')er la(ers a%& wi%&ow
la(er '( 6!?* scie%tists ca% there=ore 'e )se& a%&
a&apte& =or 6<:* solar cells. 7evertheless, =or high
e cie%c( solar cells the processes )se& =or 6!?* so-
lar cells will %ee& to 'e t)%e&. :he ') er la(er, i%
partic)lar, will have to 'e tailore& i% or&er to a&-
j)st the lattice-/atchi%g, the vale%ce a%& 'a%& osets
with 6<:*K
- the grai% 'o)%&aries (?L) see/ to have the sa/e 'e%-
e cial properties =or 6<:* as =or 6!?*, s)ch as e%-
ha%ce& /i%orit( carrier collectio% ta@i%g place at the
?L C30D.
PVD / annealing
Electrodeposi on /
annealing Colloids in
!dra"ine / annealing
#anopar cles
$onograin
Coe%apora on
Re
co
rd
eff
ici
en
cy
(%
)
3 $rystallo!raphic and optoelectronic
properties
:his paper is =oc)se& o% s(%thesis processes o= 6<:*,
a%& th)s will o%l( 'rie ( & a&&ress the cr(stallographic a%&
optoelectro%ic properties. +or /ore i%=or/atio% o% cr(stal
a%& 'a%& str)ct)re a%& &e=ects i% @1esterites, the rea&er
ca% %& a rece%t review &e&icate& to these topics here C31D.
3.1 $rystalline structure
!% the literat)re 6)
2
<%*%*
4
a%& 6)
2
<%*%*e
4
(as well
as 6)
2
<%?e(*, *e)
4
C32D) are &escri'e& '( the str)ct)ral
/o&els o= two %at)ral /i%erals" sta%%ite (space gro)p I
-42m) C33B35D a%& @1esterite (space gro)p I -4) C33D. :hese
cr(stal str)ct)res are ver( close, i% 'oth str)ct)res the
catio%s are locate& o% tetrahe&ral sites ')t their &istri-
')tio%s o% pla%es perpe%&ic)lar to the c-a>is are %ot the
sa/e. !% a&&itio%, the positio% o= the chalcoge% ato/ is
slightl( &i e re%t i% these str)ct)res C33B35D.
- @1esterite" (6) M *%) # (6) M <%) # (6) M *%), chalco-
ge% i% positio% (x, y, z), +ig)re 2K
- sta%%ite" 6) # (<% M *%) # 6), chalcoge% i% positio%
(x, x, z).
!% the rest o= the paper, G@1esteriteH will 'e )se& =or the
cr(stallographic str)ct)re, a%& G@1esteritesH will 'e
)se& =or 6)
2
<%*%(*, *e)
4
co/po)%&s that are cr(stalliIe&
i% @1esterite t(pe str)ct)re. N will 'e )se& =or the
chalcoge%s * a%& *e whe% a% eect or properties ca% appl(
to 'oth o= the/ (=or e>a/ple 6)
2
(*, *e) will 'e %ote& 6)
2
N).
D)e to their str)ct)ral si/ilarities, @1esterite a%& sta%-
%ite are ver( &i c)lt to &isti%g)ish '( N-,a( Diractio%
a%& ,a/a% spectroscop(, a%& it is %ecessar( to )se %e)-
tro% &iractio% C33, 35D to tell the/ apart. ;ccor&i%g to
a' i%itio calc)li, the /ost sta'le cr(stalli%e str)ct)re is
@1esterite C3$B42D a%& o%e st)&( '( a' i%itio calc)latio%
eve% s)ggests that all o'servatio%s o= sta%%ite str)ct)re =or
6<:* co/po)%&s were &)e to partial &isor&er i% the !-!!
(001) la(er o= the @1esterite phase C32D. ,ece%t %e)tro%
&iractio% C35D a%& a%o/alo)s &i)sio% C43D characteriIa-
tio%s show that 6<:* cr(stalliIes i% the @1esterite str)c-
t)re, a%& s(%chrotro% N-,a( e>peri/e%ts show that this
str)ct)re is &o/i%a%t =or te/perat)re <$53

6 (tra%sitio%
to a sphalerite c)'ic str)ct)re) C35D.
:he str)ct)ral &iere%ce 'etwee% 6)
2
<%*%*
4
a%&
6)
2
<%*%*e
4
is %ot clear. !t see/s that the *e co/po)%&
has larger lattice para/eters as well as higher electric co%-
&)ctivit( tha% the * co/po)%& C20D. 6o%cer%i%g /echa%-
ical a%& ther/o-ph(sical properties o= 6<:*, %o e>peri-
/e%tal &ata are availa'le, ')t a' i%itio si/)latio%s were
per=or/e& C44, 45D.
*)l=)r @1esterites have N,D pea@s ver( close to those o=
<%* a%& 6)
2
*%*
3
C33D, a%& ,a/a% spectroscop( is %ec-
essar( to tell the/ apart C43D. 7evertheless, it is %ot possi- 'le
to have a 2)a%titative &eter/i%atio% o= the seco%&ar(
phases '( ,a/a%. +or s)ch p)rpose, NE7;* has 'ee%
)se& C45D.
+i!. 2. 6)
2
<%*%(*, *e)
4
co/po)%& i% @1esterite str)ct)re, ac-
cor&i%g to C33D.
3.2 .ntrinsic point defect formation
:he @1esterite str)ct)re allows =or several t(pes o= poi%t
&e=ects which /a@e &iscrete e%erg( levels appear, allow- i%g
p-t(pe &opi%g. ;s i% the 6!?* /aterials, the &op- i%g is
o'tai%e& '( stoichio/etr( variatio%s a%& %ot '( e>tri%sic
&opi%g. 7evertheless, accor&i%g to a' i%itio cal- c)li, the
@1esterite str)ct)re is less tolera%t to these varia- tio%s tha%
the chalcop(rite str)ct)re C3A, 4$B51D. ;ccor&- i%g to poi%t-
&e=ect /eas)re/e%ts, the @1esterites are s)s- cepti'le to
higher carrier reco/'i%atio% tha% chalcop(- rite C52D.
9eas)re/e%ts o= the &eep &e=ects o= 6<:* are reporte&
here C53D.
?e%erall(, the *%-*e 'o%& is /)ch stro%ger tha% the
<%-*e a%& 6)-*e 'o%&, lea&i%g to a high =or/atio% e%-
erg( o= F
Sn
C51D. 6o%trar( to 6!?*, the accepti%g &e=ect
the /ost easil( =or/e& is %ot F
$u
')t 6)
,n
C3A, 4A, 54, 55D.
7evertheless so/e a)thors s)ggest the co%trar( C52,53,55D.
<%
$u
s)'stit)tio%s occ)r at the 2c site a%& 6)
,n
at the
2& site C33, 5$D (see +ig. 2). :he accepti%g &e=ects are eas-
il( =or/e&, lea&i%g to &i c)lt n-t(pe &opi%g C54D. :he
eas( =or/atio% o= 6)
,n
accepti%g &e=ects also lea&s to
low charge separatio%, a &raw'ac@ that co)l& 'e overco/e
tha%@s to the t(pe-!! 'a%& alig%/e%t o= the 6<:*#6&*
i%ter=ace C4AD. :he /ost active reco/'i%atio% ce%ters are
e>pecte& to 'e 6)
Sn
(!%
$u
=or 6!?*), a%& the lac@ o= &e-
=ect co/ple> (2F
$u
M !%
$u
=or 6!?*) is tho)ght to lea&
to the higher &e=ect co%ce%tratio% o'serve& C5AD.
3.3 /etal composition
:he si%gle phase co/positio% regio% is /)ch %arrower
=or 6<:* tha% =or 6!?*. ;ccor&i%g to the :alli%% tea/,
si%gle phase 6<:* /o%ograi% pow&ers ca% 'e s(%thesiIe&
o%l( =ro/ a prec)rsor /i>t)re co/prisi%g /etal ratios o=
6)#(<% M *%) O 0.A20.A5 a%& <%#*% O 1.01.03 C30D.
7evertheless, a ,ietvel& re %e/e %t o= a%o/alo)s &isper-
sio% /eas)re/e%ts reveale& a 6)#(<% M *%) O 0.A5, a%&
<%#*% O 1.42 co/positio% =or @1esterites cr(stals C43D, s)g-
gesti%g that the si%gle phase co/positio% regio% is %ot as
%arrow as the :alli%% tea/ s)ggests.
8%til %ow, o%l( <%-rich a%& 6)-poor /aterials gave
high e cie%c( (see +ig. 3), as was alrea&( %ote& '( the
7agao@a tea/ C31D. !% <%-rich growth co%&itio%s, the
@1esterite str)ct)re is tolera%t to stoichio/etr( &eviatio%s
1,40
1,00
0,60
0,70 1,00
Cu/(Zn+Sn)
+i!. 3. 6o/positio% /ap o= the 'est 6<:* solar cells. :he &ia/eter o= the circles is proportio%al to the co%versio% ecie%c(. *ee
:a'le 2 =or the re=ere%ces.
'( Ii%c e>cess a%& copper lac@i%g C31B34D, i% the =or/ o=
<%
$u
a%& V
$u
vaca%cies C51, 35D, ')t high <% co%te%t also
lea&s to str)ct)ral &isor&er C33D.
3.4 0and!ap measurement
;'sor'a%ce /eas)re/e%ts are %ot s)ita'le =or e>tract-
i%g the 'a%&gap val)es, 'eca)se the a'sorptio% coe -
cie%t &erive& =ro/ spectrophoto/etric &ata o% thi% l/s is
&eter/i%e& '( &e=ect a'sorptio% a%& '( /eas)re/e%t
acc)rac( li/itatio%s C33D. !% partic)lar, <%*e C35D a%& <%-
ca)se& &isor&ers C33D lea& to i%correct 'a%&gap &eter-
/i%atio% whe% it is &eter/i%e& =ro/ a'sor'a%ce /eas)re-
/e%ts. PJ /eas)re/e%ts %ow co%r/ that the 'a%&gap o=
6)
2
<%*%*e
4
is i%&ee& aro)%& 1.0 eF at roo/ te/per-
at)re C3$D, whereas 'e=ore that p)'licatio% the /eas)re&
'a%& gap was aro)%& 1.5 eF. *)ita'le /etho&s =or /ea-
s)re/e%t o= 6<:* 'a%&gap are PJ, :,-PJ a%& EPE /ea-
s)re/e%ts.
4 Synthesis strate!ies
4.1 #ne%step or two step processes for thin
films
+or 6!?*, the &epositio% tech%i2)es )se& to 'e clas-
si e& as vac))/ a%& %o%-vac))/ tech%i2)es. +or 6<:*,
the sa/e approach was also )se& i% a review C3AD. 7ever-
theless, =or 6<:*, this classi catio% is %ot acc)rate, 'e-
ca)se rece%t wor@s showe& that low-cost &epositio% &oes
%ot /ea% low-cost solar /o&)les C50D, a%& 'eca)se o= the
pro'le/atic o= 'i%aries co%trol &)ri%g 6<:* s(%thesis (see
%e>t paragraph). 4e there=ore &eci&e& to classi=( the pro-
cesses i%to o%e-step or two-step processes"
- :wo-step processes, where the %ee&e& ele/e%ts are
rst i%corporate& &)ri%g a% a/'ie%t te/perat)re pro-
cess, =ollowe& '( a% a%%eali%g step. :he chalcoge% ca%
'e i%corporate& i%to the prec)rsor or &)ri%g the
a%%eali%g step. :hese processes allow the )se o= =ast
a%& low-cost tech%i2)es =or prec)rsor &epositio%. 8%- til
%ow, a%& co%trar( to the 6!?*, two-steps processes
(iel&e& the 'est e cie%cies (/ore tha% 10E) C14D. !L9
wor@s o% three s)ch processes, the h('ri& sol)tio%-
particle tech%i2)e C14D, electro&epositio% C51D a%& co-
evaporatio% C52D. ther tea/s i%vestigate& %)/er- o)s
other &epositio% tech%i2)es, s)ch as co&epositio% '(
evaporatio%, sp)tteri%g, ;-6FD (pe% ;t/o- sphere
6he/ical Fapor Depositio%), %a%oparticles, sol- gel (see
:a'. 2).
- %e-step processes, where all the ele/e%ts are i%corpo-
rate& si/)lta%eo)sl(. :his t(pe o= processes (iel&s the
'etter res)lts =or 6!?*, ')t )%til %ow it was %ot the
case =or 6<:*. :he 'est e cie%c( )%til %ow is A.15E '(
coevaporatio% C53D. %l( a =ew gro)ps p)'lishe& res)lts
=or s)ch processes, a%& ver( =ew ha& sig%i - ca%t
res)lts i% ter/s o= solar cell e cie%c(" 7,EJ C53D, :alli%%
8%iversit( C54D, Q<L C55D. ther gro)ps trie& reactive
sp)tteri%g a%& p)lse& laser &epositio% (PJD) (see :a'.
2). :he /etho& o= :alli%% 8%iversit( also i%tro&)ces a
h)ge &iere%ce i% cell architect)re, where
50 / 6<:* /o%ograi%s are s(%thesiIe& i% /olte%
R!, wrappe& i% the ') er la(er a%& attache& to the
s)'strate '( epo>( gl)e C53D.
:hese processes are &iere%t, ')t the two t(pes o= pro-
cesses (o%e-step a%& two-steps) reache& high e cie%cies
(>AE). 8%til %ow, it &oes %ot see/ that o%e or the other is
i%tri%sicall( 'etter, 'eca)se, as we will see i% the %e>t
paragraphs, the @e( poi%t is te/perat)re a%& at/osphere
co%trol &)ri%g the o%e-step &epositio% or a%%eali%g step.
10 % 8 % 6 % 4 %
Zn
/S
n
"able 2. *(%thesis /etho&s =or 6<:* solar cells.
*(%thesis /etho& 6halcoge% a%& /etho& (E) Isc Voc ++
o= i%sertio% (/;#c/
2
) (/F) (E)
*pi%-coati%g o= /etal-chalcoge% colloi&s i% a h(&raIi%e sol)tio%, 540

6 *, *e (i% the colloi&s) 10.1 C14D 31 515 34
ther/al treat/e%t C14, 2A, 34, 130, 131D *#(*M*e) 0.4 10.1 C2AD 3A 423 32
*#(*M*e) 0.03
6oevaporatio% o= /etals a%& *e, three-stage process C53D *e &)ri%g coevaporatio%, A.15 C53D 35.4 355 35
40 ;#s
6oevaporatio% o= /etals a%& crac@e& * o% low-te/p P)re s)l=)r, $.4 C52D 1A,5 331 33
(150

6 s)'strate) =ollowe& '( 5 /i% a%%eal coevaporate&. 9i> o=
at 550

6 at at/ospheric press)re C52, 120D coevaporate& * a%&
6oevaporatio% o= /etals =ollowe& '( 540

6 with *, *e (5.5E) C121D
5 /i% CA4, 103D
9o%ograi% solar cells with *#*e gra&ie%tC54D 6<:*e /o%ograi% 5.4 C54D 1$.4 520 30
(50 /), *%*2
a%%eali%g ca)si%g a
0.1B2 / * &i)sio%.
9o%ograi% cells C1A, 23, 53, 132D *(,12 , *e(,22 C53D 5.3 C23D 1A.A 3A3 5$
*e2)e%tial electro&epositio% C51, 133B141D 5$5

6 i% *#72 5.3 C51D 22 535 5$
=or 12 /i%
Lla&e-coati%g o= 6<:* %a%oparticles i% he>a%ethiol. * i% the colloi&s, *e ther/al treat/e%t 3.5 C142D 30.4 420 52
Lest ecie%c( (5.2E) a=ter light-soa@i%g. 3.$E (20 /i% 500

6) 3.$ C25D 21.5 340 4A
with 6)2 <%*%(.3 ?e(.1 (*(.2 , *e(.2 )4
6osp)tteri%g o= <%*, *%*, 6) C13, 35D 3 h at 5$0

6 with Q2 * 3.5 15.A 310 32
*tac@e& &epositio% o= <%* (sp)tteri%g) # 30 /i% i% *e at/osphere 3.0 31.5 3A0 4A
6) (evaporatio%) # *% (evaporatio%) C103D
*tac@s o= evaporate& /etals C15, 113D, 3.1E *)l=)riIatio% 5.$ 15.$ 31$ 30
with 6& ')er, 5.$ with 6&-=ree ')er.
Fariatio% with evaporatio% o= <%*, *%, 6) C100D
pe%-;t/osphere 6he/ical Fapor Depositio% (;-6FD). 520B530

6 =or three ho)rs 3.0 13.5 35$ 55
*pra( p(rol(sis o= /etal-o>i&e prec)rsors C143D i% 5 volE Q2 *
'ala%ce& with 72 .
6oevaporatio% o= 6), <%, *%, *e CA$D :her/al treat/e%t i% 5.4 20.0 4A5 54
the prese%ce o= *% a%& *
*ol-gel" /etals a%& s)l=)r i% etha%ol C144D ;%%eali%g )%&er 72 MQ2* 5.1 1$.A 515 53
(5E) at/osphere at
530

6 =or 30 /i%
*.
De
l'
os"
R1
est
eri
te
thi
%
l
/s
=o
r
ph
ot
ov
olt
aic
s"
a
re
35
00
4-
p5
"able 2. 6o%ti%)e&.
*(%thesis /etho& 6halcoge% a%& /etho& (E) Isc Voc ++
o= i%sertio% (/;#c/
2
) (/F) (E)
*p)tteri%g o= 6)#<%*%#6) C10$D ;%%eali%g 30 /i% 530

6 4.3 15.4 545 55
9etallic prec)rsors i% alcohol CAAD :her/al treat/e%t 4.2 23.2 305 55
i% *e at/osphere
9etal chlori%es i% &i/eth(l s)l=o>i&e C145D :hio)rea i% sol)tio% a%& 4.1 24.A 400 41
*e at/osphere, 500

6
+ast coevaporatio% (20 /i%) o= 6), *%, <%* C55D 6rac@e& s)l=)r 4.1 13.0 541 30
&)ri%g evaporatio%
6osp)tteri%g o= 6), *%, <% C143D. * i% seale& glass t)'e 3.5 C143D 13.5 425 53
Fariatio%s with 6)#*%, <% a%& 6)#*%,
<%* C145, 14$D a%& with *e
ther/al treat/e%t C14AD
%e-step electro&epositio% o= /etals C13, 32, $5, 104, 150B153D. Q2 * i% ;r at 550

6 3.4 C32D 14.$ 533 41
%e-step electro&epositio% (i%cl)&i%g s)l=)r) C154B155D =or the recor&. ther
tech%i2)es i%cl)&es * i% ;r,
Q2 * i% ;r, * i% 72 ,
*e a%& Q2
,eactive cosp)tteri%g o= 6), <%, *% i% Q2 *#;r C30D 50E Q2 * # ;r /i>t)re at 5 /torr 3.4 12.4 42$ 34
*e2)e%tial sp)tteri%g o= 6), <%, *% C15$D *e vapors at 500

6 =or 30 /i% 3.2 20.5 35A 43
PJD =ro/ 6<:* 'ase& o% si%tere& 6)2 *, <%* * i% the 6<:* pellets 3.14 $.$ 351 55
a%& *%*2. 72 ther/al treat/e%t
at 500

6 &)ri%g 1 h C15AB132D
*ol-gel sol)tio% Q2 * 3E i% 72 2.23 10.2 52A 42
(/etals#/etho>(etha%ol) CA1, 133D.
7a%oparticles o% &e>i'le ;l =oil, 1.A4
<%* as ')er la(er C11$D
*)ccessive io%ic la(er a&sorptio% a%& reactio% * 1.$5 3.2 2$0 32
(*!J;,) C134, 135D (/eas)re/e%ts at 30 /4#c/

)
*e2)e%tial e-'ea/ evaporatio% o= 6), <%, *% C133D * vapors =or 2h at 530

6 1.5 A.5$ 45$ 3$
,eactive sp)tteri%g =ro/ 6)2 <%*% Q2 * plas/a 1.35 A.52 0.343 41
target C135, 13$D
6he/ical 'ath &epositio% o= *%*, <%*, Q2 * 0.13 2.4 210 31
6) io% e>cha%ge C13AD at 500

6 =or 2 h
Evaporatio% =ro/ a 2)ater%ar( so)rce C150D 0.33
EP
J
P
ho
to
vo
lta
35
00
4-
p3
35004-pA
*. Del'os" R1esterite thi% l/s =or photovoltaics" a review
(a) (')
+i!. 4. *E9 cross-sectio% o= 6<:*e l/s grow% at the sa/e te/perat)re a%& co%sta%t &epositio% )>e & s, e>cept 6) rates were
a&j)ste& to pro&)ce o%l( (a) 6)-rich growth or (') 6)-poor growth C5AD.
ther /etho&s o= s(%thesis that &i& %ot pro&)ce solar
cells i%cl)&e" cosp)tteri%g o= 6), *%, <% =ollowe& '( a%-
%eali%g i% a hot t)'e i% prese%ce o= Q
2
* C55D , &ip-coati%g i%
a /etha%ol sol)tio% =ollowe& '( a%%eali%g at 200

6 i% air
C5$D, 6<:* %a%oparticles i% ole(la/i%e C5AD , che/ical 'ath
&epositio% C$0D , sp)tteri%g o= a si%tere& /i> o= 6)*e, 6)*e
2
, <%*, a%& *%*
2
C$1D.
4.2 $,"S formation
*i/ilarl( to 6!?*, 6<:* %ee&s te/perat)re 'etwee%
500 a%& 300

6 to 'e s(%thesiIe&. 7evertheless, the che/-
ical reactio%s are %ot (et co/pletel( )%&erstoo&, eve% i=
a reactio% path was propose& C$2D. :here are s)ccessive
reactio%s ta@i%g place i% the ')l@ o= the la(er 'etwee%
the ele/e%ts lea&i%g to 'i%aries, ter%aries a%& % all( the
2)ater%ar(.
;t roo/ te/perat)re, o%l( /etal 'i%aries ca% =or/, =or
e>a/ple 6)
3
*%
2
C$3D, 6)
2
<%
4
C$4D , 6)
3
*% a%& 6)<% C$5D.
;t higher te/perat)re, 'etwee% 200 a%& 450

6, /etal-
chalcoge%i&e 'i%aries s)ch as 6)N, 6)
2
N, a%& *%N
=or/ C$3B$$D, a%& =or te/perat)re >450

6, 6)
x
N 'i%a-
ries the% react with *% to =or/ 6)
x
*%
y
* C$0D. ;t higher
te/perat)re ('etwee% 550 a%& 5$0

6 C51, $5, $3, $AD), a%&
=or lo%ger a%%eali%g ti/e ($ h) or o%e-step &epositio%
at 500

6 C53, $3D , <%N reacts with 6)
2
*%N
3
to =or/
6)
2
*%<%N
4
accor&i%g to the e2)atio% propose& '( C$2D "
6)
2
*%N
3
M <%N 6)
2
<%*%N
4
. (1)
!% or&er to co%trol which reactio%s ta@e place &)ri%g the
a%%eali%g step o= a two-step process, it is %ecessar( to
closel( /o%itor the te/perat)re o= the la(er, 'eca)se, =or
e>a/ple, too =ast a% a%%eali%g ca% lea& to li2)i& *%
')''les =or/atio%, preve%ti%g the =or/atio% o= large grai%s
CA0D. +or processes )si%g ele/e%tal s)l=)r or sele- %i)/, =ast
a%%eali%g (a =ew /i%)tes) is possi'le, whereas =or processes
)si%g Q
2
*, which is less reactive tha% ele/e%- tal s)l=)r, a
lo%g a%%eali%g ti/e (23 h) is %ecessar( =or
the 'i%aries to react co/pletel( a%& to =or/ large grai%s o=
6<:* CA1, A2D.
+or o%e-step processes, 6)-rich growth co%&itio%s are
%ee&e& at the 'egi%%i%g o= the reactio% i% or&er to =os-
ter growth o= large grai%s C53, A3D, as show% i% +ig)re 4.
7evertheless, =or 'oth processes, the %ishe& la(er /)st
'e <%-rich (see part 4.3), a%& i% partic)lar 6)
2
N-=ree C30D
i% or&er to get high photovoltaic e cie%cies. != the la(er
is %ot 6)
2
N-=ree at the e%& o= the s(%thesis process, the
s)'se2)e%t c(a%i&e etchi%g lea&s to possi'le voi&s a%& &e-
=ects C$AD. != <%-rich growth co%&itio%s are )se&, <%N =or-
/atio% is pro/ote& C4$, 4AD.
:here=ore, =or o%e-step processes it is %ecessar( to
a&apt the rate o= &epositio% o= each ele/e%t with respect
to the reactio% path, as well as co%trol &epositio% te/-
perat)re, 'eca)se higher te/perat)res ca% also i%crease
grai% siIe C5AD. +or two-step processes it is %ecessar( to
closel( /o%itor growth co%&itio%s, a%& i% partic)lar pre-
ve%t 6)
2
N =or/atio% a%& i%crease <%N reactio% with
6)
2
*%*
3
.
4.3 Atmosphere control
8%=ort)%atel(, co%trar( to 6!?*, the ele/e%ts i%-
volve& i% 6<:* s(%thesis are pro%e to evaporatio%
a%& s)'li/atio%. <% s)'li/ates at 430

6 CA4D, *%*e at
350

6 C$$D, *%* at 350

6 a%& *% evaporates at
430

6 CA5, A3D. 9oreover, high te/perat)res pro/ote
6<:* &eco/positio%, accor&i%g to the che/ical e2)ili'-
ri)/ 'etwee% 6<:* a%& soli& a%& gaseo)s 'i%aries CA5,A$D.
6)
2
<%*%N
4
(s) 6)
2
N(s) M <%N(s) M *%N(g) M N(g).
(2)
!= this e2)ili'ri)/ is &isplace& towar&s the right /e/-
'er, <%N, *%N a%& N =or/atio% a%& losses will occ)r,
lea&i%g to a 6)
2
N-rich la(er, i%creasi%g la(er resista%ce
a%& preve%ti%g goo& photovoltaic e cie%cies (see 5.3). !t
is there=ore o= the )t/ost i/porta%ce to preve%t 6<:*
&eco/positio% as well as 'i%aries losses. :he @e( to that
res)lt is at/osphere co%trol.
:he e2)ili'ri)/ o= e2)atio% (2) ca% 'e &isplace& to-
war&s 6<:* '( sat)rati%g the at/osphere i% o%e o= the
right-si&e /e/'ers o= the e2)atio% CA3,A5D. !t is possi'le to
co)%teract *%N evaporatio% '( i%tro&)ci%g gaseo)s *%N
&)ri%g the ther/al treat/e%t CA$D, or '( i%creasi%g the
partial press)re o= the chalcoge% CAAD, '( per=or/i%g the
chalcoge%atio% i% a s/all close& vol)/e C100D, or '( )si%g
a cap o% the prec)rsor la(er &)ri%g a%%eali%g C101D. != the
a%%eali%g ta@es place i% a Q
2
at/osphere, <% loss ca% 'e
preve%te& '( )si%g <%* as a prec)rsor C102D. 6o%ti%)o)s
evaporatio% o= <% towar&s the s)'strate preve%ts the &e-
co/positio% o= 6<:* i% a coevaporatio% process C53D. !t
also see/s that the prese%ce o= 9oN
2
at the 'ac@ co%tact
p)shes the reactio% towar&s the right /e/'er C103D.
!= at/osphere co%trol is %ot goo&, a%%eali%g ti/e is the
%e>t 'est lever o% 6<:* &eco/positio%, 'eca)se i= 6<:*
is s(%thesiIe& a%& coole& rapi&l(, o%l( a s/all 2)a%tit(
o= 'i%aries will 'e lost. %e paper co/pare& slow a%&
=ast a%%eali%g C104D. !t co%cl)&e& that =ast a%%eali%g is
'etter tha% slow a%%eali%g 'eca)se /a%( &iere%t sec-
o%&ar( phases were =o)%& with slow a%%eali%g, witho)t
/ore e>pla%atio%. 7evertheless, i% this case slow a%%eal-
i%g co)l& 'e li%@e& to a 'a&l( co%trolle& reactio% at/o-
sphere, lea&i%g to 6<:* &eco/positio% i%to 'i%ar( a%&
ter%ar( phases.
6o%cer%i%g the @e( poi%t o= at/osphere co%trol,
strategies o= s(%thesis sho)l& 'e slightl( &i e re%t =or o%e-
step or two-step processes. +or two-step processes, there
see/s to 'e two stages &)ri%g the a%%eali%g step" o%e
short (a =ew /i%)tes) step o= 6<:* =or/atio%, a%& o%e
lo%ger ()p to a =ew ho)rs) step o= grai% growth. :he co%-
trol o= the at/osphere sho)l& 'e ver( acc)rate i% the sec-
o%& step, a%& the reactio% at/osphere co)l& also 'e co/-
pletel( &iere%t =ro/ the rst step CA3D. +ort)%atel(, it
is 2)ite eas( a%& i%e>pe%sive to &esig% a%%eali%g e2)ip-
/e%ts that provi&e goo& static at/osphere co%trol (that
is to sa(, e2)ip/e%ts where %othi%g ca% either go i% or
go o)t). 7evertheless, vapor i%jectio% is /ore tric@(, as it
re2)ires carrier gas, press)re /eas)re/e%ts, lea&i%g to a%
e2)ip/e%t rese/'li%g a% evaporator.
+or o%e-step s(%thesis, at/osphere co%trol is %ot so
eas(, 'eca)se reactio% cha/'ers are &esig%e& =or co%-
trolli%g the &epositio% rate a%& %ot the partial press)re
o= each ele/e%t. !% or&er to preve%t 6<:* &eco/posi-
tio% a%& 'i%aries losses, *% a%& chalcoge% &epositio% rate
sho)l& re/ai% high &)ri%g the cooli%g phase, i% or&er to
co)%teract *% loss C53D.
4.4 $omposition !radient
:he co/positio% gra&ie%t either create& '( a variatio%
o= the rate o= &epositio% o= each ele/e%t i% a co&epositio%
or '( stac@e& ele/e%ts, has a% i% )e%ce & o% 6<:* l/
properties, 'eca)se o= 6) &i )si o%, *% loss a%& che/ical
/echa%is/s o= =or/atio%.
6o%cer%i%g 6), its &i )si o% ca% create voi&s at the
'ac@ co%tact. :wo-step processes, especiall( whe% the
prec)rsor la(er is a co&eposite& /etal la(er or stac@e&
/etal la(ers with 6) as rst la(er, are s)'ject to these
voi&s C$A, 103D. *eco%&ar( phases are o'serve&, preve%ti%g
the total =or/atio% o= 6<:* C105D.
;s e>plai%e& i% the previo)s paragraph (see E2. (2)), *%
evaporates i= the at/osphere is %ot well co%trolle&.
7evertheless, the loss o= *% co)l& also 'e preve%te& '(
havi%g the 6) la(er o% top C33, A3D.
6o%cer%i%g the reactio% /echa%is/, =or stac@e& /et-
als, it is 'e%e ci al to have 6) a%& *% i% close co%tact =or
the =or/atio% o= large 6<:* grai%s C103D. != the( are sep-
arate& '( <% or <%(*, *e), the reactio% 'etwee% copper
chalcoge%i&es a%& ti% chalcoge%i&es, which is %ecessar( to
=or/ 6)
2
*%N
3
C$2D, co)l& 'e i%hi'ite& C105D. +or stac@e&
/etals, 6) o% top see/s to =oster =or/atio% o= 6)
x
*,
which /a( res)lt i% larger grai%s a%& &e%ser l/s C10$D.
+or o%e-step processes, high 6) co%te%t at the 'egi%-
%i%g o= the &epositio% pro/otes the =or/atio% o= large
grai%s C53D.
6o%cer%i%g the co/positio% gra&ie%t,
- =or two-steps processes, the 6) /)st %ot 'e &eposite&
rst, a%& 6) a%& *% sho)l& 'e i% close co%tact.
:he possi'le co/'i%atio%s =or stac@s are there=ore
9o#<%(N)#6)#*% or 9o#<%(N)#*%#6). :he co&epo-
sitio% see/s also possi'le, ')t with a 6)-poor co/po-
sitio% %ear the 'ac@-co%tactK
- =or o%e-step processes, the la(er /)st 'e 6) rich at
the 'egi%%i%g o= the &epositio% i% or&er to pro/ote
the growth o= large grai%s.
4.2 Sodium
*o&i)/ see/s to have the sa/e e ects o% 6<:* as o%
6!?*" it pro/otes the growth o= larger grai%s, e%ha%ces
co%&)ctivit( a%& has a sig%i c a%t e ect o% l/ /orphol-
og(, as was &e/o%strate& '( *J? # 'orosilicate s)'strate
co/pariso% a%& &ippi%g i% 7a
2
* C10A, 110D. 7evertheless,
co%trar( to 6!?*, 7a was %ot &etecte& '( NP* at the
s)r=ace, /ea%i%g that the 7a &i )si o% i% 6<:* is s/aller
tha% i% 6!?* C111D.
4.3 5evice properties
6<:* &evices are si/ilar to 6!?* &evices. :he archi-
tect)re is )s)all( *J?#9o#6<:*#6&*#i-<%#<%";l,
as prese%te& i% +ig)re 5. 6alc)latio% showe& that 6&*
has a s)ita'le 'a%& oset with 6<:* C112D a%& )%til %ow,
the /ost e cie %t solar cells were o'tai%e& with a 6&*
') er la(er. >i&atio% o= the 6<:* a'sor'er '( &ippi%g i%
&eio%iIe& water C13D or
2
a%%eali%g C53D 'e=ore &epositio% o=
6&* see/s to i/prove e cie%cies. ;s =or 6!?*, re&)c- i%g
the ti/e 'etwee% a'sor'er s(%thesis a%& 6&* &eposi- tio%
to the /i%i/)/ is o= the )t/ost i/porta%ce C103D.
; =ew variatio%s o= the architect)re are @%ow%, espe-
ciall( o% the ') er la(er. P)re <%* &oes %ot see/ to 'e a
s)ita'le ') er la(er 'eca)se o= too high a 'a%& o set C112D,
')t goo& res)lts were o'tai%e& with <%(*, , Q) '( *olar
+i!. 2. 6lassical architect)re =or 6<:* solar cells.
+ro%tier C113D. 7evertheless =or s)ch a ') er la(er the opti-
/al co/positio% o= the a'sor'er la(er see/s to 'e less <%-
rich (<%#*% 1) C113D. ther architect)res were propose&"
*J?#9o#6<:*#a-*i#!: C114D, a s)perstrate architec-
t)re (glass#+:#6<:*) C115, 113D, a%other s)perstrate
(glass#+:#:i
2
#!%
2
*
3
#6<:*#9o) C115D, a e>i'le & s)'-
strate (;l =oil#9o#6<:*#<%*#i-<%#!:#;l-7i) C11$D.
:he literat)re is still 2)ite poor co%cer%i%g &evice
properties, 'eca)se ver( =ew high-e cie%c( &evices were
s(%thesiIe& (et. :he !L9 tea/ starte& to i%vestigate this
el& C14, 52, 11A, 120D co%cl)&i%g that their &evices were
li/ite& '( the reco/'i%atio% at a'sor'er#') er i%ter=ace,
/i%orit( carrier li=eti/e a%& *chott@(-t(pe 'arrier i% the
'ac@ co%tact, which appears to 'e ca)se& '( seco%&ar(
phases a%&#or 9o*
x
i%ter=acial la(er 'etwee% 6<:* a%&
9o C121D.
6o%cer%i%g the a'sor'er # ') er i%ter=ace, it see/s
that the s)r=ace o= the 6<:* is 6)-poor, si/ilarl( to
6!?* C111D, or eve% 6)-=ree C122D. :he R67 etchi%g, which
is also )se& i% 6!?* processes to re/ove 'i%aries =ro/
the s)r=ace, see/s to etch 6) pre=ere%tiall( a%& *% i%
a lesser e>te%t CA3D. !t see/s also 'e%e cial =or re/ov-
i%g 6)
2
N that i%crease the resistivit( o= the la(er C123D.
:his ca)ses a wi&e%i%g o= the 'a%&gap witho)t t(pe i%ver-
sio%, which co)l& 'e a% eas( wa( to tailor 'a%&gap alig%-
/e%ts C124,125D. !t see/s also that the electro%ic str)ct)re
o= a *%-&eplete& s)r=ace is %ot =avora'le =or the =or/a-
tio% o= well wor@i%g p-n j)%ctio% C54, A3D. :he 6o%&)ctio%
La%& set, a'o)t 0.40.5 eF, is so/ewhat a'ove the
opti/al ra%ge o= 00.4 eF a%& /a( co%tri')te to lower
J
sc
a%& ll =actor i% the 6<:**e &evices C123D. Letter
lattice /atchi%g 'etwee% a'sor'er a%& ') er co)l& li/it
reco/'i%atio% at the i%ter=ace, a%& )si%g &i e re%t ') er
with s/aller lattice s)ch as !%
2
*
3
or <%(*, , Q) co)l&
i/prove the e cie%c( o= the &evices C125, 12$D.
6o%cer%i%g the 'ac@ co%tact, <%N was o'serve& at
the 'ac@ co%tact C5A, 103D, as show% i% +ig)re 3, a%& it
see/s that i%creasi%g the <%N co%te%t stro%gl( i/pairs e=-
cie%c( C45D. !t was %evertheless spec)late& that <%* co)l&
'e less &etri/e%tal tha% previo)sl( tho)ght C52D, acti%g as
a si/ple G&ar@H /aterial. Li%aries losses that occ)r &)r-
i%g a%%eali%g /a@es 6)
2
N to &i )se towar&s the rear o=
the cell, co)l& lea& to a 6)
2
N#9oN
2
/i>, lea&i%g to high
resista%ce at the 'ac@ co%tact.
6o%cer%i%g /i%orit( carrier li=eti/e, it /ight %ot 'e
s)ch a pro'le/, 'eca)se as i% 6!?* a%& 6&:e, grai%
'o)%&aries collect /i%orit( carrier a%& provi&e a c)rre%t
pathwa( =or the/ to reach the n-t(pe 6&* a%& <% la(-
ers C30D a%& =or coevaporate& a'sor'ers, high /i%orit(
carrier &i )si o% le%gth was /eas)re& (several h)%&re&s
+i!. 3. 6<:*e with <%*e segregatio% at the 'ac@ co%tact C5AD.
o= %/ C52D). 7evertheless, it see/s that grai% 'o)%&aries are
6)-rich, which co)l& i%crease reco/'i%atio% rates a%& th)s
&i/i%ishi%g V
#$
C2AD. 6)-rich a'sor'ers were =o)%& to
have lower V
#$
tha% 6)-poor o%es C30D, pro'a'l( i% re-
latio%ship with 6)
2
N =or/atio%. Jo%ger /i%orit( carrier
li=eti/es were /eas)re& i% low 'a%& gap /aterials, s)ch as
6<:*e, tha% i% high 'a%& gap &evices C2AD. :he &i e r- e%ce
'etwee% E
!
i% eF a%& V
#$
i% V , calle& F
#$
&e cit, ca%
there=ore 'e &ecrease& '( &i/i%ishi%g the 'a%g gap as
well as tightl( co%trolli%g the =or/atio% o= 6)
2
N or its
re/oval '( R67 etchi%g.
+or high e cie%c (, it is i/porta%t to =oc)s 'oth o% a'-
sor'er 2)alit( a%& o% i%ter=aces 'etwee% the a'sor'er a%&
the 'ac@ co%tact a%& ')er. :he 6)
x
N 'i%aries co%trol
see/s to 'e a @e( poi%t =or 'oth a'sor'er a%& i%ter=ace
2)alit(. +ort)%atel(, the 6!?* co//)%it( has a stro%g
e>perie%ce o% s)ch pro'le/s, a%& hope=)ll( it will 'e pos-
si'le to opti/iIe these i%ter=aces /)ch =aster tha% =or the
6!?*.
2 $onclusion
:he pro'le/atics e%co)%tere& '( research tea/s wor@-
i%g o% 6<:*-'ase& solar cells were prese%te& a%& &is-
c)sse&. :he el& o= 6<:* solar cells is (o)%g, a%& )%til
%ow it is &i c)lt to poi%t to certai%ties. 7evertheless, it
see/s that these ass)/ptio%s start to 'e viewe& as Gco/-
/o% @%owle&geH i% the co//)%it("
- 6<:* has @1esterite str)ct)reK
- the 'a%&gap is t)%a'le 'etwee% 1.0 eF (6)
2
<%*%*e
4
)
a%& 1.5 eF (6)
2
<%*%*
4
)K
- the s(%thesis at/osphere /)st 'e co%trolle& care=)ll(K
- 'i%ar( =or/atio% co%trol is a @e( poi%t =or high e-
cie%c( &evicesK
- <%-rich /aterials (iel& 'etter res)lts (whe% )si%g a
6&* ') er la(er).
7evertheless, there are %)/ero)s 2)estio%s still, s)ch as"
- what are the cr(stalli%e &e=ects, how are the( =or/e&K
what role &o the( pla( i% the str)ct)reK
- what is the reactio% path to 6<:*, how to co%trol
'i%aries =or/atio%K
- what is the role o= so&i)/ &)ri%g growth.
35004-
p1212
9ore a%& /ore scie%tists =ro/ the 6!?* co//)%it(
wor@ o% 6<:* solar cells. :he pro'le/s e%co)%tere& i%
6<:* solar cells are 2)ite si/ilar to the o%es o= 6!?* so-
lar cells, a%& si/ilar /etho&s ca% 'e )se& to solve the/.
:here is %o clear s)periorit( o= two-step processes over
o%e-step processes, eve% i= )%til %ow the 'est res)lts were
o'tai%e& with o%e-step processes. +or 'oth t(pes o= pro-
cesses, a =oc)s o% 'i%ar( co%trol =or/atio% '( at/osphere
co%trol a%& a&aptatio% o= i%ter=aces to @1esterites /aterials
are the @e( poi%ts =or i%creasi%g photovoltaic e cie%cies
=or 'oth t(pes o= processes.
:he a)thor is tha%@=)l =or % a%cial s)pport o= the +re%ch
;ge%ce 7atio%ale &e la ,echerche (;7,) )%&er gra%t 7o-
v;6E< (;7,-10-Q;L!*J-00$).
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J.9. Peter, Progress i% Photovoltaics" ,esearch a%&
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