Review Article 2018,3{4} ?

74-283 Advanced Materials Proceedings

Symmetrical and unsymmetrical squaraine

sensitizers for dye-sensitized solar cells:
Present day advances and future challenges
Sultan A Al-hcraibi, S.T, Gaikwad, Aniali S -Raibhoi*

Department of Chemistry, Dr- Babasaheb Ambedkar Marathwada {fniversity, A*rangabad, Maharashtra 4il0il,India
*Corresponding author

DOI: I 0.5 I 85/amp .2A181826

www.vbripress.com/amp

Abstract
The reguirernent for enerry is ever increasing in the past few years due to the need for the innovation of clean energy
and
ec+.friendly technologies.-3ynr*etric and asymrnetric SQdyes have received increasing attention and great potential for use
as Se-sersitizers for application in dye sensitized sclar cells (DSSC).This review article gives a synopsis of the
advanLrents on Se-sensitizers io the domain of DSSC and the chance used to enhance thet overall energJ conversion
efficieocy. Specifically, the primary factors in charge of the low values of open-circuit voltage (Z*) short-circuit
pn*ocurrent i"fs4 ana An factor (fF) ms debated in detail. Future orientations in rese"arch and expanded absorptions of near-
infrared.egion NfRl by development organic substances aud tleir ryplications ae suggested from a prsonal point of view.
Copyright @ 2018 VBRI Press-

Keywords: Dye-sensitized solar cell; synr?netric aad asyrmetric squaraine dyes; energy convetsion.

Introductisn (D-A-D) zwitterioaic molecular structure having squaric

Solar radiatioa is the plentifirl source af erergy se etrth-
Dye seasitized solar cell is orle ofpromisirg clean €a€rgy
sourc€s due to the sua wkich supplies about 120,{H0 TW
of energy to the earth's surface, &*t ma*s 6,ffi times
more than tle curred rate cf the \rorld's euergy
exhaustiol. The traditional silicon cells tlat rely st solat
cells are aot prefered l:rrgely due r5 &e higler mst of
productioa and effective manufacttriag tectriquas- Dye
sensitized solar cells (DSSC) have acquired coc$id€rable
attention because it envkorxnenBlly *iedly rature,
attractive appearaace, low cf csst, ease of manufacture,
flexible a*d it doesa't need ta cornplex fahrication
procedures. In 1991, Ctratzel md O'Regan presented the
notion of low cost, high efficiency DSSC by relying on
t}re mesoporous nanapa*icles of TiQ [1i. Siece the tiae
of a large number of erganometallic ad orgaoic firc*
which were utilized h BSSC have been desiryd [2-3]
and in a kied endeavor te mmr:factwe solsr eells:rit}
expand power diversioa efficiencies (PCEsXa]- ESSC
have been used tremendo*s in tle previous decade
because their poteatial use in low-east ouryIs Gf
renewable resource and i& large-area, celourlirl,
lightweigtrt device [I]. In 1965, T'rib€s st a] [5], fir*
reported about squaraine dyes- Sguaraine dyes seirsitirers
are oae of the poteatial filters due to thek slap aad
intense absorption to light ia rrear iaferred md visible
region. They essentially eadme a &nor- acceptor{oa*r
aeid center fls acceptor. SQ-dyes have wavelength that
caa be begua &em:risible light spectrum to rear infrared
wavelelgth regicn relying on wise molecular design with
various daacr-moieties to extended zt-conjugation [6]'
DSSC are buift of a SQdye absorbed broad band gap
semicon ductor such as tit*nium dioxide(Ti0z) or Zinc
oxide {ZnO}, liquid electrolyte containing the iodide/
triiodide G/L-) redox, aad a Pt-soated counter electrode
[7-14], (FgJ].The ele.tru] irjecticn into the TiO: and
dye renewal qdth bole transport to the redox couple,
called sstr$itirer iil which is oae of the most critical
c<>mponent the light hervesting and the charge
to for 'SSC
separation process [1 5J,
Ilr the ffear-IR region the photoelectric conversion
efficiency of DSSC is i*suffcient, so troreover studies
are ceedd te develop new sensitizers to irrprove light-
harvesting ia fulI area of the spsctra of sunlight, including
visible and NIR regiots [6]. Squaraine dyes (SQ) are
viewed as oae of the best substitutes betweea tle different
Ru-ftee orgaaic dyes available. They have higher molar
extinc*ion cesfficierts ad much cheaper Ru-free orgaaic
dyes {e.g- exfensicq c*efEcient ofsquaraine is -3 x 105
M-icn*l) [17-19], &an conventiocal dyes (Ru complexes
is -l x t# M*tc,m-l) [20]. They have ability to absorb
photo*s with a kmg waveleng& &om 500 to 700 rm. In
addition, S*seasitizers are utilized to aggregate very
easily orl the Ti*z wfacq which dimiaish the solar cell
efficiency {21,227 aad ttreir absorption band is very tight

Copyighl @ 2018 VBRI Press 274

Review Article
compared to Ru-complexes [1?-19]- will be huge It
challenge to evolve novel SQ-seasitizers in erhancing and
generation of high efficieacy DSSC.
Fig.1 Tbe processes i* operational DSSC- Blue arrows indieate
beneficial procsses ad real arows i*dicate mdesircd *osses-
Squar*i*e structares for Dye-sensitiwd solsr cglls
SQdyes were initially applied ia ZnO pletoc*rd*ctors,
non-linear optics, ard optical data storage [23]-
Kamat and co-workers were observed that the iaitially
to invastigate the sensitive behaviour of SQ-sensifizers for
the cells structure by utiliziag these sensitizers had a very
low incideat photon-to-curreni transfereqce efficiency
[241.
Ia 1999 Zhao et al introduced symrnerical
as sensitizers dyes in DSSC [25J-
Since 2010 there has b€e'r1 wid€ atte!*ion in
utilizing SQdyes as sensitizers dyee in dye-secsitized
solar eells.
SymmArical sqaaroine dyes as sensitiwrs
Symmetric SQ-sensitizers are synthetic via intensifrcation
of one equivalsat cf 3,4-dihydroxy -cyclobut-3-eae-1,2-
dione {squaric acid) with two equivalents of a quaternized
methylene base such as 2-(N-methyl-N-pheaylamino)
acetic acid and 2-metlylbeazo[d]thiazole, indole
derivatives (Scheme 1). Struct*re can be achieved by
using various preflrs€)rs of a quaternized methlene base
witl squaraic acid.
o..ol
\__/ I I tu = quaterdzed mgfryleo€ hase
_ a,
l-l nhmanol\oluenef l:l volua) -{( V
HOOHo
Scheoe 1. General method proce&re for syxmeirical sqraaine
sensitizers,
Zhao atd. co-workers syn&etic 3dyes *f SQ-
sensitizers 1-3 and utilized them ia DSSC- The
absorption spectra of SQ-sensitizers were progressi -vcly
Convriohi (o 2018 VBRI Pre-s:s
2818,?(4|27+283 Advanced Materials Proceedings
in the order of (CHzlSOfy> CI{zCll:z OH > CH:upon
changiag the substituent on the heterocyclic N-atom. A
similar way, fhe SQ-dye3 show the performance better
thau 1 and2 with a conversion efficieucy of 2.16%[26].
o:S
I
The carboxl groups in four SQ-dyes &om 4-Tcontain
dialkyi-substihrted anilines avail as the anchor and donor,
squaraine and studied &e effects of tle length of the alkyl halides
chain of tte dialkyl-aminophenyl unit on the dye-
seasitized solar cells performance 127]. Tltey fou:rd that
&e SQ-dyes 6 and 7 have shorter spacer leng& led to
higLer IPCE valaes because their increased absarption
intensity and vigorous light harvesting i* the near in&ared
region (NIR), iadsced by H-aggregation in the green and
blue regions of visible light reftecting tlat the methyl
carboryl acceptors groups dialkyl-substituted anilines
may improve the interactions betweea dye molecules with
TiOz thus leading to more efficient electror injection..
.dlso, SQ-dyes 5 and Tcaused to higher /oc due to the
restrain of charge recollection between I:- and the
electrcrx injected on fhe TiOz by the long alkyl chain on
anili*e. The SQ-sensitizer 7 based on solar cells has ry
vatue of 3.4lYo, and the iacident photon to converted
o elecfon valu€ rerched vp to 72.9'/t at 671 *m.
Ad}- e,
(
)
COOH HOOC
,75
Review Article 2018,3(4) 274-283 Advanced Materials Proceedings

Asy**effiml ry*araine dyes ** senxilizers

\ Asym*icat SQ-seasitizers caa be synthetic from
( dibr*yl esquarateby 3-steps (scheme 2). In the initial step
)
the dibr$tl quarate reacts with one equivalent of
\: ) rel}yle,ts base or an aniline derivative with
-) ahasolin paticipation cf the triethylamiae which act
cataiyit to grve &e corresp-cadiagmonosquaraine.
\ Hydrolysis of tle rnonosqua -raine by NaOII and HCi
yields marc-squaraine tllrich when reactedwith another
\*, ) mstlyleae base leads to ccrrespoading asymmefic SQ-
dye.

Newly, Yao and his colleagues reportd 3-Slioeline

based oo symmetrical SQdyes from 8-1O [29]- In these
SQdyes, the aovel acceptor groups arc coajugative
coryrected to tlre quiaolire do*ar moiet -ies The e&ct of
various acceptor groups and additionally the level of
conjugation between -COOH acceptor grosps and -CH:
donor groups on the photo-physical and photo-chemical
properties. Maximum absorption of,SQdyp 10 reached qp
77A trrn afrofrEthese three SQdyes sensitizers because of
iongest zr-electroa conjugation leng& and its highest
polarity. In light of experimental and their theoretical that
studies quinolioe-based SQ-sensitizers with a stronger
acceptor group, greate{ coajugpted &ameworh and highel
polarity are valuable for the conversion efficiency of
DSSC because of an increase io the &iving force fcr
photo-hduced eleckoc-injection and a diminishment in
electron recombination likelihood. In spite of tle best ry
obtained of result just 0-41% under AM 1.5G solar
iradiation, it reveals some SQ-dyes desrgn rules on such
sort ofsensitizsrs.
Seheme 2" Geoeral sylthetic metlod for unsymmeaical squaraine
sensitizers.
In 2005, Alex et al. Meihodically shdied &e variance
befwee* different symmetrical a*d unsynmetrical SQ-
sensitizers (11-17)t311. The rese -archers found that the
effrciencies of dye-sensitized solar cells based on
asymmetric SQ-seositizers are beuer than those
symmetrical sensitizers- The aggregatiol of the
synrmetrical SQ-sensitizer on the TiOz surface lead to
decrease the performaaee of DSSC. Notwi&standiog, tbe
electrons of the excited state of asymmetric SQ-
sensitizers exhibit in one direction flow that lead to more
efftcient charge separation and higher performance for
DSSC. The DSSC based on SQ-sensitizerl6 showed the
best performance with an efficiency up tc ?.-081ok-

276
 ReviewArticle 2018,3{4i 274-28.3
\Alr
\"oo,
Otsuka aad othcr researchers have modified the
structure of
asymmetric SQ-dyes by synthesiziag 3-
dyes(18-20) and utilized themis nanocrystalliae TiOr
based DSSC [32]. By introducirg long-chai* kryl alkyl
to the 2, 3, 3-trimethyl-3H-indolium rnaiety, H-
aggregation of SQ-sensitizer 2B ld to higher lpCE'thac
dye 18 which to based an DSSC. Finaltn the DSSC based
on 20 as a sensitizer with long carboxylic acid as a co-
adsorbent gave a q of l-51% wi& alsc of 4.$4aAcm-2, a
Voc of 4.62 Y, and a FF of 0-63, which are aktr$st
correspond the efEciencies of the BSSC based on yeliow
and purple-colared sensitizer dyes.
I* 2047, Yum et al reported penetratioa work on
improved asyrmtetric SQ-seasitizers for irylernertation
in DSSC [33]. They irrrrroved a*d syu&esized &e novel
SQ-dye 21 which contaired a novel rnolecular desip ts
directly link a cartarylic acid grerry to thn Z, 3, 3-
trimethyl-3H-indolium moiety. The electrm de*sfu
distributions are useful fcr electrer iajectiom aad efficier*
charge separation- Finally, the DSSC based on 2l oxhibits
a peak in tle IR region at 650 nm abt$t IPCEup to 85%.
The ./sc value obtained was 10.50mAcm-2. The tr oc was
0.603V, and the Ff was 0.72, correspondent to an overall
ry of 4.52Ya, which vras the highest value reported for a
DSSC basedon SQ{ye.
Geiger et al. syntletic of novel asyrmnetric Se-
sensitizer dye22, which red-shifted the absorption
spectrum of SQ-dye 21 by adjusting tle molecular
structure [34]. Io SQdye 22, one of l-ethyl-2,3,3-
trimethyl-3H-indolium moiefy was substift]te by a
benzindoli -um moiety which ca:r be displayed on the Ieft
side ring of the indoiiurl structrre. ln spite of if comprises
Copyright @ 2018 VBRI Press
Advanced Materials Proceedings
oaly a short augrnentation of the molecular spine, the
absorptio* ard rnolar extinction coefficient were
especially enhmced which lead to improved light
karvesting a*d expsnd IPCE runge. The excited state
electron distributioa of22 is delocalized on the indolium
moiety beariag the COOH acceptor group that brought
about a streng electronic coupting with &e conduction
band (CB) cf TiCz and subsequemtly a high efficiency of
elmtron-injection At last, 4 : 5-48%, correspoods to
excess of Tlt/o as conkasted to 21 mder the similar
coaditions. The struetaral advantages of SQ-dyes lead to
their tight absorptioa at almost 600-800 nm and then it is
necessary to excess the absorption intensity in the short-
wavelength to enhance scope ofthe sun spectrum.
Beveri*a et aL selected the residues ofthe diethyl the
obarbites as the electron-pull group instead an oxygen
atom of the SQ<ore which provide aa additional high
energy absorpdon baad and improve the cis-shape Se-
dye sersitizer 23[35]- The DSSC based on SQ-dye 3 as
sensitizer prsdBced a higher Jsc vaiue (11.87mAcmr)
than that based on dye 2l t1O.5 mAcm2) and an improved
r7 of 4.7Ye as coopared te 4.5%o in the dye Zl-based dye-
sensitized sola cells. Another strafegy is to extend the n-
conjugatioo lergth of the molecular backbone for
bathochromically shiftiag the absorptior spectra of Se-
dyes.
//1N
The asymmetrical dimeric SQ-dye 24 reported by
Kuster et al [36]. The absorption of SQ{ye 24 reached up
to 725 nrn because ofthe expanded linear a-conjugation,
sEucture and the executed planar of tle naphthalene
moiety. Also, the extinction coeffic -ient amounted to
389000 Lmol-rcm-l, because of the existence of two
chronro -phoric units in the molecule dye 24. However,
the cell performance 8/a) is small although the
{7-3
excellent absorption spectr -um because of intense H-
aggregation, that arises from the broadly extended zr-
backbone.
277
-_
ReviewArticle 2018,3{4} 27+283
Pandey et al. methodically str:died t&e sfrn:chrre prop -
erfy relationships of asym -uetrical and symmekical SQ-
dyes through the iotegraticn of various alkyl
fluorinated-alkyl substi -tueat [37]- Dye-seasitized solar
cells based on aqrmmetrical squaraine 28 atrd 29 gave
higher ry values than tlose of 25, 26 Ml 27- Tfu
efficiency of SQ-dye 29 (3 -35%t is a little Sreats *raa thc
dye 28 {3.1W becatse of the utilized of leugthy chain
substitueat, that efectively suppressed H-aggregaiioa
between SQ-sensitizers. In view of the exlreri:neltal datg,
tle autlors proposed that the Yalue of &17 eV between
the highest occupied molecular o*ital {HO&{O} and the
oxidation/ reduction potential- AIso ktween &e lowest
rmoccrryied molecular (LUMO) d CB of TiOr is
adequate for dye regeneration aad elestrotr injectioa,
respectively.
Maeda and collegues jained heterocyclic c<xnpo*ds
rich in electrons, for example quinoliniue, benz[cd]
indoliunr, and benzopyrylium groups, into tle strucfere of
SQ-dyes to afford dyes 3&-33[38]- In spite cf the
absorptioa peaks are broadly red-shifted as contrasted to
their parallei &ye 21, &e highest general 4 betweet the
fonr squaraine dyes {abraiaed with 34} wz* iu$t L.62yu
{.Isc
: 8.20 mAcm-2, l/oc4-4t Y, -FF: 0.5*} beeause of
the low IPCE'response &om the Eear-iafrared {f{IR.} to
the visible region-
For SQ-dyes 34 aad 35, benzothiazole rqiacernents
were introduced into the sensitizer sfirchre
[39]. Solid-state DSSC based oa fhese two-dyes showed
total r7 : 0.90 and A.68ys, reryectively.
Copyright @ 201 I VBRI Press
Advanced Materials Proceedings
Choi et al. introduced a massive hexyloxyphenyl motif
i*to &e SQdyes fltructsre and developed three SQ-dyes,
36-iSI4Si- Dye aggregation was efficiently stifled
because ef&e introduction ofgreat steric groups' A very
high rate af 52lo/o xas achieved ia DSSC based on
magnificeatJscof 13,93 rn Acm-z.
\e)\L
H
\\-l'
and
A similar research grcup firther iatroduced another rc-
spa€er stnrchtre into &e SQdy*, ia rfris way developing
sensitizers 37 end 38 1411. The absorption peaks ofthese
SQsensitizers rached rry arormd 665 nm. By improving
the caneentratifir of carlorylic acid aad TiOz film
thickness, DSSC based ol dye 37 had m efficiency of
6.298/o {Jx::13.93 mAcs', Yoc : 0.61 E FF : A.74).
The DSSC based on dye 37 achieved an overall r7 of
1.95%- Both vala+ wers between the highest efficiencies
sbtair€d at that time utilizing SQdyes. In spite of the
conversioil efficimcy of tte DSSC based on the dye- 38
dye was less ttan 37o/o. The previous cell showed
lolg term when aa ioaic liquid
excelleaa stability over f&e
was utilized as &e electrolyte. Iocrease efftciency to
3.01% ol the iaitial value of 2-4T* a*$ 1000 hours of
light soeki*g at 60t due to hexylory anrl ditferent equity
group direfhylfluorene srbstitrted *mino prevent €ofitact
of &e accqltor wi& TiOz surface resulting in a decrease
in the dark currert.
278
ReviewArticle 2A18,3(4) 274-283 Advanced Materials Proceedings

Li et aI" A similar skategy was chosen to achieve
panchromatic respoos€ of asymmetric SQdyes by
introducing a rich electron 3y'-ethylenedioxythiophene
IEDOT) and bithiopheae(BT) u:dt$ betweea the certsr of
squaraine and the hexyloxyphenylamino [a2]- The
resulting dyes 41 md 42 had a maximum absorption at
690 and 655 arn, respectively. A small sEuctural change,
which is a 3, 4-ethylenedioxythiophene ring replacement
in dye 42 by bithiopheae {BT) moiety resulted in a blue-
shift of 39 nm and a loqrer molar extiactioa coefrcient.
The higher -rsc (11.12rnAcm-] and 4 values (?.-61Y9 af
the DSSC based on dye 39 is due to a seperior light-
harvesting ability- This finding uncovered the iryact of
spacer groups on the photocurreat ard efFrciency though
improvement of tle spectra. Based on the supert light-
harvesting performaace of 41 as a result of
a introduction of rich electron 3, 4-ethylenediox
ythiophene moiety, tleaufhors additionally synthesized
two new unsymmetrical SQ-seusitizers, 43 and 44, by
chaaging the indolium unit to quinoline so as to extend
lhe IPCE response into the long-wavelengfh system [43].
Of conrse, the IPCE response was shetched out to 1050
nm for DSSC based on both of the two SQ-dyes.
.4 values were 1ow e1.9%)
Nevertheless, the overall
becsuse of &eir low Yoc aad lcf'. Maeda and co-workers
created tlree novel NlR-absorbiag SQ-sensitizers (45, 46,
a*d 47) with a linearly extended a-conjugated structure
tbrougb Pd-catalyzed cross-coupling reactions utilizing
stannylcyclobutenedienes [44].
The absorption peaks of these SQdyes were situated
at 777, 779, and 800 nrrt, respectively, Nevertheless, the
the total 4 values reduced *om 2.26Yo n dye 44,2.81% ia,
dye 45, tD 1.82% in dye 46. The humble ef&ciency values
are *re ts &e decrease is Yrx, aad electoa traasfer again
w&, j$ values are u*expectedly Iow resulting from the
aggregatioa of dye-molecules.
Warnan et al. A novel molecular procedure for
obtaining a panchromatic SQ- dye was discovered by
covalent linking ofsquaraine dye aad boradiazaktdac -ene
{BODIPY}, which brought about the first tri-
ckcrcph*ric dye ,*9[45]. The SQsensitizer 49 has
abscrptio* spira at 66*, 528 and 42?, allid 552 nm,
whieh are set in shifts cf the squaraine, a*d the BODIPY
chromophores. The similar states of DSSC creation, the
phatocurrent aad the photo- coaversiorr efficiency showed
a progressive fucremelrt in the followirg ofier 47<48<49.
In spite of tke efficiency of &e DSSC by dye49 was just
3.Y/a,tbexe $ufcqrrles affirmed that sr:ch a design strategy
to join the covalent tiree diverse dyes is successful in
imgrove panchrcmatic SQ-sensitizers.

Copyright @ 2018 VBRI Press ?79

Review Article 2018,3{4} 274-283 Advanced Materials Proceed ings

In 2011, Shi and colleagues crated an aslannretric

bis(indoline) SQ-sensitizer 5ll far use ilr SSSC[46J. In
this novel SQ-sensitizer structnre, ore fhiophee rcit was
covalently cormected to an i*dalium mcie{ which
prompting the band to gai* additio*al posrer absorptioa.
Besides, utilizirg a stronger electron pull the
carboxycanorinyl group also resulted &om tle acc€ptor
rather than the COOOH in a very Doppler shift of 23 am
for maximum absorptior comp*red ta 2&- T\e IPCE
curve for dye 50 was observed, surpassing 5{Plu ia &e
wavelength range of 42!-735 n* and reaches aboul 67%
at 710 nm in a standard iodine-based solution cell- The
fraal 4 of 6.76% was obtained with a Jsr:: 14-7 mAcm',
a Yac of t.651 Y, and a FF of A-73. At once, by utiliring
the presence oforgaaic hole once, transfer ofsolids state
rather thsn electroll'te liqui{ the efEciency af Z.68Yo bas
been achieved. This plan metlodology is by all accounts
extremely e*couragiag and indicates that both the
maximum absorption of the red shift and the
panchromatic absorption can be.
Funabiki et al. qmthetic Z-SQ{yes, 51 and 52,
coryrising 2, 3, 3-trimethyl-3H-indole unit as the donator
that is directly related to 3, 4-dihydroxycyclo $ut-3-ene-
1,2-dione without any linker group [47].
In 2$15, Seong Hee Biae et *l lrla,re synthesized
asyrnmetrical SQdye 55 and utilized as sensitizers dyes
for DSSC wi& changiag r-bridge units, based on the D-z-
A SQ{yes. The phenothiazine was used as a doaor group
csrmected to a squaraine certer unit by different
thiopheae derivatives. SSsemitizer has a cyanoacr -ylic
acid {C+H:NO) as an electron accepti:rg group wilh
greater vigor and joiaed directly to SQdye. These SQ-
sensitizers showed intease absorptior: ia tle NIR region
aad powerful fluorescence. Consequently, a DSSC based
oa the SQ-seir.sitizer dye 55 iaclude a thiophene unit as a
r-bridge unit and -COOH group as aa electron-aachoring
graup show &e best photovoltaic performance of 6,01
mAsa41*, 447 rnY *f Yo, atd 0.73of FF to give total
conversioo effi ciency ?, af 2 -A1% 1491.
Fadi M- Jradi aad co-w+rkers reporkd eight SQ-
selsitize{s 5ffi3 with thiophene, zr-bridges with
clmoacetic acid 5G59 and cyaaophosphon -ic acid 60-63
contaias donor/ accep{or glo$Fs synthesized to extend the
absorSioa af SQ-seasifizers- SQ-sensitizers with
cyaaoacsfic add 5t59 acceptor groups have higher
power conversioll efficiencies compared to
cyaaoplesphoric acid 6S{3, with the highest bero:g8.9oh
for t}e SQ-seusitizer 59, this is because of high short'

In2014, Chi Hwan Lee and cs-work€rrElorted a nenr

strategy to promote ths transfer of charge for SQ-dyes and
TiOz by increasirg the acceptor gror4x.
Symmekical (53) alrd asymmetrical SQ-54 dyes wi&
various anchoring gor+s- SQ-se*sitezer 53 coataining a
two anchoring groups displays wirh TiGz elecfror:ic
coupling better thaa the SQ-sensitizer 54 dye which
contain mono-bridge that lead$ 53 to show better
photovoltaic performaace- The opiaaized SQ-53
sensitized solar cells displays 7-7{ mAc*-z sf 1,., *.61V
af Y,", and 0.64 of FF, to give overall conversion
eflrcieucy of 3.19il/a, rrhich is apprcxinxtely 25% higtrer
than the SQ-54 sensitized solar cells [48].

Copyright O 2018 VBRI Press 280

Review Article 2018,3{4} 274-?83
circuit currents (Jsc) and increased open circuit voltages
(Yoc). SQ-sensitizers with cyanophosphonic acid
(CHNO3P) 60-63 anchoriug goups showed lower Jsc
of diminished charge injectioa efEciency, as
because
determined by femtosecond impermanent absorption
spectroscopy. This study suggests that out-ofplare bulky
substituent may increese dye sensitized solar cells
performance by increasing open circuit vollages {ltoc) and
short circuit curreots (Jsc) through decreased aggregation
onTio:/electrolyte recombination [50].
-*xfar&SSC
Slrmmetrk verfius asryfitelric sqa*r*i
The development of the SQ-dye &om the molecular
structure of the symmetric to the asymmefic cae has been
transformed. As previously meatioued, two research
groups studied tle different effests af asymmetric a*d
symmetric sensors (dyes 1}-19 arad27-31) oa ltre DSSC
performance. The two groups conckrded &at asyrunetric
structures were help*rl for en&aacing aad irqJrraving
DSSC performance.
Yuu et al. firtber displayed that the asynrmetrical
SQ-dye 2l gave good conversio* effieieacy bec*r:se cf
the directional electron transfer iE *ie type of m*lecula
Copyright A 2418 VEIRI Press
Advaneed Materials Proceedings
stucture. Nonetheless, modern shrdies have cast
suspicion about the coaclusioa that asymmetric structures
outcome in DSSC with ii:rproved perform -ance in
comparisoa wilh sym:netric structares. Park and co-
wsrkers accurately coryared the symmerrical SQ{ye 64
wftL ia uasymmetrical coogerer 2l [51], The researchers
found that the symmetric dye # generany bad to a higher
totAl 4 : 4.6lYa tha* dye 21 4 : 4.22Yo ua*er
the saae test situafions.
Madad co-worters. specified that a symmekic SQ-
dye ca
led to b€{rsr DSSC perfermnce. The researchers
lord tlat tk SQ{ye 65 pve a high€r total ry of 3.58%
Goryared with its asymmetric peer SQdye 66 4 of 2.8Yo
[52]-The Js *atue of the DSSC based on 65 was
isreasd W 35% (ftom 10-3 - 14.2 mAcm2) with
sryad to dye #- Tk rsffiek referred that the
ircr€se in lsc cot only to fhe effect of panchromatic
abso{Sion but also to tk decrease ic erergy loss caused
by the *oto isomers. Thme results have revealed
signifiaut effecs on DSSC perforoance by refiniag the
steric $nrcttre of &e SQ{yes. From now on, we should
csfiifire to consider various vsiaats for the design of
ilew mleccles SQ*ye in the firture.
Squaraide dyes for C*sexsitized DSSC
To esharce aad evolve the efficieacy of DSSC, many
rmeschers have focused their attention or the
parrchrumaticdyes to exgand the absorption of SQdyes
&sm700-2500 nm [53]. The SQ-sensitizer is an excellent
promi$ng flter for utilize as a co-sensitizer to expand and
ircreeeat the light-harvestiag at near-in&ared
wavelugths regicn as a rosult of its very high molar
exfi*ction coefficienl in the long-wavelength region.
Below ve LigLlight a few cases io whieh SQ-sensitizers
dyes xere *ilized as co-sen$itizers b DSSC-
281
Revierry Article 2018,3(4) 274-283 Advanced Materials Proceedings

Chen and his colleagues co-sensitized SQdye 26 With the global increasing request for energy saving aad
with yellow merocyanine (CzeI{:zN:NaOrS) dye 00 a"d alternative energy, technologies, will contioue the search
red hemicyanine fluorescent dye {R) 1541. T\e IPCE for best organic materials for aa enhancing arrd
display high values greatff than TOYo with a broad band developmert tle DSSC by using SQ- seasitizers.
range of400-800 run, due to the contributian from three Coasidered &e SQ- dyesa very promising
seasitizers
dyes with various absorption properties- This patl lead to tle near-
candidates due to high absorption coefficietts in
:
total q of 6.5To with a Jsc 15-8 m/$m-2, a Yac of 0.525 IR regior aad stable *ea-IR abso*ing so should be
V and a FF of0.63. nsing ia &e technology erd l&eir applicatioas for
conskucting futegrated photovoltaics. It is important and
')'-"""' feasible to seach ad eadeavor to get on asrs high
efficiency SQ-sensitizers for dye sersitized solar cells. So
\ the absorpioa of pmchro -matic with bigh absorptior
/''-\
/L// //-- csefrsierts of the visible to near-IR spectral area of SQ-
scssitiz€rs dyes remairu a major challenge for scientists'
research in &e comilg yers.
lt.'\-tr t\_ /
\A,/-:-\_/-\ \/cHrcoo HO
Refere*es

l. C'regm, B-; G:auel W; aaase.J991353, 737140.

rxl1: !0jQj.8_3jlljja9
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DC{:10.1021 cr900356p
Yum et al. mixed SQ-dye 2t with&e crpdc d}E JKz Alasd, S,; C-xiIla.EI-; {k&r}" M.; Nazwraddin, lvllL; Energ &
which exhibits a major absorpfion bar:d at aremd 45& mr E*rtonxxral Sciszce ?3r3, 6, 343 9-3464 -
-

nfi: 0. I0i9.clEE4I888J
[55]. The effectiveaess of such salm cell awararress
r

lrtrska, A; Fisck
, MK R;
Eauerle" P-; Angewawlte Chemie
participated higher than cells ksed on flre irldivi&Bl Itrmofia*l F.ditisn -ffig, 48, 2474-2499.
sensors because of IPCE spectrurfi resultilrg *om tle BDL i0.i001 arie.200S0.i709
expaasion of the features of the abs+rprfim T A; and Jac€&, K-;Angewandte Chemie International
ryectra
complementar)r. The securities Jsc : l5-5 rAcna-z ad
Ed'xiril ia Erylish,lg$s, 4. 694.
IEI: I lt. I tl02 anie. I 96,s06941
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represetts q af 7.43Va rxing }iquid electrolytes. It has 588-
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7.
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