Structure-Property Interrelations in Non-Crystalline Semiconducting Polymers for Organic Electronics

1
S uc u e-P ope y In e ela ions
in Non-C ys alline Semiconduc ing
Polyme s o O ganic Elec onics
May 2024
W i en by
Nicolás Ramos Gómez
S uc u e-P ope y In e ela ions in Non-
C ys alline Semiconduc ing Polyme s o
O ganic Elec onics
A disse a ion submi ed o he
Uni e si y o he Basque Coun y (UPV/EHU)
p esen ed by
Nicolás Ramos Gómez
In pa ial ul illmen s o he equi emen s o he deg ee o
DOCTOR IN APPLIED CHEMISTRY AND POLYMERIC MATERIALS
Resea ch conduc ed unde he supe ision o
D . Jaime Ma ín Pé ez (UPV/EHU)
Donos ia, May 2024
(cc) 2024 Nicolás Ramos Gómez (cc by-nc-sa 4.0)
I
I u i zaha e ik
eda en du ,
u be ia eda en,
be i be i den u a,
be iko i u i zaha e ik.
De la ieja uen e
bebo,
bebo el agua nue a,
el agua que siemp e es nue a,
de la uen e que siemp e es ieja.
Joxean A ze

I
Acknowledgemen s
I wan o hank all he people ha s ay wi h me du ing his yea s and suppo me in
his new knowledge ield o me. The made me imp o e mysel and expand my esea ch
ca ee . This hesis i is no only he ui o my wo k, i is made hanks also o all he
people ha was a ound me help me in and ou side he job.
En p ime a ins ancia que ía da las g acias a mi di ec o Jaime Ma ín, ya que
en e los dos hemos sacado es e abajo adelan e a pesa de odas las inclemencias
debido a los cambios p oducidos du an e es os años po la pandemia, aslados, e c. Ha
sabido da me espacio pe o ambién me e me caña cuando e a necesa io. También
quie o da las g acias al es o del g upo. Muchas g acias a Sa a po acoge me y
ayuda me cuando llegué a una ciudad comple amen e nue a y empecé en un campo
o almen e di e en e a odo lo que yo había es udiado. G acias a ella le cogí el gus illo a
las noches de sinc o ón y a a amien o de da os con el maldi o Fi 2D. Po o o lado
que ía da le las g acias a mi pos doc Edga . En ó casi igual de pe dido que yo en la
écnica de lash DSC pe o conseguimos en ende la y busca le uqui os jun os. Nos
mejo ó mucho la calidad de ida au oma izando p ocesos an o del lash como del
sinc o ón poniendo en pelig o su pelo al hace una as a inmensa! También quie o da le
las g acias a Valen ina po es a ahí y apoya nos mu uamen e en los peo es momen os
y ayuda me a cen a me y no dispe sa me.
G acias ambién a Daniele Cangialosi y Vale io, que desde el CFM me han
enseñado lo complicado y boni o que puede llega a se el es udio de la ase í ea de
los políme os.
G acias ambién a odos mis compañe os de la uni e sidad y de polyma po
acoge me cuando quedé hué ano de je e aquí en Donos i. G acias a Elena, Mi yam,
Ma a, Xabi, Ainhoa, Paula, A i z, Giulia, Lucas, los Iones, Emelin, Fe mín, Ál a o…
G acias a odos los que han es ado y es án aho a po odos los buenos momen os que
hemos pasado y nos quedan po pasa !! También a Da id po acoge me en su g upo y
enseña me a abaja happy pe o ambién ha d. A odo el pe sonal de la de la
uni e sidad como Mai e o el pe sonal de la ca e e ía y de limpieza que hacen que odo
uncione como un eloj suizo.
Muchísimas g acias a mi no ia Raquel que ha es ado es os úl imos dos años
aguan ándome y sopo ando odas las ho as que he echado en casa haciendo la esis.
Ha conseguido que me sien a en San Sebas ián como en casa y ha sido mi uen e
cons an e de apoyo y alien o a lo la go de es a a dua a esía académica. Es e log o no
solo es mío, sino nues o, y quie o exp esa mi g a i ud po su amo incondicional, su
apoyo inqueb an able y su con ibución in aluable a mi ida, an o pe sonal como
académicamen e.
G acias po odo (menos po ayuda me en la esis jejeje) a odos mis amigos y
amilia an o de Salamanca, como mis abuelos Abue y Cani, mis ías Sonia y Belén y
las p imas. De To ecaballe os a odos (que sois muchos) y los amigos de mi peña.
También a los de oda la ida con los que he compa ido odos los años de mi ida y mi
educación Desde la in ancia como Ma eo, Diego, Ja i, Ana… has a la uni e sidad y el
mas e como Ca li os, Ana, E a, Samu, Maya, Sil ia, And es, Rulo, P e us, Fe ni…
Y ambién a los nue os de San Sebas ián como Gab iel, Luna, Da id y Ál a o y mis
colegas del A lé ico de San Sebas ián.
Y po úl imo, muchas g acias a oda mi amilia en especial a mis pad es Jose
Manuel y Susana y a mis he manos Ma ía y Miguel. En acaciones me han echado la
b onca y me han hecho a anza en la esis cuando menos me ape ecía. Nos hemos ido
de iajes y me han c iado y han conseguido un (mini)doc o en la amilia.
III
Summa y
Nowadays, all he semiconduc o indus y is go e ned by he silicon echnology.
The inc easing o he ene gy consump ion and he use o elec onic de ices o ce o
de elop and ound new ma e ials wi h less ene gy consump ion, less ha m ul and new
p ope ies. In he las decades he o ganic semiconduc o s (OSC), including
semiconduc ing polyme s, appea as a new, p omising al e na i e. Flexible and
anspa en de ices can be de eloped wi h hese new ma e ials. The scalabili y and he
easy p ocess om solu ions compa ed o molecula beam epi axy (MBE) o a omic laye
deposi ion (ALD) used o he common semiconduc o de ices make he mos impo an
di e ence and make he OSC as a new p omising echnology. Howe e , o ganic
elec onic echnologies a e s ill a hei ini ial s eps and he communi y is s ill ocused on
unde s anding hese impo an ma e ials.
This hesis p esen s 3 imely s udies on ma e ials science aspec s o polyme ic
semiconduc o s. The idea is o unde s and and con ol he mo phology o he
polyme s o imp o e and une hei op oelec onic p ope ies.
The i s chap e (chap e 3) deals wi h he s udy o he ac i e laye o an o ganic
sola cell. The glass ansi ion o he bulk he e ojunc ion is s udied o de e mine he
composi ion o he in e mix phase on he ac i e laye .
The second chap e (chap e 4) is ocused on he s udy o he solid-s a e
mic os uc u e o he high-mobili y polyme IDTBT, which has been claimed o be “nea ly
amo phous” polyme and hus con on s he gene al idea ha good elec ical p ope ies
s em om high c ys allini y.
In he hi d expe imen al chap e (chap e 5) I s ablish ha , like c ys alline egions,
glassy egions can be also manipula ed o op oelec onic p ope ies in semiconduc ing
polyme s.
IV
3
1) In oduc ion
A semiconduc o is a ma e ial ha is capable o ac ing as a conduc o o insula o
depending on he ex e nal s imuli. No mally he empe a u e, p essu e, adia ion,
magne ic o elec ic ield a e he mos common ac o s ha change he semiconduc o
p ope ies1. This ype o ma e ials is e y in e es ing o use as de ec o s, senso s o
ampli ie s because hei elec ical conduc i i y can be une changing, con olling o
knowing he en i onmen whe e is he de ice and ice e sa.
Semiconduc ing ma e ials e olu ionized he elec onic echnology ob aining
smalle de ices (swi che s and ampli ie s) han wi h he mionic al es. The la e elies
on he low o elec ons om a hea ed ca hode o a posi i ely cha ged anode in a
acuum-sealed glass ube. In con as , semiconduc o s ely on he p ope ies o
ma e ials like silicon and ge manium o con ol he low o elec ons and can be much
smalle 2.
The mos common and well-s udied semiconduc o is he silicon (Si). The
abundance o his ma e ial, oge he wi h i s in insically good semiconduc o p ope ies
a e he easons why silicon domina es he indus y. Fu he widely used semiconduc ing
ma e ials a e among o he s: ge manium (Ge), sul u (S), selenium (Se), gallium a senide
(GaAs), e c3. Semiconduc o s a e di ided in wo ypes: in insic ma e ials which possess
inhe en semiconduc o p ope ies and ex insic ones which need o be doped wi h o he
a oms o ob ain semiconduc o p ope ies. Doped semiconduc o s can be ei he N- ype
o P- ype depending on whe he he ee cha ges a e elec ons (e.g. wi h bo on (B),
indium (I) and gallium (Ga) as dopan s) o holes (e.g. wi h phospho ous (P), a senic (As)
and an imony (Sb) as dopan s)1.Combining N- and P- ype semiconduc o s (e.g he
in en ion o he p-n junc ion) he humani y has been able o c ea e a wide ange o
elec onic de ices including diodes, ansis o s, senso s, sola cells, e c.
Ne e heless, he abo e ino ganic semiconduc o s ha e shown some
disad an ages. The mos signi ican one is he complexi y o ab ica ion because hey
need e y expensi e echniques such as molecula beam epi axy (MBE), a omic laye

4
deposi ion (ALD), e c. These echniques equi e a high echnology le el like high acuum
o high in ensi y. Mo eo e , he classic semiconduc o s ha e no oo much lexibili y and
duc ili y so hey a e no able o use o example in lexible de ices.
Cu en ly, he g ow h o he semiconduc o indus y is exponen ially g owing. The
size o he ansis o s e ol ed om cen ime e s o nanome e s in ew decades. Moo e
de eloped a heo y s a ing ha he size o he ansis o s in an in eg a ed ci cui will be
doubled e e y wo yea s4. Nowadays, expe s p edic ed ha in his decade he physical
limi o dec ease he size o de ices is almos eached due o he physical challenges
associa ed wi h minia u iza ion.
Figu e 1 Miles ones o he op oelec onic indus y.
The i s scien i ic publica ion on o ganic semiconduc o ma e ials da es om 1954,
in which he elec ical conduc i i y o o ganic polysul ones was desc ibed5. In he 70s,
he i s semiconduc ing polyme , i.e. doped polyace ylene (PA), was epo ed by Chiang
e al. These de elopmen ises he possibili y o b eak he ba ie o he classical
semiconduc o s and ob ain be e mechanical p ope ies, non haza dous and
biocompa ible de ices ha allow o link he elec onic wo ld and biology , i.e.
1870s
1887
1904
1947
1954
2010s
2000s
1990s
1980s
1962
1960
The mionic
al e
Semiconduc o
de ice
T ansis o
Sola cell
O ganic
semiconduc o
Lase
In eg a ed
ci cui
LED
OLED
Blue LED ligh
Flexible and
anspa en
o ganic de ice
5
bioelec onics67. Du ing he 80s and 90s, di e en ypes o o ganic semiconduc o s we e
de eloped as small molecules o polyme s.
The common and mos used commodi y polyme s a e insula o s. These include.
e.g. polye hylene (PE), polye hylene e eph hala e (PET), ac yloni ile bu adiene s y ene
(ABS), e c. These amilies a e composed o epea ing uni s connec ed by single co alen
bonds. These sp3 hyb idiza ion a e s ong, non-pola , and ha e low elec on mobili y. As
a esul , commodi y polyme s ha e limi ed elec ical conduc i i y and a e mainly used as
insula o s, ilms o o mechanical pu poses8.
I he polyme s ha e a oma ic ings o double bonds, a sp2 hyb idiza ion occu s.
Wi h his con igu a ion, he elec on ha is no linked wi h he adjacen a om is o ming a
π-bond ins ead o a σ-bond. The elec ons ha a e in he π-bond a e weake and
delocalized so he elec ons can mo e mo e eely. I his explana ion is mo ed o he
elec onic band s uc u e, in he insula o polyme s, he space be ween he alence band
o highes occupied molecula o bi al (HOMO) and he conduc ion band o lowes
unoccupied molecula o bi al (LUMO) is la ge so he elec ons canno climb o he
conduc ion band o mo e eely9. In he case o conduc o polyme s, ha space does no
exis so he elec on can mo e a will. Finally, in he case o he semiconduc ing polyme s
ha space, named bandgap, is less so, applying some ene gy o he sys em he ma e ial
can conduc he elec ici y10.
6
Figu e 2 a) Hyb idiza ion sp2 o he o bi als, b) Link be ween wo sp2 o bi als and c) Chemical s uc u e o
he polyace ylene.
As desc ibed abo e, semiconduc ing o ganic molecules o conjuga ed polyme s
owe hei op oelec onic and magne ic p ope ies o he sp2 bonds bu also o he
conjuga ion. Conjuga ion is he delocaliza ion o mul iple π-bonds ha o m la ge and
mo e s abilized molecula o bi als. I is achie ed by al e na ing single and double bonds
along he backbone. The o bi al p ha is no linked can ei he be in-phase o ou -o -
phase wi h neighbo ing o bi als, o ming bonding (π) and an ibonding (π*) in e ac ions
espec i ely. The plana i y o he conjuga ed molecule is impo an o maximize he
o bi al in e ac ions1112. The bandgap o hese ma e ials is usually in he ange o isible
ligh . This means he ma e ial can be exci ed op ically o e ing new solu ions in he ield
o op ical senso s o pho o ol aic applica ions13.
Doping in hese polyme ic ma e ials e e s o chemical oxida ion in he case o he
p- ype polyme s and educ ion in he case o he n- ype. When he p- ype polyme s a e
exci ed he Fe mi le el is displaced o he alence band so elec ons mo e o lowe le el
o he bandgap and he anspo o he cha ge occu s in he alence band ( he posi i e
hole ha he elec on le can mo e). I he ma e ial is n- ype occu s o he wise and he
σ bond
sp
2
o bi als
p o bi al
π
bond
a)
b)
c)
σ
π
7
elec on (nega i e cha ge) can mo e h ough he conduc ion band14. This p ocess is he
same as he exci on pai elec on-hole in he classic semiconduc o s15.
One molecule is no enough o he cha ge anspo so some π-o bi als ha e o
be o e lapped wi h hei con iguous o ha e a con inuous pa h o he conduc i i y.
In insically, he ma e ials wi h π-bonds y o heap hem wi h he π-bonds o o he chains
o s abilize all he sys em so all hese conjuga ed polyme s ha e π-π s acking ha also
con ibu es o enhance he ca ie mobili y16.
The adi ional conjuga ed polyme s ha e poo s abili y, which limi s hei e iciency
and pe o mance so, o o e come his issue, push-pull polyme s we e de eloped. This
new amily o conjuga ed polyme s has wo pa s in eg a ed in he same molecule. I has
a dono and an accep o pa balancing he elec on dis ibu ion and enhancing i s
s abili y. Also, his esul s in e icien cha ge sepa a ion and imp o ed elec ical
conduc i i y.
Figu e 3 Indacenodi hiophene-co-benzo hiadiazole (IDT-BT) push-pull polyme . In g een he dono pa
and in g ay he accep o pa .
Keeping his in mind, he mobili y o he elec ons on he conjuga ed polyme s no
only depends on he o mula ion o he polyme . I depends also on he o ien a ion o he
backbone and he side chains, he plana i y, he packing, he dis ibu ion… In o he
wo ds, he mic os uc u e.
The e a e se e al ad an ages o conjuga ed polyme s wi h espec o ino ganic
ma e ials. The ab ica ion o he de ices is cheape because hey do no need complex
8
echniques like MBE. This is ela ed o he easy and low-cos echniques o deposi he
polyme s like spin coa ing o blade coa ing and he acili y o scale hese echniques.
Polyme ic ones ha e, also, less agili y and mo e lexibili y. This gi es he op ion o
de elop cu ed displays o lexible mic op ocesso s17. They a e anspa en o
anslucen so he e is a possibili y o de elop anspa en sola cells o windows o
example. And one o he mos p omising ad an ages is he biocompa ibili y o he
conjuga ed polyme s o expand he de ices o medicine and biological esea ch due o
he in e ac ion wi h he en i onmen which was p e iously una ailable7. Wi h o ganic
polyme s ac ually, he e a e de ices like ansis o s, diodes, in eg a ed ci cui s, memo y
de ices, sola cells, senso s and sc eens and displays based on hem.
To unde s and p ope ly how he op oelec onic p ope ies a y in a semiconduc o
polyme is essen ial o s udy hei mic os uc u e. On he solid s a e, ma e could ha e
some mic os uc u es depending on he o de o hei a oms. In he case o polyme s, i
depends on he o de and con o ma ion o he chains. I a ma e ial has a diso de ed
molecula s uc u e whe e he polyme chains a e andomly a anged, i is e e ed o as
amo phous. This mic os uc u e has singula quali ies as anspa ency o lexibili y
be ween o he s.
I he polyme was comple ely o de ed, wi h he same pe iodici y be ween hei
a oms i would be a c ys alline ma e ial. I is impossible in polyme s o ob ain a 100% o
c ys allini y so he polyme s ha c ys allize a e denomina ed semic ys alline. I he
ma e ial has some deg ee o o de bu no enough o call i c ys als (i could be c ys als
wi h a lo o de ec s) hey a e named pa ac ys alline polyme s. They a e cha ac e ized
by he p esence o a lo o s uc u al de ec s ha gi e hem localized andom domains
wi h di e en s uc u al p ope ies bu a ce ain pe iodici y in he sys em18. Be ween bo h
models o o ganiza ion o he polyme chains he e a e o he one. The semi-
pa ac ys alline model shows some deg ee o long- ange o de and egula i y like he
pa ac ys als bu wi h a mo e limi ed deg ee o s uc u al o de . I has he dense
a angemen o e y small pa ac ys alli es coexis ing wi h mo e diso de ed si es in an
amo phous ma ix19. This opens he ield o mo e lexible and adap able de ices han
semic ys alline ma e ials. Also, he las yea , ou g oup de eloped a new heo y o he
possible s uc u a ion o he polyme s. The semi-pa a-c is allini y19.

9
The las mic os uc u e is he liquid c ys al. This is a dis inc phase in he liquid
s a e ha exhibi s p ope ies o liquids and c ys alline solids. I has an in e media e s a e
be ween solid and liquid, whe e hei molecula s uc u e aligns o some deg ee while
s ill e aining luid-like beha io . Liquid c ys al polyme s possess chains ha can o de
hemsel es in o a pa ially c ys alline a angemen unde ce ain condi ions. This s a e is
cha ac e ized by hei aniso opic na u e, meaning ha hei p ope ies can a y
depending on he di ec ion. These polyme s can exhibi di e en deg ees o molecula
alignmen o o ien a ion, which can be in luenced by ex e nal ac o s.
Focusing on he ansi ion be ween he s a es o solid ma e , polyme s ha e
ce ain empe a u e named glass ansi ion empe a u e o Tg. I he polyme is abo e
his empe a u e, i can mo e and i he polyme is below Tg is eeze he sys em. This
pa ame e is e y impo an because he ma e ial expe iences huge changes in he ee
olume, densi y, speci ic hea , mechanical p ope ies, e c.
Figu e 4 Scheme o he polyme he mal ansi ions.
T
c
T
m
T
g
T
LCST
10
The e a e ou ansi ion empe a u es. The Tg ha was explained be o e, he
c ys alliza ion empe a u e (Tc), liquid c ys al-liquid ansi ion and he mel ing
empe a u e (Tm). The c ys alliza ion empe a u e is he poin when he polyme chains
mo e om a diso de ed s a e o an o de ed s a e. When he sys em equalizes and goes
abo e Tc, he ee ene gy o he polyme sys em is minimized and he polyme chains
begin o a ange hemsel es in o an o de ed s uc u e. This c ys als a e composed by a
epea ing, long- ange s uc u e and a e a unc ion o he polyme 's chemical composi ion,
molecula weigh , and p ocessing condi ions2021. The mel ing empe a u e is he poin
when he polyme goes om solid o liquid s a e. A his empe a u e, he sys em akes
enough ene gy (hea ) o su pass he in e molecula o ces ha main ain he c ys als
linked. The las empe a u e, less knowledgeable and i has only a ew polyme s ha e i
is he liquid c ys al-liquid ansi ion (LCST). The LCST is he empe a u e a which he
polyme changes om liquid c ys al o iso opic liquid. This is an impo an ansi ion
alking abou p ocessing due o i s special mechanical p ope ies being a iscoelas ic
liquid in a ange o empe a u es. The s a e o ma e named liquid c ys al has p ope ies
be ween liquids and solids. Is a pa ially o de ed liquid wi h long- ange a angemen who
go i aniso opic p ope ies like bi e ingence, pola izabili y o dich oism22.
Figu e 5 Classic solid-s a e s uc u al models o polyme s.
The classical heo y o conjuga ed polyme s said as many c ys als, as much
conduc i i y. This is because, no mally, he de ec s and la ice diso de a ec as aps
educing he conduc i i y23. Fo his eason, he heo y o he conduc i i y in
semic ys alline o pa ac ys alline polyme s is h ough o de ed domains in e connec ed.
The mos common “links” be ween o de ed egions a e he agg ega es and he ie
chains. Agg ega es a e clumpings o polyme chains wi h some o de and ie chains a e
Tempe a u e
Amo phous
Semi-c ys alline
Pa a-c ys alline
Liquid
Liquid
Liquid
T
g
T
g
T
m
T
m
T
c
11
lexible chains ha connec c ys als o o de ed egions in a polyme ne wo k ac ing as
wi es h ough which elec ici y is conduc ed.
The e o e, he high mobili ies in polyme s a e no dependen only on he
c ys allini y. They ha e many complex s uc u es (some o hem e en conside ed
amo phous) well connec ed ha conduc elec ici y.
The cha ge anspo always inc eases he empe a u e o he sys em like he Joule
e ec in he conduc o ma e ials. Due o his, op oelec onic de ices based on polyme s
ha e o ha e high he mal s abili y. To be su e ha he ma e ial will no change i s
s uc u e and p ope ies high Tg and Tm alues a e p e e ed. On he o he hand, low Tg
and Tm con e s o he sys em mo e lexibili y so he e has o be a balance.
This wo k is ocused on how con ol he op oelec onic p ope ies in sund y
p omising de ices o applica ions in ansis o s sola cells and senso s.
In summa y, conjuga ed polyme s a e p omising ma e ials o ad anced
applica ions, such as lexible elec onics and bioelec onics. To ge he mos ou o
conjuga ed polyme s is necessa y o unde s and, con ol and know how o une hei
s uc u e. No mally, classical s udies a e ocusing on unde s anding he c ys allini y bu ,
nowadays, he i eous phase is aking mo e impo ance. Knowing and swi ching he
i eous phase he op oelec onic p ope ies also could change signi ican ly.
12
19
down o -80 o -90 Celsius ( he minimum empe a u e is eached by he FSC) and
immedia ely hea ed up o he highe empe a u e. Finally, he ma e ial is cooled wi h he
same cooling a e and i is made ano he hea ing amp o use i as a e e ence (hea ing
wi hou he iso he mal s ep).
Figu e 7 FSC p o ocol wi h Ta (annealing empe a u e) and a (annealing ime).
The a o emen ioned o e shoo can be explained wi h he own de ini ion o he Tg.
The glass ansi ion empe a u e (Tg) is de ined as he empe a u e (o ange o
empe a u es) whe e he glassy phase unde goes a change be ween an immobilized
s a e (ou -o -equilib ium glass) o a molecula mobili y s a e.30 In he case o calo ime y,
i he ma e ial in he immobilized s a e e ol es h ough a less ene gy le el ( educing i s
en halpy) an endo he mic o e shoo can be seen a empe a u es close o he Tg. This
p ocess is called physical ageing. In conclusion, he glass ansi ion empe a u e and he
me as able equilib ium o an o de glassy phase below ha empe a u e can be s udied
by esea ching he endo he mic o e shoo s o med by ageings below Tg.
Tmax
Tmin
Tempe a u e (ºC)
Time
Annealing
Re e ence
Ta, a

20
Figu e 8 Tempe a u e dependence o he en halpy o a ypical glass o me cooled down a a gi en
cooling a e β.
Figu e 9 E ec o an ageing in a DSC expe imen . In g een he sample aged and in g ey he sample
unaged.
When he annealing ime is changed (a he same empe a u e all de annealings),
s udying he e olu ion o he endo he mic o e shoo , he kine ics o c ys alliza ion and
o de ing can be s udied o know i he peak is due o he glassy phase, nuclea ion o
T
g
En halpy
Tempe a u e
Cooling a e = β
T
a
< T
g
physical ageing
Ta > Tg No physical ageing
H
e
=H
aged
H
a
H
e
H
e
=H
a
W
Tempe a u e
21
g ow h o c ys als. The o al a ea o he endo he mic o e shoo s a e i ed wi h a
sigmoidal-like law (e.g. Kohl ausch-Williams-Wa s, A ami, e c.). The pa ame e in
which we a e in e es ed is β, he A ami exponen .
∆𝐻=𝑒(𝑘𝑡)𝛽
Equa ion 1 Kohl ausch-Williams-Wa s o A ami-like law.
Whe e ΔH he maximum en halpy alue measu ed in he expe imen s, k is a
cons an associa ed wi h he a e o he ad ance o he he calo ime ic p ocess, is ime
and β, is a pa ame e ela ed wi h how he ad ance o he p ocess depends on
empe a u e and i is ypically e e ed o as he A ami cons an .
2.2.1.1.2) Isoch onous “annealing”
De eloped by Cangialosi e all, i is used o iden i y he Tg o he samples by FSC.31
The same p o ocol as in he iso he mal Figu e 7 is used bu , ins ead o a ying he ime
o annealing, is a ying he empe a u e o he annealings. In his way, when he
empe a u e is below he Tg, in he iso he m he i eous phase is o de ed (e e y ime
he ma e ials y o each he low ene gy s a e) ha is ansla ing in o an endo he mic
o e shoo in he hea ing cu es o he DSC. The poin when he o e shoo becomes 0
can be ex apola ed when some measu emen s a e made inc easing he annealing
empe a u e. A his poin , he i eous phase canno e ol e. The e o e, his means ha
we ha e eached he ea ly pa o he Tg egion called Tg onse 32.
The e olu ion o he c ys alline phase abo e Tg can also be s udied wi h his
me hod.
2.2.1.1.3) Modula ed DSC
The idea o his p o ocol is, ins ead o using a linea hea ing amp, o use a pe iodic
empe a u e modula ion (s ep esponse o sinusoidal usually) o a ce ain ampli ude and
equency.
22
Thanks o his p o ocol, we can sepa a e p ocesses due o e e sible Cp and
i e e sible Cp. In his way, o example, cold c ys alliza ion p ocesses and e e sible
p ocesses such as he glass ansi ion can be sepa a ed.
Figu e 10 Schema ic scheme o one pseudo-wa e o he modula ed DSC.
This p o ocol in FSC consis s in a pseudo wa e ha simula es an ha monic hea ing
p o ocol. One hea ing amp o wo deg ees, a small iso he m, one cooling amp o 1
deg ee and ano he iso he m wi h he same ime o he p e ious one. Repea ing his ou
s eps x cycles a modula ed DSC is ob ained wi h a s ep o 1 deg ee33. The maximum
eloci y o he equipmen o he da a acquisi ion wi h his small hea ing and cooling
amps is 1000 K/s. Changing he ime o he iso he mal s eps we a e able o change he
modula ed equencies ( ypically be ween 1 and 20 Hz). I is necessa y o use he Fou ie
ans o m o ea he da a and sepa a e he Cp e e sible om he non e e sible34.
2.3) X- ay echniques wi h synch o on adia ion
A synch o on is a ligh sou ce emi ed by elec ons mo ing e y as (almos ligh
speed) inside a ing. The spec um o synch o on ligh eaches om he a in a ed o
nea γ- ays. The adia ion is emi ed angen ially and o wa d om he pa icle o bi due
o he na u e o he ela i is ic pa icles. The angle o he collima ed ligh co esponds o
1/γ whe e γ is he Lo en z co ec ion ac o o he pa icle ela i is ic mo ion:
γ = (1 − β2)−0.5, whe e β = /c and is he elec on eloci y and c he speed o ligh in
acuum. The wa eleng hs ob ained om he synch o on adia ions include om he a
23
in a ed o nea γ- ays.3536 We le e age he ha d X- ays o his ligh hanks o he
monoch oma o s.
Due o he wa e-pa icle duali y, he elec ons can be conside ed “wa e packages”
and, he e o e, pa icles named pho ons in he case o he ligh . Also, hey can ha e all
he wa e p ope ies such as di ac ion, e lec ion, e c. 37 This is because hey can be
conside ed “ma e wa es” wi h hei own wa e unc ion so knowing he mass and he
eloci y, he wa eleng h can be known hanks o he de B oglie equa ion λ=h/m whe e
lambda is he wa eleng h, h is he Plank’s cons an , m is he mass o he pa icle and
he eloci y.38
The synch o on has 5 di e en ia e pa s. The elec on gene a o o “Elec on gun”
whe e he elec ons a e gene a ed by hea ing a me al up o 1000 Celsius ( ungs en wi h
ba ium oxide no mally), a linea accele a o (Linac) whe e he elec ons we e accele a ed
up o 100 MeV using adio equency ca i ies. Then, he elec ons accele a ed up o 3
GeV in a boos e ing wi h elec omagne ic ields. Finally, he elec ons a e deli e ed in o
he s o age ing. Main aining unde acuum o minimize he sca e ing o ai , i keeps he
elec ons spinning un il he ex ac ion o hem angen o he ing in he beamlines wi h
he help o magne s. Then, in he beamline, hey a e used some sli s, mi o s and
monoch oma o s o ob ain he desi ed wa eleng h.3940
24
Figu e 11 Synch o on g aph. a) Elec on gun b) Linac c) Boos e ing d) S o age ing e) Beamline.
The synch o on adia ion ligh sou ce is used because he in ensi y is highe han
in he con en ional X-Ray ubes and he ligh is e y pola ized and collima ed.
2.3.1) G azing incidence wide-angle and small-angle X- ay
sca e ing (GIWAXS and GISAXS)
X-Ray echniques a e good o s udy he s uc u al and mo phological aspec s o
he semiconduc o polyme s in a b oad ange. In ou case, he maximum ange we use
is be ween 0.006 and 25 nm-1 app oxima ely. All he dis ance da a a e exp essed in
sca e ing ec o , momen um ans e o wa e ec o ans e sca e ing ec o ,
momen um ans e o wa e ec o ans e (q) which is in e sely p opo ional o he eal
dis ance (d).
Mo eo e , he B agg law41 ela es he dis ance be ween adjacen pe iodic planes
(d), he wa eleng h (λ) and he angle be ween he sca e ed wa e and he inciden wa e
(𝜃). I his law is ul illed, he pe iodic dis ances o he ma e ial can be s udied.
a)
b)
c)
d)
e)

25
𝑞=2𝜋
𝑑 𝑛𝜆=2𝑑sin𝜃
Equa ion 2 a) q-d ela ionship and b) B agg's law.
In he speci ic case o GISAXS and GIWAXS, ins ead o knowing he in e plana
dis ances, he shape, ex u e and o ien a ion can also be shown.
Figu e 12 GIWAXS and GISAXS geome ies.
The de ec o whe e he in ensi y alues o he sca e ing a e collec ed is plana so
i is necessa y o make some co ec ions in GIWAXS. In he case o GISAXS, he
de ec o is e y a om he sou ce so i is conside ed ha he image in he de ec o is
e acious. The sca e ing o he sample is iso opic ( ec o ially speaking) so, ha ing a
plana de ec o , he dis ances in he plana de ec o a e no he eal alue o q. A
sphe ical de ec o is needed o ob ain he eal dis ances in he ecip ocal space o ha e
all he de ec o s equidis an o he de ec o . Wi h he plana de ec o , he Ewald sphe e
co ec ion is used4243 as you can obse e in Figu e 13.
q
R
q
R
q
Z
q
Z
GIWAXS
GISAXS
a)
b)
26
Figu e 13 Ewald sphe e co ec ion scheme.
Mo eo e , as much o de ed he ma e ial (mo e pe ec is he pe iodici y), he peak
obse ed in he de ec o is sha pe . Knowing he wid h a he hal way up he peak
(FWHM o ull wid h hal maximum) and he posi ion in he q ange, can be de e mined
he cohe en leng h (Lc) hanks o he Sche e equa ion (Equa ion 3)44 whe e k is he
shape ac o (be ween 0.9 and 1)45 and Δq is he FW M.
𝐿𝑐=2𝜋𝐾
∆𝑞
Equa ion 3 Sche e equa ion.
This pa ame e is di ec ly ela ed wi h he pa ac ys alline pa ame e (g). Wi h his
pa ame e is measu e de s a is ical luc ua ion o indi idual la ice spacings45. Fo highly
diso de ed sys ems, he g pa ame e can be ex ac ed om he wid h o he i s o de
di ac ion peak19 only i he peak is en i ely desc ibed by cumula i e diso de and i
pa ac ys allini y is mo e signi ican han la ice pa ame e luc ua ion46. I hese wo
condi ions a e ul illed
𝑔=√∆𝑞
2𝜋𝑞
Equa ion 4 g pa ame e equa ion.
27
whe e Δq is he FWHM and q is he maximum peak posi ion. The g pa ame e can
oscilla e a lo be ween 0.01 (1%) and mo e han 0.20 (2%) using as scale-based ma e ial
he a-SiO2. Ig g > 1% he ma e ial is highly c ys alline, i 1% < g < 10% he ma e ial has
impe ec c ys als and/o mesophases and, i g < 10% he ma e ial is amo phous30.
Fo GIWAXS he incidence angle used was 0.12º (li le below he Si angle) bu he
measu emen s we e ca ied wi h 4 di e en angles be ween 0.08 and 0.2 o ob ain he
bes da a. 3 di e en ypes o in eg a ions we e ca ied ou . Comple e (in he whole
di ec ions), in-plane aking he 45 deg ees below o see he o de in he chains ha a e
pa allel o he subs a e and ou o plane o s udy he pe pendicula subs a e di ec ion
planes. The empe a u e expe imen s we e conduc ed in a Linkam® in a N2 a mosphe e.
All he expe imen s we e pe o med a he BL11 NCDSWEET beamline a ALBA
Synch o on Radia ion Facili y (Spain). The inciden X- ay beam ene gy was se o 12.4
eV using a channel cu Si (1 1 1) monoch oma o . A Rayonix® LX255- HS a ea de ec o
was used. The se up was calib a ed using C 2O3 as e e ence.
Figu e 14 GIWAXS pa e n and scheme o a) Low diso de ou o plane, b) To ally diso de , c) Ou o plane
and d) In plane.
Fo GISAXS he ho izon al in eg a ion was used a he Yoneda peak o ob ain he
maximum ange o in ensi y. The expe imen s we e de eloped a Alba and Ele a
a)
b)
c)
d)
28
synch o ons. In bo h cases he calib a ion sample was AgBH (Sil e Behena e) and he
de ec o s we e he Pila us 1M de ec o om Dec is®4748. Fo he empe a u e
expe imen s a Linkam® in a N2 a mosphe e was used a Alba and an An on Paa model
DHS1100 was used a Ele a48.
2.3.2) NEXAFS
Unde s anding he molecula a angemen and o ien a ion o polyme chains is
pi o al in ailo ing he p ope ies o ad anced ma e ials. In his pu sui , Nea Edge X- ay
Abso p ion Fine S uc u e (NEXAFS) spec oscopy was employed as a powe ul ool o
elucida e he in ica e de ails o polyme elec onic s uc u es. The unique ad an age o
u ilizing synch o on adia ion as he X- ay sou ce u he enhances he p ecision and
sensi i i y o NEXAFS, o e ing unp eceden ed insigh s in o he o ien a ion o polyme
chains.
NEXAFS is based on he p inciple ha X- ays inciden on a sample can be
abso bed by co e-le el elec ons, causing hem o ansi ion o unoccupied s a es. Nea
he abso p ion edges o speci ic elemen s, such as ca bon o ni ogen, he abso p ion
spec um exhibi s ine s uc u es ha a e sensi i e o he local elec onic and molecula
en i onmen . The o ien a ion o polyme chains can be in e ed by exploi ing he
pola iza ion dependence o NEXAFS. The abso p ion c oss-sec ion is sensi i e o he
o ien a ion o he abso bing molecule wi h espec o he pola iza ion ec o o he
inciden X- ays.
Analysis o he NEXAFS spec a in ol es compa ing he in ensi ies and shapes o
spec al ea u es o di e en pola iza ion di ec ions. This in o ma ion can be used o
deduce he a e age o ien a ion o he polyme chains in he sample.
35
"La ciencia y la ecnología e olucionan
nues as idas, pe o la memo ia, la
adición y el mi o nos ag upan como se es
humanos."
Michael C ich on

37
3) Using he i eous phase o
un a el he mo phology in
bulk he e ojunc ions
3.1) Summa y
O ganic sola cells a e he u u e o sus ainable and en i onmen al iendly ene gy.
The s udy o how is he beha io o he ac i e laye (Bulk e e ojunc ion) is key o
imp o e his echnology. Thanks o he Flash DS , X- ay sca e ing and o he echniques
is possible o unde s and i .
The s udy o he mix u e o PBDBT- l (dono ) and ITI -Th1 (accep o ) is used o
his wo k. Thanks o he p e ious wo k o Liang e al he be e concen a ion o he
mix u e is 50:50 %w wi h a sol en annealing. Wi h his knowledge and s udying he
i eous phase o he mix u e, he p opo ion be ween he mixed phase and he single
componen phase can be de e mined in he same de elopmen condi ions o he eal
sola cell.
39
3.2) In oduc ion
The ene gy consump ion in he wo ld is inc easing exponen ially in he las
decades. The pe oleum ese es a e no in ini e and, nowadays, nuclea ene gy has he
po en ial o be he bes op ion bu om he poin o iew o he popula ion i is e y
dange ous. Due o hese handicaps, enewable ene gies a e aking he lead. The
enewable ene gies a e aken om he wind, he sunligh , he biomass, he mo emen
o he wa e and he geo he mal hea 56.
Focusing on he sun’s ene gy, he e exis h ee ways o ex ac ene gy. ea ing a
luid o boil i and p oduce ene gy wi h a u bine, hea ing wa e o some spaces like a
pool o a es au an and di ec ly con e he sola ene gy in o elec ici y57.
To ex ac elec ici y om he sun is necessa y o ha e a ma e ial o ma e ials ha
a e able o abso b he ene gy o he sunligh and gene a e ee cha ge ca ie s (elec ons
and holes). This mechanism is called he pho o ol aic e ec . When he pho ons o he
sunligh a i e a he sola panel a e abso bed by he a oms o he semiconduc o
ma e ial. I he ene gy o he pho ons is enough, an elec on o he a om can “jump” om
he balance band o he conduc ion band and become ee om hei a om. The eleased
elec ons mo e h ough he semiconduc o ma e ial owa ds an elec ode, c ea ing an
elec ic cu en 585960.
The e a e se e al ypes o sola cells depending on he ma e ials and he
deposi ion o he ac i e ma e ial echniques. The mos common a e pe o ski e sola
cells, silicon sola cells and o ganic sola cells61.
As o o ganic sola cells, hey could no be iable wi hou he disco e y o Alan
Heege in he 1980s who la e ecei ed he Nobel P ize in Chemis y o his wo k62. The
i s iable o ganic sola cells o o ganic pho o ol aics (OPVs) consis on a single laye
o o ganic ma e ial be ween wo elec odes. In he nex decade mo e complex s uc u es
s a ed o de elop like mul i-laye o andem bu wi hou good esul s. Since 2000, he
combina ion o imp o ed ma e ials (polyme s and ulle ene o non- ulle ene accep o s),
40
de ice a chi ec u es and unde s anding he undamen al physics o hem had imp o ed
signi ican ly hei e iciency.
The sola cells ha a e being s udied a e p ima ily composed o wo main
ma e ials. A dono ha “ epels” elec ons and an accep o ha a ac s elec ons. These
wo ma e ials a e ypically blended, o ming a so-called bulk he e ojunc ion (BHJ)
mo phology., so ha he blended ma e ial con ains h ee well-de ined egions: dono
domains, accep o domains and in e mix ace be ween bo h whe e he cha ge sepa a ion
occu s.
Nowadays, o ganic sola cells con inue ha ing less e iciency han silicon ones bu
hey ha e he po en ial o de h one hem hanks o he easie and cheape manu ac u e.
This makes hem ideal o la ge-scale applica ions educing a lo he ene gy consump ion
in he p ocess o de elop hem. Also, hey a e ligh e and, hanks o hei lexibili y, hey
can be in eg a ed in o a wide ange o applica ions like clo hing, building ma e ials o
po able elec onics. They need o imp o e hei li espan because hey lose p ope ies
when he ime exposu e is oo long o in some en i onmen s.
One o he mos auspicious ad an ages is he uneabili y o he ma e ials. They
can be chemically o physically al e ed o ha e speci ic p ope ies. The abso p ion
spec a o he ma e ials can be modi ied by selec ing he ligh wa eleng hs depending
on he coun y o egion, he season o he hings ha a e below i . Fo example, i you
wan o ha e a sola cell in he ceiling ( anspa en o semi anspa en ) o a g eenhouse
and you a e plan ing le uces, you can make a de ice ha abso bs in a ange o sola
ligh bu a oiding he wa eleng hs ha he le uce needs o g ow63.
O ganic sola cells ha e he po en ial o be a key echnology in he ansi ion o a
low-ca bon economy. They use a clean and enewable ene gy sou ce and can be cheap
and easily p ocessable. Wi h hei anspa ency and lexibili y hey can be used, no only
on he op o buildings o sola a ms, bu also in a eas whe e i was p e iously impossible
such as windows, g eenhouses, o i egula su aces among o he s.

41
O cou se, he e a e a lo o a iables o ha e in o accoun . The angle o incidence
o he sunligh , he esis ance o he ma e ials, he joule e ec , e c. This wo k is ocused
on how he mic os uc u e o he bulk he e ojunc ion a ec s he pho o ol aic p ope ies.
3.2.1) E olu ion o dono s
As was men ioned in he in oduc ion o he hesis, he adi ional conjuga ed
polyme s a e homopolyme s composed by only one epea ing uni . In he 70s
polyace ylene was disco e ed.
A e wa d, in he 80s, hanks o he inco po a ion o ing s uc u es in he backbone,
2D s uc u es, mo e s able and be e soluble polyme s han he p ecu so s
polyace ylene-based could be made. This is he case o a ew speci ic s uc u al polyme
amilies such as poly luo enes, polyphenylenes o poly hiophenes like well-s udied P3HT
(poly(3-hexyl hiophene-2,5-diyl))646566. These new ma e ials allowed o be e con ol
o e he polyme 's elec onic p ope ies, esul ing in high e iciencies in o ganic sola
cells.
In he nex decade, he dono -accep o o push-pull polyme s we e de eloped. As
i was b ie ly explained in he in oduc ion, his ype o polyme s is composed by wo
di e en s uc u es al e na ed so i is possible o say ha he monome is made by wo
componen s blended. One compound is elec on- ich ying o ca ch an elec on. They
usually ha e a high concen a ion o elec on-dona ing g oups such as ni ogen o sul u
o inc ease hei mobili y and elec on densi y. The o he compound is he opposi e,
elec on-poo ha dec eases he elec on mobili y hanks o elec on-wi hd awing g oups
like ca bonyl67. These new polyme s eme ged as he mos p omising ma e ials in he
ield o OLEDs and OPVs since he 90s o nowadays.
The mos used polyme o sola cells ac ually is he PBDB-T. The poly[(2,6-(4,8-
bis(5-(2-e hylhexyl) hiophen-2-yl)benzo[1,2-b:4,5-b']di hiophene))-al -(5,5-(1',3'-di-2-
hienyl-5',7'-bis(2-e hylhexyl)benzo[1',2'-c:4',5'-c']di hiophene-4,8-dione))] was i s
epo ed in 2012 by Qian e al and an e a in he polyme sola cells s a ed hanks o i
and i de i a es68. PBDBT has a lo o names bu he mos known one is PCE12. This
42
ma e ial has a high powe con e sion e iciency (PCE) due o i s b oad abso p ion
spec um, high cha ge ca ie mobili y, and good mo phological s abili y. The de i a es
consis on add a oms o he p incipal s uc u e o imp o e i s p ope ies as he PBDBT-
Cl, PBDBT-2F, e c.
Figu e 18 a) P3HT molecula s uc u e and b) PBDBT.
Ac ually, he ongoing esea ch has ocused on de eloping new conjuga ed
polyme s wi h highe p ocessabili y, s abili y and solubili y o be a p omising i al in he
sola ene gy ca ee .
In summa y, while homopolyme s a e composed o iden ical epea ing uni s, push-
pull polyme s ha e a mo e complex chemical s uc u e wi h bo h elec on-dona ing and
elec on-wi hd awing g oups. This s uc u e leads o imp o ed cha ge ans e and
b oade abso p ion spec a, esul ing in highe e iciency and pe o mance o o ganic
sola cells.
a)
b)
43
3.2.2) E olu ion o accep o s
The i s accep o s de eloped o OPVs consis on ph halocyanines and pe ylenes.
C ea ed in he 70s, hese o ganic dyes con e ed low e iciencies due o hei limi ed
abso p ion and elec on mobili y. Du ing he 90s he pe ylene diimide (PDI) was
syn hesized as a be e accep o 69 and, du ing he 2000s, PDI de i a es ob ained be e
and s ong abso p ion in he sunligh ange and upg aded he hole mobili y.
I was no un il 2002 ha ulle ene de i a i es we e de eloped. These s uc u es
composed by ca bons o e excellen compa ibili y wi h conjuga ed polyme s esul ing in
a good powe con e sion wi h a ela i ely good e iciency. The incon eniences a e he
ela i ely low hole mobili y compa ed wi h he conjuga ed polyme s, he agg ega ion, low
solubili y and he limi ed ange o abso p ion70. The mos impo an ulle ene accep o s
a e [6,6]-phenyl-C61-bu y ic acid me hyl es e (PCBM), [6,6]-phenyl-C71-bu y ic acid
me hyl es e (PCBM70) o [6,6]-phenyl-C61-bu y ic acid bu yl es e (PCBB) be ween
o he s.
In 2009 he non- ulle ene accep o s (NFAs) began o be explo ed owing o he
limi ed sunligh abso p ion ange. These accep o s consis on small molecules
syn hesized and designed wi h p ecise con ol o e hei p ope ies71. The pionee ing
we e he quinolines and diimide de i a es (mo e complex). In 2012 he de elopmen o
used- ing elec on accep o s (FREAs) inco po a ing mo e elec on-de icien a oma ic
ings in he co e like used hiophene o benzo hiadiazole ma ked a b eak h ough. The
mos impo an p oblem is he agg ega ion, bu , changing hei chemis y o s uc u e, i
is possible o une he abso p ion ange and he ene gy le els main aining he high
mobili y and s abili y72.
3 yea s la e , in 2015, Zhang e al syn hesized he miles one o he NFA. The
indacenodi hieno[3,2-b] hiophene o ITIC73. The co e s uc u e o ITIC is o med by
using wo hiophene ings o an indacene co e con e ing a plana and igid s uc u e. I
is a push-pull accep o wi h a dono pa be ween wo accep o pa s. Also, he elec on
mobili y and he cha ge sepa a ion inc ease hanks o he sul u a om o he hiophene
and he used ing. A wide ange o de i a i es is ob ained by changing he side chains
44
o subs i uen s ha a e a ached o he co e s uc u e. Some de i a es we e de eloped
by he in oduc ion o an elec on- ich g oup like me hyl in o he end-capping uni s (ITIC-
M)74, by he inco po a ion o elec on-de icien a oms such as luo ine (ITIC-2F)75 o
chlo ine (ITIC-2Cl)76 o by he subs i u ion o he phenyl uni s by hienyl g oups (ITIC-
Th)77. Ano he p omising ype o small molecules in his ield we e he accep o -accep o
(A-A) ype polyme s like poly[N,N′-bis(2-oc yldodecyl)-naph halene-1,4,5,8-
bis(dica boximide)-2,6-diyl]-al -5,5′-(2,2′-bi hiophene) (P(NDI2OD-T2)787980 and i s
de i a es.
In he las yea s o he 2010s, Y6 o ITIC-4F (a de i a e o he ITIC) inc ease he
PCE up o 13% (combined wi h a dono polyme ) consolida ing he NFA as a iable
al e na i e agains he ulle ene accep o s8182. O-IDTBR o IDIC we e de eloped also.
Figu e 19 Chemical s uc u es o he mos impo an small molecules: a) PCBM, b) PDI, c) ITIC and d) Y6.
Nowadays, in his decade, he endency is o con inue wi h he ITIC de i a es
de eloping new small molecules mo e symme ic as N3 (de i a e o he Y6) o example.
a)
b)
d)
c)
51
is possible o ex apola e a calib a ion cu e o know he Tg o one unknown in e mix
composi ion bu knowing i s Tg.
By he isoch onous annealing me hod, i was impossible o de e mine he Tg o he
in e mix phase due o he o e lap o he cold c ys alliza ion on he hea ing amp o he
small molecule and he ageing o e shoo o en halpy eco e y o he PDCBT-Cl. This
issue can be clea ly seen in he Figu e 24. I can be obse ed also how in his 75:25 chip
o polyme and small molecule espec i ely a he annealing o 70 o 80 Celsius o
example, he c ys alliza ion and he peak due o he physical ageing a e supe posed.
Fo his eason, he modula ed me hod has been used. Wi h he empe a u e
modula ed DSC, he non- e e sible p ocesses, such as cold c ys alliza ion, a e idded.
All he sys ems we e s udied by his me hod o main ain he same c i e ia wi h all he
samples.
Figu e 25 Tempe a u e modula ed DSC o all he sys ems (a) and hei de i a es (b).
To es ima e he Tg o he in e mix phase in all he measu emen s, 10 Hz we e used
in he expe imen s.
-50 0 50 100 150 200 250 300
TMDSC
CP e (a.u.)
Tempe a u e (ºC)
PDCBT-Cl 10 Hz
75:25 10Hz
50:50 10Hz
25:75 20Hz
ITIC-Th1 10Hz
020 40 60 80 100 120 140 160 180 200 220 240
De i a e od he TMDSC expe imen s
d(Cp e )/dT(a.u.)
Tempe a u e (ºC)
PDCBT-Cl 10Hz
75:25 10Hz
50:50 10Hz
25:75 10Hz
ITIC-Th1 10Hz
a)
b)

52
A e he Fou ie - ans o m o he da a, i is mo e isible ha he cold c ys alliza ion
is dele ed and can be clea ly he glass ansi ion and he mel ing o he nea ma e ials.
To ha e a common c i e ium wi h all he esul s, he 1s de i a e was de elop. The
maximum o he peak o he de i a e in he egion co esponds wi h he Tg. To no make
mis akes, he peak was i ed o a Gaussian unc ion and ex ac ed he maximum.
In ui i ely, in he panel b o he Figu e 25, a clea obse a ion eme ges: he Tg o
he in e mix phase is displaced om he Tg o he polyme o he Tg o he small molecule
when he weigh pe cen age o he las one is inc eased. I is app ecia ed also he mel ing
o he wo nea ma e ials, making su e ha he measu emen s a e well done. In he nex
igu e, i can be obse ed a able wi h he ex ac ed Tgs om de modula ed expe imen s
and hei i ing o a Go don-Taylo equa ion o ha e a calib a ion cu e o he sys em
PDCBT-Cl:ITIC-Th1.
% w PDCBT-Cl:ITIC-Th1
Tg (°C)
1:0 (PDCBT-Cl)
73
75:25
87
50:50
105
25:75
122
0:1 (ITIC-Th1)
140
Figu e 9b shows ha he expe imen al da a can be adequa ely i ed o he Go don-
Taylo equa ion. Once he calib a ion cu e is done, he sola cell wi h he bes elec onic
p ope ies can be s udied. To s udy he sola cell a hin ilm o 50:50 % in weigh was
deposi ed in a silicon wa e wi h he condi ions o Liang e al. Immedia ely, a sol en
annealing in CS2 a oom empe a u e 2 minu es. The Tg o his sys em only can be
measu ed in he i s hea ing because he SA con e s o he sola cell be e p ope ies.
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
70
80
90
100
110
120
130
140
150 Calib a ion cu e
Tg (ºC)
% w o ITIC-Th1
Model Go don-Taylo
Equa ion (x*T1)+(K*(1-x)*T2)/x+(K*(1-x))
T1 140.18653 ± 0.87813
T2 72.55195 ± 0.85846
K1.12155 ± 0.06563
Figu e 26 Tgs o he di e en in e mix phases and Go don-Taylo i calib a ion.
53
I we use he second hea ing o ex ac he Tg he he mal his o y o he sys em was
dele ed so we a e no seeing he eal Tg. Fo ha , he hin ilm was deposi ed in a silicon
wa e . Ha ing his, we a e able o sc a ch his ilm and ake a small pa o measu e. We
can ake many samples om he same ilm o measu e many i s hea ings o he same
sample.
Figu e 27 Tg o he sola cell imp o ed by Liang e al. and he ex ac ed composi ion o i .
This esul show how, wi h he sol en annealing, he pe cen age in weigh o he
small molecule in he in e mixed domains dec eases conside ably o 37.5 %. This can
be a ionalized in e ms o mig a ion o he ITIC-Th1 om he in e mixed phase o a
composi ionally pu e phases, o example in o he c ys alline domains.
Cp e
050 100 150 200 250 300
d(cp e )/dT
Tempe a u e (ºC)
96
0.0 0.2 0.4 0.6 0.8 1.0
70
80
90
100
110
120
130
140
37.5
Tg (ºC)
% w o ITIC-Th1
96
54
Figu e 28 GIWAXS pa e ns o 50:50 %w o PDCBT-Cl:ITIC-Th1 wi hou (a) and wi h (b) sol en annealing
o 2 minu es.
Indeed, in he Figu e 28 i can be obse ed how he sol en annealing imp o e he
c ys alliza ion o he small molecule con e ing o he sys em mo e PDCBT-Cl in he
in e mix phase. This is cong uen wi h he esul s o he lash DSC because he Tg is
lowe han in he case 50:50 wi hou sol en annealing.
To see he mo phology he AFM echnique was used. An image o he bes sys em
was analyzed o see he domains. In he phase image o he AFM i is clea ha he e
a e sepa a ed domains and be ween hem a isible bounda y we e he in e mix phase is
loca ed. The domain size is app oxima ely 85 nm o diame e and i was measu e by
image J so wa e.
a)
b)
55
Figu e 29 Heigh and phase AFM images o 50:50 wi h sol en annealing hin ilm.
To suppo he AFM images a small GISAXS s udy was ca ied on. The mix u es
ha e mo e sca e ing han he nea ma e ials due o he highe elec onic con as in he
ilm. When he ilm does no ha e sol en annealing, he domains ha e a plane disc
shape wi h 30 nm o adius app oxima ely. Then, a e he SA, he domains inc ease hei
size o 45 nm o adius and he discs swell un il hey acqui e he shape o a ac al sphe e.
a)
b)
c)
d)
56
Figu e 30 GISAXS in eg a ions o he Yoneda peak o a) di e en sys ems and b) he hin ilm 50:50 wi h
and wi hou sol en annealing.
Knowing he s uc u e, i is impo an o check he op ical p ope ies. Fo his, he
UV-Vis abso p ion o he sys em was analyzed. In he nex igu e, i is shown how wi h
he 50:50 mechanical mix u e is ob ained he highes ange o abso p ion o he ligh in
all he ange be ween he nea ma e ials. In addi ion, wi h he sol en annealing, i is
demons a ed ha he abso p ion ange is inc easing a li le bi inc easing also he o al
a ea o he ligh abso p ion bu dec easing he maximum o abso p ion.
Figu e 31 UV-Vis spec a o all he sys em.
0.1 1
1E8
1E9
1E10
In ensi y
q (nm-1)
PDCBT-Cl
7525
5050
2575
ITIC-Th1
0.1 1
1E8
1E9
1E10
In ensi y
q (nm-1)
No SA
SA 2 min
350 400 450 500 550 600 650 700 750 800 850 900
In ensi y no malized
Wa eleng h (nm)
PDCBT-Cl
75:25
50:50
25:75
ITIC-Th1
350 400 450 500 550 600 650 700 750 800 850 900
In ensi y no malized
Wa eleng h (nm)
50:50
50:50 SA 2min
a)
b)

57
Figu e 32 Ex e nal quan um e iciency o he e e ence sola cell.
Finally, in he Figu e 32 we can obse e ha i has he same shape o he
abso p ion spec a. This indica es ha he elec onic cu en gene a ed is along all he
abso p ion o he pho ons co obo a ing he good sola cell p ope ies.
3.4) onclusions
In summa y, he u iliza ion o he TMDSC (The mal Modula ed Di e en ial
Scanning Calo ime y) has enabled p ecise ep oduc ion and composi ional analysis o
sola cells. By ai h ully eplica ing he sola cell using a lash DSC chip, we can
in es iga e he mo phology o he eal ac i e laye h ough calo ime y.
An in iguing inding is ha he In e mix phase o he sola cell, when combined
wi h he SA (Sol en Annealing) p ocess, de ia es om he 50:50 composi ion expec ed
om he p ecu so solu ion. Ins ead, i comp ises 37.5% o he weigh o ITIC-Th1,
a ibu ed o i s a o able c ys alliza ion beha io du ing sol en annealing.
300 400 500 600 700 800 900
0
10
20
30
40
50
60
70
80
90
100
EQE (%)
Wa eleng h (nm)
58
Addi ionally, he examina ion o he i eous phase allows o a de ailed analysis o
he sola cell's composi ion. This comp ehensi e app oach sheds ligh on he in ica e
aspec s o sola cell s uc u e and beha io , p o iding aluable insigh s o u he
ad ancemen s in sola echnology.
59
"El descub imien o consis e en e lo que
odos han is o y en pensa lo que nadie
más ha pensado."
Albe Szen -Gyö gyi
67
pa adigm (much o de , be e p ope ies) exhibi ing high mobili y while lacking o
c ys alline-like long ange o de 109–116. IDTBT is a push pull polyme composed by
indacenodi hiophene and benzo hiadiazole. I s backbone has a e y low o sion angle
con e ing i a igid and plana s uc u e115117. These cha ac e is ics gi e o he polyme
a low diso de s uc u e bu no c ys alline. Also, in he ee ca bon o he hiophene
g oups, alipha ic chains a e loca ed o gi e solubili y o he sys em.
Figu e 35 IDTBT chemical s uc u e.
In summa y, he FETs ha e e olu ionized mode n elec onic. Thei low powe
consump ion, ease o in eg a ion and p ecise con ol o he cu en make hem an
in aluable ool o new complex in eg a ed ci cui s. The abili y o manu ac u e he o ganic
ac i e laye on lexible and anspa en subs a es using low- empe a u e deposi ion
echniques open he doo o new eme ging applica ions.
The objec i e o his pa o he wo k is o unde s and he he mal beha io
o he IDTBT amily o de e mine why is one o he bes o ganic ma e ials o
ansis o s and is called amo phous.
4.3) Resul s and discussion
In his chap e he IDTBT and de i a es we e s udied. An exhaus i e analysis o
he IDTBT ( wo di e en molecula weigh s) was made and a supe icial one o he

68
de i a es. A e se e al expe imen s, he dichlo obenzene was decided as he bes
sol en o made ilms.
One o he mos impo an esul s is ha he mobili y does no change wi h he
he mal ea men s gi en o he ansis o s. Fo he he mal ea men o he ansis o , i
is impo an o say ha i was made when he ac i e laye (IDTBT in his case) is on he
op. Then, a e he ea men , he insula o laye and he op ga e was g own so he
annealing was made wi h he same condi ions o he samples o he o he echniques.
Figu e 36 Mobili y da a o he IDTBT ansis o s.
The cha ge ca ie mobili y alues a e mo e o less he same in each sample. The
small di e ences migh be associa ed wi h changes in he ideali y o he I-V cu es, which
do no seem o be mic os uc u e- ela ed. I he e a e changes in he mobili y due o he
annealings, he esul s a e shielded by he in insic e o ela ed o he ex ac ion o
pa ame e s om he I-V cu es o ansis o s.
RT
100 °C
140 °C
200 °C
260 °C
300 °C
1
2
m
sa (cm2/Vs)
Annealing
empe a u e
(º )
Mobili y
sa u a ion
(cm2/Vs)
S anda d
de ia ion
RT
1.17674528
0.07222518
100
1.21399166
0.21989346
140
1.21949628
0.35537115
200
1.22493352
0.19324101
260
1.19403097
0.33225271
300
1.23069779
0.23940238
69
Figu e 37 I-V da a IDTBT ansis o s.
In o de o unde s and he elec ical beha io , i is impo an o know i he e a e
changes on he solid-s a e mic os uc u e.
On he as cas GIWAXS pa e n o he IDTBT hey a e obse ed essen ially h ee
di ac ion peaks. One hick in he ou o plane (010) a q = 14 nm-1 ela ed wi h he
s acking o he π-π bonds o π-π s acking and he e ec ion in he in plane (001) due o
he pe iodici y o he backbone o he polyme . I is cu ious ha he IDTBT does no ha e
he ypical ou o plane e ec ion (100). This means ha i does no ha e pe iodic
al e na ion o alipha ic and a oma ic egions con a y o wha usually happens wi h
conjuga ed polyme s.
The molecula o ien a ion was also measu ed by NEXAFS showing less ene gy
peaks on he π-π* bonds. This means ha he chains a e p e e ably ho izon al, al hough
he e is a small p opo ion o chains in a e ical o ien a ion, sus aining he GIWAXS
esul s.
-60 -40 -20 0
10-10
10-9
10-8
10-7
10-6
10-5
IDS (A)
VGS (V)
RT
100 ºC
140 ºC
200 ºC
260 ºC
300 ºC
a)
b)
70
Figu e 38 a) GIWAXS pa e n and b) NEXAFS o he IDTBT.
To de e mine he he mo opic beha io , wo di e en empe a u e- esol ed
expe imen s we e aking. In si u aking GIWAXS pa e ns e e y 5 deg ees and ex si u
images (annealings o 10 minu es) e e y 20 deg ees. The da a eco ded was in eg a ed
along he in plane and ou o plane di ec ions as a unc ion o he sca e ing ec o (q).
The s uc u al beha io o his polyme a empe a u es be ween oom empe a u e
and 300 ºC whe e i is o ally mel ed. Inc easing he empe a u e, he polyme acqui es
mo e ene gy so i is able o mo e easily. Thus al e ing he sho - ange molecula o de
and p omo ing he sup amolecula one. In o he wo ds, swi ching o les q he π-π
s acking e lec ion and appea ing he (100). This changeo e can be explained like he
ansi ion om c ys al o liquid c ys al in o he conjuga ed polyme s like PBTTT.
270 280 290 300 310 320 330
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
No malized in ensi y
E (eV)
Ve ical
Ho izon al
285 286 287 288 289 290
71
Figu e 39 In eg a ions o IDTBT in si u expe imen .
The mo opic ma e ials, in he ield o semiconduc o ma e ials, a e semic ys alline
o semipa ac ys alline (pa ially o de ed) in he low- empe a u e egion bu in his case i
happens he opposi e. A low empe a u es i is diso de ed bu , inc easing he
empe a u e, i becomes mo e o de ed un il 260 ºC app oxima ely. The mos a ional
hing o why i becomes mo e o de is he o ma ion o c ys als bu by GIWAXS i is
demons a ed ha no. The e mos accu a e al e na i e is he unde cooled liquid. In his
case, he molecules ends o sel -assemble spon aneously in o a mo e-o -less o de ed
s uc u es. In addi ion, he o de inc ease du ing he hea ing eo ganizing and
compac ing he la ice. Consequen ly, when semiconduc ing polyme s a e hea ed up
(below he o de -diso de ansi ion empe a u e, TO-D) bo h (100) and (010) di ac ion
peaks end o inc ease and/o become na owe . When his empe a u e is su passed,
he s uc u al o de disappea s.
To s udy his we used he pa ame e g118119. In he Figu e 40 is ep esen ed he
e olu ion o his pa ame e in he h ee ep esen a i e e lec ion on he GIWAXS
expe imen s. In he (001) and he π-π s acking e lec ions, he o de inc ease modes ly
510 15 20
300
260
220
180
140
100
60
qZ (nm-1)
20
510 15 20
300
260
220
180
140
100
60
In ensi y
qR (nm-1)
20
510 15 20
Ou - o - plane
qZ (nm-1)
510 15 20
20
60
100
140
180
220
260
300
Tempe a u e (ºC)
In - plane
qR (nm-1)
min max
(001)
(010)
(100)
72
om 150 ºC app oxima ely ha co espond exac ly wi h he o ma ion o a clea (100).
This p ocess means ha he chains a e mo e nea be ween hem and he pe iodici y o
he backbone becomes mo e egula . Also, in he same way, he dec easing o he (100)
g pa ame e wi h he empe a u e indica es he appea ance and a angemen o he
lamella s acking.
Figu e 40 E olu ion o he g pa ame e in he in si u GIWAXS expe imen .
Based on hese indings, a mo e comp ehensi e in es iga ion in o he he mal
cha ac e is ics o his ma e ial is wa an ed, p omp ing he applica ion o Flash DSC.
The i s expe imen was ca ied ou using he isoch onous annealing explained in
he ma e ials and me hod chap e . The ime iso he m ime was 1h each annealing, he
maximum empe a u e 400 Celsius and he minimum -80. All he coolings we e a 4000
K/s o cing he ma e ial o be eeze in he s a e o he ageing. In he nex cha a e
ep esen ed he hea low agains he empe a u e o each ageing ( he hea ing amp jus
a e he ageing and a e e ence).
20 40 60 80 100 120 140 160 180 200 220 240 260 280
10
12
14
16
18
20
22
24
26
28
g pa ame e (%)
Annealing empe a u e (ºC)
p-p
100
001

73
Figu e 41 Isoch onal annealings o 1h om -60 ºC o 180 ºC.
To cla i y he in o ma ion o he Figu e 41, he excess o he hea low (ΔHF) was
ep esen ed e sus he empe a u e. ΔHF was calcula ed sub ac ing he e e ence line
o he measu emen . Wi h his simple ope a ion, any peaks (no nea ze o alues)
e idence calo ime ic ea u es. In his case, IDTBT e eal 3 di e en endo he mic peaks
which means h ee di e en he mal ansi ions27.
The hi d p ocess is easy o de e mine. I is s ange because he endo he mic peak
is loca ed a 10 ºC, e y low empe a u e ha ing in accoun ha he minimum ageing
empe a u e whe e i appea s is 80 ºC. The e o e, his p ocess canno be associa ed
wi h some hing physical ha occu s in he ageing like physical ageing o c ys alliza ion
du ing he annealing. Du ing he cooling i canno be also a c ys alliza ion because he
ma e ial does no ha e enough ime o o de so he peak ( o ejec ion) is he mel ing o
c ys als. In his he mal egion, he IDTBT ies o sel -assemble in o an o de ed s uc u e
composed by laye s o a oma ic and alipha ic nanodomains. Then, he alipha ic egions
a e able o c ys allize. The peak o he p ocess 3 is due o he mel ing o his c ys als.
74
The i s p ocess (blue) is due o he physical ageing o a egion o he IDTBT. I
occu s a -10 Celsius and we hink ha is associa ed o he Tg o he la e al chains. We
a e no able o link his ansi ion wi h he la e al chains bu obse ing he shape, he
posi ion and he beha io we can say ha i is a i eous ansi ion. We can disca d he
deg ada ion and he mel ing o c ys als due o he low empe a u es and he shape o
he endo he mic peak.
The second p ocess is he mos in ica ed one. I encompasses a e y wide ange
o empe a u e so is impo an o explain p ope ly his. I is impo an also o ma k ha
appea s abo e wha we associa e as he Tg o he la e al chains. When his Tg is
exceeded, he sys em s a s o gain mobili y. I could lead in h ee di e en easons: a
mel ing o he o de ed domains in he sys em, s uc u al elaxa ion o he glassy phase
o a ansi ion om liquid c ys al o iso opic liquid. The liquid-liquid ansi ions he
endo he mic peak is no shi ed so much so his heo y can be disca ded. Also, he
appea ance o he peak a an annealing a 20 Celsius s a s a 60 deg ees and, isually,
a oom empe a u e he ma e ial seems solid. As i his we e no enough, a his
annealing empe a u e, he π-π s acking begins o de e io a e in he GIWAXS analysis.
I is in e ed ha his dis up ion is associa ed wi h he diso de o in e molecula
agg ega es cha ac e ized by a limi ed sho - ange o de . This ansi ion is e y b oad
sugges ing a e y big he e ogenei y due o he la ge ange in which his p ocess appea .
I is also ag eed wi h he (100) GIWAXS peak. I is isible un il oom empe a u e (when
he p ocess 2 in Flash DSC s a s o con ibu e) bu s a s o acqui e impo ance a 140
Celsius app oxima ely and disappea a he same empe a u e in bo h echniques
( empe a u e o de -diso de o TO-D = 260 ºC) when he domains become diso de ed.
75
Figu e 42 In eg a ion o he ΔHs alues and ex apola ion o he he mal ansi ions.
Las o his, he hi d p ocess seems o be ela ed wi h he side chains only. I is
in e es ing because he o e shoo appea s when he ageing empe a u e is abo e 80
deg ees bu he peak is loca ed a 10 deg ees app oxima ely. A his empe a u e, he
(100) peak in he GIWAXS s a s o ake impo ance. Tha means ha in his he mal
egion he backbone and he alkyl chains o he IDTBT inc eases i s o de in o a laye ed
s uc u e. When he nanodomains a e o med, maybe he linea chains can c ys allize o
physically aged du ing he cooling s ep. I is possible because his endo he mic peak
disappea s when he ma e ial does no exhibi mo e peaks (in he es o he ageings)
and no be o e.
The p ocess 2 explained be o e is only a heo y. This expe imen does no b ing
ligh o cla i y o ally his. I is no clea i his p ocess is due o he mel ing-like ansi ion
o he o de ed egions o i i is ela ed wi h he glass ansi ion. To disclose his pa adigm,
a sequence o 2 o 3 consecu i e iso he mal s eps in an ascending o a descending way
we e de eloped.
76
Figu e 43 Descending (a) and ascending (b) isoch onal annealings.
The physical ageing was inally disca ded because in he ascending sequence
wi h he annealings a 20 and 100 Celsius and he annealing a 100 does no ha e he
same esul . I his p ocess we e due o physical ageing, he annealing a 100 a e he
annealing a 20 should dele e he he mal his o y gene a e by he less empe a u e
ageing. Fu he mo e, when 100 and 20 deg ees o annealing a e done, h ee peaks
appea due o he h ee p ocesses bu i he same sequence is done in ascending o de
only he peaks a 20 and 200 ºC app oxima ely pop up. This implies ha , when he e
was an annealing a 100 Celsius, i e ec i ely e ases he he mal changes ha occu ed
du ing he p io iso he mal ea men a 20 ºC. Howe e , when he o de is e e sed, he
annealing p ocess a 20 ºC induces u he modi ica ions in he ma e ial, esul ing in he
appea ance o an addi ional peak.
This disc epancy be ween he esul s om ascending and descending sequences
explain he compa ibili y wi h he o de ed egions heo y. When he e is an annealing o
100 p eceded by ano he o 20, he mel ing empe a u e inc ease due o he imp o e o
he g ow h and a anged o he o de ed egions. Con e sely, when he 100 ºC is ollowed
by he 20 ºC annealing, wi h he i s s ep o de ed egions a e c ea ed ha mel a 200
ºC app ox. Du ing he subsequen annealing a 20 ºC, hese c ys alli es o med a 100
ºC emain unal e ed, main aining hei mel ing poin a a ound 200 ºC due o hei
o igina ion unde mo e he modynamically a o able condi ions. Howe e , i 's impo an
a)
b)
83
5) Glassy Phase Enginee ing
o Tunning
Pho oluminescence in PFO
5.1) Summa y
The chap e analyzes i eous polyme s' he modynamic s a e, ocusing on he
concep o ic i e empe a u e (T ). Poly(9,9-di-n-oc yl luo enyl-2,7-diyl) (PFO) is
sc u inized, e ealing c ucial insigh s in o i s glassy beha io connec ed o op oelec onic
p ope ies. I is es ablished ha he con ol o T is key (like c ys allini y) in shaping he
op oelec onic p ope ies o semiconduc ing polyme s.

85
5.2) In oduc ion
Ligh emission and de ec ion a e impo an miles ones o scien is s, aiming o
unde s and how o make e icien emi e s and pho ode ec o s. They ca ch
en i onmen al ligh and ans o m i , hanks o he cones and ods, in o elec ici y and an
image is in e p e ed by he b ain. Nowadays, a wide quan i y o di e en senso s is
de eloped o co e an ex ensi e wa eleng h ange.
This ype o senso s is used in di e se applica ions, om measu ing he ligh
adia ion in he dese o adjus he ime exposu e in a came a. Also, hey a e impo an
in mic oscopy and as onomic obse a ions bu he mos impo an one is he da a
ansmission. To use ligh pulses ( as e ) han elec ic pulses o send in o ma ion.
In ecen decades, echnological ad ances ha e led o signi ican inno a ion in he
ield o ligh senso s, pa icula ly in he de elopmen o o ganic ligh senso s (OLD).
These new ma e ials based on o ganic ma e ials ha e p o ided signi ican ad an ages
in e ms o lexibili y, p oduc ion cos s, and ene gy e iciency.
5.2.1) O ganic ligh senso s
The o ganic ligh senso s (OSD) a e one o he mos inno a i e ma e ials in he
ield o ligh de ec ion and op ic p ope ies. Modi ica ions on he conjuga ed polyme s o
small molecules p ope ies a e used o de ec ligh changes in he en i onmen . They
ha e also high sensi i i y and a e y wide ange in he ligh spec um ac ing om UV o
nea in a ed wa eleng hs. This makes hem an a ac i e op ion o applica ions such
as digi al came as, ligh ing con ol sys ems, medical de ices o mo ion senso s.
The ligh de ec ion p ocess o hese senso s is almos he same as he wo k o
each componen in an o ganic sola cell. Fi s ly, he ligh ha is going o be de ec ed hi s
he OSD. Then, he ene gy o he pho ons is abso bed and, i his is enough, an elec on
o he ma e ial is exci ed and jumps o a high ene gy s a e le el. When elec ons ha e
ene gy in excess, hey can e u n o he basal ene gy and emi ligh wi h ano he
86
wa eleng h o sepa a e om he a om and mo e eely. In he la e case, hey can be
collec ed (applying a po en ial o help hem o mo e) and used o ex ac elec ical cu en
o be ecombined wi h a hole and also emi he ene gy.
Wi h espec o ino ganic senso s, OSD p esen he ad an age o being lexible
and ligh , he e o e exhibi ing he possibili y o being in eg a ed in clo hes o bandages.
Changing he chemical s uc u e, hey a e able o sweep a b oad spec um o
wa eleng hs, hus p o iding speci ic senso s o pa icula pu poses. Fu he mo e, hei
e iciency is e y high, i means ha almos all he pho ons ha all in o he senso a e
abso bed by he OSD. Las bu no leas , one o he mos impo an ad an ages is hei
scalabili y. No mally, he way o p oduce hem is by solu ion cas ing on a subs a e. By
his me hod, la ge quan i ies o OSD can be made wi h low cos s and in a sus ainable
way.
In con as , he e a e some obs acles ha need o be o e come. The i s one is
he compe i i eness wi h adi ional semiconduc o s based on he silicon echnology.
They a e e y well es ablished in he ma ke and he whole niche cu en ly is co e ed by
hem. Rela ed o i , hey mus ul ill some s anda ds and egula ions ha nowadays a e
se up o con en ional ino ganic semiconduc o s.
To be compe i i e wi h he ac ual senso s, OLDs ha e o imp o e hei quan um
e iciency and, mo e impo an ly, hei s abili y and du abili y. These ma e ials should be
e y sensi i e o he humidi y because he wa e ac s as amps o he hole and
elec ons. Also, hey ha e o o e come hei esis ance o he oxida ion, sha p
empe a u e changes… All o hese ac o s can a ec hei s abili y, du abili y and,
he e o e, hei usabili y.
These ma e ials ind hei mos c ucial applica ions in he ealm o o ganic ligh -
emi ing diodes (OLEDs) o image- ela ed de ices. In he ma ke , we can wi ness a
p oli e a ion o ele isions and sma phones equipped wi h OLED sc eens, p ima ily due
o hei excep ional abili y o deli e deep blacks and high- esolu ion displays. Mo eo e ,
he adap abili y o hese ma e ials has gi en ise o lexible sc eens and senso s o
digi al came as, con ibu ing o hei widesp ead adop ion.
87
Ano he signi ican applica ion a ea is he domain o da a ansmission ia op ical
ibe , whe e hese ma e ials shine due o hei high e iciency and cos -e ec i eness,
making hem ideal o add essing a wide ange o bandwid h equi emen s. Beyond his,
hey play a pi o al ole in p oximi y and ges u e/mo emen ecogni ion echnologies,
enhancing use in e aces and in e ac ion wi h a ious de ices.
In he con ex o image- ela ed de ices, hese ma e ials ex end hei impo ance o
he ield o biomedical de ec ion, se ing as nea -in a ed (NIR) de ec o s o he analysis
o issues and he diagnosis o diseases. This di e se ange o applica ions unde sco es
he e sa ili y and signi icance o hese ma e ials in ou mode n echnological landscape.
No mally, he uning o he p incipal cha ac e is ic o OLDs a e achie ed by wo
main s a egies, ha a e he de elopmen o new ma e ials by changing he chemical
s uc u e and by changing he c ys alline s uc u e. Howe e , he glassy phase is also
eme ging c ucial o une ma e ial pe o mance. This wo k will be ocused speci ically on
he cha ac e iza ion o he glass he modynamic s a e ia he ic i e empe a u e, whose
de ini ion will be in oduced in he nex subsec ion.
5.2.2) Fic i e empe a u e
The ic i e empe a u e (T ), o iginally o mula ed by Tool120 and associa ed wi h
he ' ozen-in' liquid s uc u e in he glassy s a e, se es as a concep ual ool o
cha ac e izing he non-equilib ium s a e o a glass p e iously cooled om i s high-
empe a u e, mol en s a e121. T is de ined as he empe a u e a which a glass wi h gi en
he modynamic s a e would be a equilib ium. Hence, T quan i ies he ex en o de ia ion
om equilib ium ha pe sis s in he glassy s a e122. I he glass has eached equilib ium,
i s T is iden ical o he ac ual empe a u e.
Gi en i s de ini ion, T is iden i ied as he poin whe e he glass line in e sec s he
ex apola ed equilib ium line a a speci ic en halpy. In calo ime ic measu emen s, whe e
he i s de i a i e o he en halpy is cha ac e ized, T is ypically de i ed om hea low
cu es du ing a hea ing scan a e cooling. When employing iden ical hea ing and cooling
a es, wi h he hea ing scan immedia ely ollowing he cooling scan, he esul ing T is
88
e e ed o as he limi ing ic i e empe a u e, deno ed as T ′123. The ic i e empe a u e
(T ) is gene ally de e mined by using Moynihan’s me hod124. This de ines T as he
empe a u e a which he a ea o he aged sample and ha o he unaged sample a e
he same. The equa ion is he nex :
∫(𝐶𝑝𝑙−𝐶𝑝𝑔)𝑑𝑇= ∫ (𝐶𝑝−𝐶𝑝𝑔)𝑑𝑇
𝑇>𝑇𝑔
𝑇<𝑇𝑔
𝑇>𝑇𝑔
𝑇𝑓′
Equa ion 5 Moynihan's me hod o calcula e T .
Whe e, Cpl and Cpg a e he hea capaci y o he liquid and glass, espec i ely, and
Cp is he appa en hea capaci y o he sample a each empe a u e. I is no ed ha he
di e ences in T be ween he same ma e ial ha ing wo di e en he mal his o ies a e
ela ed o he di e ences in hei en halpy o e shoo s124.
T exhibi s a dec easing end wi h p olonged ageing ime o diminished cooling
a e. As he glassy s uc u e app oaches equilib ium, T con e ges owa d he alue o
he ageing empe a u e i sel .
In essence, he glass ansi ion empe a u e (Tg) ma ks he shi o an amo phous
ma e ial om a supe cooled liquid o glassy s a e. De e mined by obse ing changes in
hea capaci y o he mal expansi i y du ing cooling, o en using dila ome y, Tg is highly
sensi i e o he cooling a e, yielding dis inc alues o he same ma e ial unde di e en
a es. Con e sely, he ic i e empe a u e (T ) de ines he s uc u al s a e o a glass
du ing hea ing. I is he empe a u e a which speci ic p ope ies, like speci ic olume o
en halpy, in e sec wi h he equilib ium liquid line when ex apola ed along he glass line.
Bo h, Tg and T , depend on he cooling a e, wi h a common assump ion o hei
app oxima e equali y unde simila condi ions. Tg signi ies a undamen al ansi ion
impac ing mechanical p ope ies, while T e lec s he s uc u al aspec s o he glass,
cap u ing he deg ee o elaxa ion du ing cooling and hea ing.

89
Toge he , hese empe a u es p o ide insigh s in o he dynamic beha io and
s uc u al ans o ma ions o glass- o ming ma e ials, enhancing ou unde s anding o
hei he mal p ope ies and p ac ical applica ions125.
Figu e 46 Fic i e empe a u e scheme.
In his chap e , he T o poly(9,9-di-n-oc yl luo enyl-2,7-diyl), a enowned polyme
wi h a e y in ense pho oluminescence, is cha ac e ized ollowing a wide a ie y o
he mal his o ies.
5.2.3) PFO
Poly(9,9-di-n-oc yl luo enyl-2,7-diyl) o PFO was syn he ized in he 80s as pa o
o he eme ging ield o o ganic elec onics, pa icula ly in OLEDs and o ganic
pho o ol aic cells. I was de eloped o exhibi s ong elec oluminescence p ope ies.
This made i a p omising ma e ial o new echnologies o la -panel displays and
ligh ing. PFO and i s de i a i es played a c ucial ole in he de elopmen o OLED
90
echnology. OLED displays o e ed ad an ages o e adi ional liquid c ys al displays
(LCDs) in e ms o be e colo ep oduc ion, as e esponse imes, and lexibili y126–130.
I is lexible, almos anspa en , low weigh and all he p ope ies ela ed o he
polyme s and, also, i can be dissol ed in he common o ganic sol en s gi ing i he
ad an age in he indus y ield.
Figu e 47 PFO chemical s uc u e.
PFO solid s a e shows all he mo phological beha io s men ioned in he Chap e
2) . In pa icula , PFO has epo ed α phase, β phase and liquid c ys alline, all in luenced
by al e a ions in he su ounding solu ion en i onmen 131132.
The α-phase o PFO is cha ac e ized by a well-o de ed hexagonal la ice s uc u e.
The epea ing uni s align in a way ha maximizes π-π s acking in e ac ions, leading o
good cha ge anspo p ope ies wi h high c ys allini y and s i ness which con ibu es o
PFO's a o able op oelec onic p ope ies133. This c ys alline s uc u e ends o be he
mos s able and dominan c ys alline phase in PFO a oom empe a u e129.
The β-phase is ano he c ys alline phase o PFO, ypically obse ed a lowe
empe a u es han he α. The exac s uc u e and p ope ies o he β-phase can be
in luenced by ac o s such as cooling a es du ing solidi ica ion and he p esence o
addi i es o impu i ies126. The β-phase s uc u e may in ol e a di e en la ice
a angemen compa ed o he hexagonal la ice ound in he α-phase130134. Compa ed o
he α-phase o PFO, he β-phase o en exhibi s lowe cha ge ca ie mobili y135128.
91
In he nema ic phase, he long lexible polyme chains o PFO end o align along
a common axis, bu hey lack posi ional o de . This means ha , while he chains ha e
o ien a ional o de , hey a e no a anged in a egula pa e n as hey a e in a c ys alline
solid136137.
The objec i e o his pa o he wo k is o une he pho oluminescence
changing he physical beha io o he i eous phase o he PFO.
In summa y, he lexibili y, ligh ness, and easy p ocessabili y make o ganic ligh
senso s a pe inen successo o ino ganic senso s, c ea ing a new on ie in lexible
senso echnology. The cu en ocus is on enhancing e iciency, s abili y, and e sa ili y,
while main aining hei a o dabili y, sus ainabili y, and po en ial o la ge-scale
p oduc ion.
5.3) Resul s and discussion
This polyme can explo e all he modynamic s a es men ioned in he chap e 2) . I
may be ei he in he amo phous, c ys alline o liquid c ys al phase. I has ela i ely low
he mal ansi ion empe a u es well de ined. The e o e, sui able he mal p o ocols can
be designed o minimize he isk o signi ican deg ada ion issues. In addi ion o (a leas )
wo c ys alline o ms, PFO exhibi s a nema ic liquid-c ys alline mesophase (he e a e
e e ed o as he NEM s a e) in he empe a u e ange immedia ely abo e he c ys alline
phase(s) along wi h an iso opic liquid phase (he e a e e e ed o as ISO s a e) a
highe empe a u es.
To unde s and he he mal beha iou o he polyme , samples we e aged o 30
min o e a wide empe a u e ange be ween -80 and 280 Celsius, ollowed by hea ing
scans a 4000 K s-1 ha a e showed in Figu e 48. Following he de elopmen o
calo ime ic ea u es esul ing om ageing, his p ocedu e allows un eiling he he mal
e en s igge ed by a gi en he mal p o ocol. In his way, h ee egions can be
dis inguished: iso he mal annealing a o below 70 ºC esul s in he a ise o an endo he m
a low empe a u es (g ay a eas o Figu e 48), be ween -20 and 100 °C depending on
92
he annealing empe a u e, es i ying he physical ageing o he glassy polyme and he
subsequen eco e y in p oximi y o he glass ansi ion. Then, be ween 70 and 110 ºC
c ys alliza ion o he  o m akes place du ing he annealing s ep, highligh ed by a
sha pe and mo e in ense mel ing endo he m aking place a 130-140 °C (pu ple a eas,
Figu e 48). Annealings be ween 110 °C and 220 °C allow he o ma ion o he liquid
c ys al phase, ha e en ually dis up s du ing he weak endo he mic ansi ion a 260 °C
( ed a ea, Figu e 48).
Figu e 48 Isoch onous me hod applied o he PFO polyme .
To p o ide a quan i a i e pic u e, he endo he mic peaks we e in eg a ed o assess
he en halpy a ia ion esul ing om each he mal e en . The ou come o his analysis is
plo ed in Figu e 49. As in he Figu e 48, he g ey da a a e associa ed o he physical
ageing o he glassy polyme , he pu ple one o he c ys als and he so ed one o he
liquid c ys al.
Ex apola ing he high empe a u e pa o he en halpy a ia ion by a s aigh line,
he uppe empe a u e limi o each he mal e en can be de e mined. This p ocedu e
deli e s he uppe limi o Tg abou 70 ºC, ha o he c ys alliza ion p ocess o 110 ºC and
ha o he liquid c ys al o ma ion a 220 Celsius.
99
The e is a clea endency o bo h peaks o he spec um o shi owa ds highe
wa eleng hs ega dless o he ini ial s a e o he polyme (iso opic liquid o liquid c ys al).
Wi h he dec easing o he T , he i s peak is shi ed o highe wa eleng hs allowing us
o une he ligh emission.
Figu e 54 a) Pho oluminescence spec as o he selec ed samples and b) posi ion o he mos ele an
peak s he ic i e empe a u e o he samples.
Wi h his i s o e iew o he possibili y o con olling he he modynamic s a e o
he i eous phase o une he pho oluminescence new possibili ies o op oelec onic
de ices a e opened. No only imp o ing he c ys alliza ion be e de ices a e ob ained.
Wi h his app oxima ion, also amo phous o nea amo phous polyme s can be used o
new elec onic echnologies.

100
5.4) onclusions
The he modynamic s a e o he i eous polyme s is a di icul ield o knowledge.
Thanks o he lash DSC, we a e able o dis inguish and unde s and how he T beha es.
In his case, he LC o m appea s o ha e a g ea e empe a u e sensi i i y and a
endency o as e elaxa ion and i i ica ion compa ed o he LQ o m.
The beha io o PFO in a 2D s uc u e is he same as in bulk so ac i e laye s on
hin ilm de ices a e possible. Also, a wide ange o T we e ob ained con olling only he
cooling a e. To enla ge he ange he cooling a e con ol we e de eloped om he
iso opic liquid s a e and liquid c ys al s a e.
Bu he mos impo an and ele an conclusion is ha he con ol o he T is also
de e minan o con ol he op oelec onic p ope ies o o ganic semiconduc o polyme s.
101
"La ciencia no consis e en acumula
da os, sino en uni los."
Si William Law ence B agg
103
6) Conclusions
As main conclusions, he u iliza ion o he TMDSC (The mal Modula ed Di e en ial
Scanning Calo ime y) has enabled p ecise ep oduc ion and composi ional analysis o
sola cells and he ac i e laye mo phology on senso s and ansis o s. By ai h ully
eplica ing he sola cell and he ansis o /senso ac i e laye using a lash DSC chip,
we can in es iga e he mo phology o he eal ac i e laye h ough calo ime y. Also, he
GIWAXS and GISAXS p o ide a lo o in o ma ion unde s anding he di ec ion and he
ange o o de . These echniques, along wi h o he complemen a y app oaches, allow
us o unde s and and modi y nano and mic os uc u es a ou disc e ion.
To know he eal composi ion on he bulk he e ojunc ion in a sola cell as in he
Chap e 3) disco e ing ha a 50:50 weigh mechanical mix u e has, in eal, 37.5% o he
small molecules and he es polyme in he in e mix phase.
To s udy a “nea amo phous” polyme as ac i e laye on a hin ilm ansis o like
in he Chap e 4) In his case is demons a ed ha IDTBT is, a a glance, amo phous
because he e a e no o de a mic oscale bu has a high o de a nanoscale wi h 4 key
empe a u es. -10 and a ound 50 Celsius associa ed o he agg ega ion o he backbone
and he sidechains, one a 150 when he backbone mobili y s a s and he o de
inc eases a 250 °C associa ed o he mel ing o he ma e ial.
To unde s and and une he amo phous phase o he polyme s modi ying he
cooling a es and he s a s a e (iso opic liquid o liquid c ys al) o con ol he changes
on he op oelec onic p ope ies. In Chap e 5, he ic i e empe a u e (T ) o PFO was
adjus ed o manipula e i s op oelec onic p ope ies, achie ing a ange o app oxima ely
30 K wi hin which T could be modula ed in a imely manne (no equi ing ex ended
du a ions). Al hough s abiliza ion o T emained elusi e, i became e iden ha
p olonged cooling imes a e necessa y o g adually dec ease i .
Now, I wan o ew i e he conclusions in Spanish o my amily and he people ha
does no know English and wan o know wha is abou his wo k.
104
Conclusiones
Como p incipales conclusiones de es e abajo se encuen an la u ilización de la
TMDSC (Calo ime ía Di e encial de Ba ido Modulada Té micamen e) que ha pe mi ido
ep oduci con p ecisión y analiza la composición de las células sola es, la mo ología
de la capa ac i a de los ansis o es y senso es. Al ep oduci ielmen e la célula sola o
la capa ac i a de un ansis o o senso u ilizando un chip de lash DSC, podemos
in es iga la mo ología de la capa ac i a eal median e calo ime ía. Además, g acias al
GIWAXS y GISAXS, comp endemos la di ección y el ango de o den en la mues a.
Es as écnicas, jun o con o os en oques complemen a ios, nos pe mi en comp ende y
modi ica a nues o an ojo la nano y mic oes uc u a del ma e ial.
Pa a en ende la composición eal de una he e o-unión de una placa sola como
en el capí ulo 3) En es e apa ado se analiza una mezcla mecánica de 50:50 % en peso
de dono y acep o con un ecocido en a mós e a sa u ada. Se de e mina que, en
ealidad, la ase en emezclada iene sólo un 37,5 % de acep o .
Pa a es udia los políme os denominados “casi amo os” como capa ac i a en
ansis o es. En el capí ulo 4) se demues a como el IDTBT que has a la echa es
conside ado de es a amilia, en ealidad iene un al o o den a escala nanomé ica
aunque no se ap ecie ningún o den a escala mic omé ica. És e iene 4 empe a u as
cla e. Asociadas a la o mación de ag egados de la cadena p incipal y a las cadenas
la e ales son -10 y 50 ˚ . A los 150 g ados la cadena p incipal comienza a adqui i
mo ilidad y o dena se y a 250 ˚ el ma e ial unde.
Pa a modi ica el es ado e modinámico de la ase amo a a an ojo modi icando la
elocidad de en iamien o y el es ado desde el que se en ía (líquido iso ópico o c is al
líquido). En el Capí ulo 5, la empe a u a ic icia (T ) de PFO se ajus ó pa a manipula
sus p opiedades op oelec ónicas, log ando un ango de ap oximadamen e 30 K den o
del cual T pod ía modula se de mane a opo una (sin eque i iempos muy la gos). Po
o o lado, la es abilización de la T no se consigue debido a que se necesi a ía un
en iamien o excesi amen e len o.

105
"En ciencia, algunos expe imen os
ienen éxi o y o os, enseñanza."
John C. Polanyi
107
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