tpe-dcn v10 si e&es - rsc.org · 1 supplementary information increasing the power outputs of a...

1

Supplementary Information

Increasing the Power Outputs of a CdTe Solar Cell via Luminescent

Down Shifting Molecules with Intramolecular Charge Transfer and

Aggregation-Induced Emission Characteristics

Yilin Lia,b, Zhipeng Lia, Yang Wangb,¶, Alvin Compaanc, Tianhui Rena,*, Wen-Ji Dongb,*

a School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai

200240, China; b Voiland School of Chemical Engineering and Bioengineering, Washington State University,

Pullman, WA 99164, USA; c Department of Physics and Astronomy , The University of Toledo, Toledo, OH 43606, USA.

Content

1. Synthesis and characterization .................................................................................................. 2

2. Absorption and emission spectra of Y083 in LDS film ............................................................ 6

3. Transition dipole moment change .............................................................................................. 7

4. Theoretical computations ........................................................................................................... 8

5. Fluorescence lifetime measurements ......................................................................................... 9

6. Images of aggregated nanoparticles ........................................................................................ 10

7. Thermal stability measurements .............................................................................................. 11

8. LDS measurements ................................................................................................................... 12

* Corresponding authors: Wen-Ji Dong, Tel: +01-509-335-5798; e-mail: [email protected]; Tianhui Ren, Tel: +86-21-54747118; email: [email protected]; ¶ undergraduate summer intern from Department of Chemistry, University of California Berkeley.

Electronic Supplementary Material (ESI) for Energy & Environmental ScienceThis journal is © The Royal Society of Chemistry 2013

1. Sy

U

Chro

NMR

reco1H-N

been

Sche

THF

malo

5-fo

K2C

chlo

Pd(P

Gen

ReM so

resu

4-bo

room

of w

dried

disso

amo

was

and

ynthesis and

Unless otherw

omatographic

R spectra we

orded on a 4

NMR, 13C-NM

n done for the

eme S1. Syn

F, 0 °C, 30

ononitrile, p

rmylfuran-2-

CO3, toluene

oride, rt, 16 h

PPh3)4, toluen

neral procedu

eaction (i): Tolution of n-B

ulting solutio

oromobenzop

m temperatur

water, the org

d over anhyd

olved in abou

ount of p-tolu

refluxed for

extracted wit

d characteriz

wise noted, al

c purification

ere collected o

4800 MALDI

MR and MA

e final produc

nthetic route

min, 4-brom

piperidine, E

-boronic acid

: MeOH = 1

h; (v) malono

ne, reflux, 16

ures:

To a solution o

BuLi in hexa

n was stirre

phenone (3.1

e with stirrin

anic layer wa

drous MgSO4

ut 80 mL of

uenesulphonic

16 h and coo

th DCM twic

ation

ll reagents w

n was carried

on a 300 MH

I TOF/TOF a

ALDI-MS. Ad

cts to prove th

of fluoropho

mobenzophen

EtOH, rt, 1

(for 1b) / 5

1 : 1, 75 °C

onitrile, piper

h.

of 3 (2.0 g, 1

nes (7.4 mL,

ed for 30 m

g, 11.9 mm

ng during a 6

as extracted w

4. The solven

toluene in a

c acid monoh

oled to room

ce. The comb

2

were used as

d out using 6

Hz spectromet

analyzer. All

dditional elem

he enough pu

ores 1a-c. Re

none, rt, 6 h

6 h; (iii)

5-formylthiop

, 16 h; (iv)

ridine (for 1b

1.9 mmol) in

11.9 mmol)

min at that t

mol) and the r

h period. Th

with DCM tw

nt was evapo

150 mL flask

hydrate (500 m

m temperature

bined organic

received and

60-200 mesh

ter at room te

l reaction pr

mental analys

urity for the sp

eaction regen

h, TsOH·H2O

4-formylphe

phene-2-boron

n-BuLi, THF

b) / Et3N (for

n 20 mL of an

at 0 °C unde

temperature.

reaction mix

he reaction w

wice and the

orated, and th

k fitted with

mg, 2.6 mmo

. The toluene

c layers were

d without fur

h silica gel fo

emperature. M

oducts were

sis (C, H, N

pectroscopic

nts and condi

O, toluene, r

nylboronic

nic acid (for

F, -78 °C, N

r 1c), DCM,

nhydrous THF

er an nitrogen

To this solu

ture was allo

was quenched

combined or

he resulting c

a Dean-Stark

ol) was added

e layer was w

dried over a

rther purifica

for flash colu

Mass spectra

characterize

percentage)

measuremen

itions: (i) n-B

reflux, 16 h

acid (for 1

1c), Pd(dppf

N2, 1 h, tribut

30 °C, 16 h

F was added

n atmosphere

lution was a

owed to war

with the add

rganic layers

crude alcohol

k trap. A cata

d, and the mi

washed with w

anhydrous M

ation.

umns.

were

ed by

have

ts.

BuLi,

; (ii)

1a) /

f)Cl2,

tyltin

; (vi)

a 1.6

. The

added

rm to

dition

were

l was

alytic

xture

water

gSO4


and

chro

RemL o

h. Th

direc

Remmo

5-fo

and

mixt

was

1) as

Re2.4 m

was

stirri

DCM

smal

Rewas

The

resid

affor

Remg,

evap

1) as

Com

evaporated to

omatography

eaction (ii): Tof EtOH was

he resulting p

ctly.

eaction (iii): ol, for 1a

rmylthiophen

K2CO3 (1.7 g

ture was stirr

removed. Th

s eluent to aff

eaction (iv): mmol) in 25 m

added tribut

ing for 16 h

M and dried o

ll portion of 2

eaction (v): Tadded 10 dro

resulting mi

due was puri

rd 1b (or 1c).

eaction (vi): 5 mol%) in

porated and th

s eluent to aff

mpound char

1a

1b

o afford the c

using hexane

To a solution

s added 3 dro

precipitate wa

A mixture o

a) / 5-form

ne-2-boronic

g, 12.2 mmol

red at 75 °C f

he residue wa

ford 2a, 2b or

1.6 M n-BuL

mL of anhyd

tyltin chlorid

. The resultin

over anhydro

2d was isolat

To a solution

ops of Et3N (

ixture was d

fied by silica

.

A mixture of

25mL of tol

he residue wa

ford 1a.

racterization

2-((4'-(Yellow

MHz, C

Hz), 7

CDCl3

133.3,

127.9,

calcd f

2-((5-((1b). Orange

MHz,

7.16-7.

crude 4. The p

es as eluent.

n of 5 (6.0 g,

ps of piperid

as collected b

of 4 (1.0 g,

mylfuran-2-bo

acid (758 m

) were dissolv

for 16 h. The

as purified by

r 2c.

Li in hexanes

rous THF at

de (2.0 mL, 7

ng mixture w

ous MgSO4. D

ed using hexa

of 2b (or 2c

or piperidine

ried over an

a gel chroma

f 2d (360 mg

luene was sti

as purified by

ns:

(1,2,2-triphenw solid (yield

CDCl3, δ): 7.

.42 (d, 1H, J

, δ): 159.4, 1

132.4, 132.1

127.0, 126.9

for C36H24N2+

(4-(1,2,2-triph

e solid (yield

CDCl3, δ): 7

.01 (m, 17H)

3

pure product

32.4 mmol)

dine. The mix

by filtration a

2.4 mmol),

oronic acid

mg, 4.9 mmol

ved in 50 mL

e resulting re

y silica gel ch

(5.0 mL, 7.3

-78 °C under

7.3 mmol) an

was quenched

Due to the de

anes as eluen

c) and malon

e). The reactio

nhydrous Mg

atography usi

g, 0.6 mmol)

irred and refl

y silica gel ch

nylvinyl)biph 82 %). Rf =

.96 (d, 2H, J =

J = 8.4 Hz),

147.1, 145.1,

, 131.6, 131.

9, 126.9, 126+ 484.1939, fo

henylvinyl)ph

d 32 %). Rf =

7.60 (d, 2H,

), 6.87 (d, 1H

4 was obtain

and malonon

xture was stirr

and washed b

4-formylphen

d (680 mg

l, for 1c), Pd

L of MeOH an

action mixtur

romatography

mmol) was a

r nitrogen wit

nd then warm

d with the ad

ecomposition

nt.

onitrile (2.0 e

on mixture w

SO4. The so

ing hexanes

, 6 (135 mg,

luxed for 16

hromatograph

enyl-4-yl)met 0.38 (Hex :

= 8.5 Hz), 7.7

7.18-7.04 (m

, 143.7, 143.

6, 131.6, 131

6.7, 114.3, 1

ound 484.226

henyl)furan-2

= 0.56 (Hex :

J = 8.6 Hz

H, J = 3.9 Hz)

ed by purific

nitrile (1.8 g,

red at room te

by EtOH twic

nylboronic a

g, 4.9 mm

d(dppf)Cl2 (8

nd toluene (1

re was filtere

y using hexan

added to a so

th stirring for

med to room

ddition of wa

of 2d on the

equivalent) in

as stirred und

lvent was ev

and DCM (1

0.6 mmol) a

h. The resul

hy using hexa

thylene)malonDCM = 1 : 2

76 (s, 1H), 7.

m, 17H). 13C

7, 143.6, 142

.5, 129.9, 12

13.2, 81.9. M

64.

-yl)methylene

DCM = 1 : 4

), 7.36 (s, 1H

). 13C-NMR (

cation on silic

27.0 mmol)

emperature f

ce to obtain p

acid (729 mg

mol, for 1b

9 mg, 5.0 m

: 1). The rea

ed and the so

nes and DCM

olution of 4 (1

r 1 h. The sol

temperature

water, extracte

e silica gel, o

n 25 mL of D

der 30 °C for

vaporated and

1 : 1) as elue

and Pd(PPh3)

lting solution

ane and DCM

nonitrile (1a)2). 1H-NMR

.72 (d, 2H, J

C-NMR (75 M

2.2, 140.3, 1

28.1, 128.1, 1

MALDI-MS:

e)malononitr

4). 1H-NMR

H), 7.26 (s,

(75 MHz, CD

ca gel

in 20

for 16

ure 6

g, 4.9

b) /

mol%)

action

olvent

M (1 :

1.0 g,

ution

with

ed by

only a

DCM

r 16h.

d the

ent to

)4 (33

n was

M (1 :

). (300

= 8.5

MHz,

36.6,

28.0,

: m/z

rile

(300

1H),

DCl3,


1c

2a

2b

2c

δ): 161

128.2,

75.1. M

2-((5-(e (1c). Orange

MHz, C

Hz), 7

CDCl3

134.2,

127.0,

C34H22

4'-(1,2,Yellow

MHz,

8.2 Hz

CDCl3

132.3,

126.9,

436.16

5-(4-(1Yellow

MHz, C

Hz), 7

CDCl3

131.6,

MALD

5-(4-(1Yellow

MHz, C

Hz), 7

CDCl3

137.7,

126.9,

found 4

tributyColorle

CDCl3

8.0 Hz

1.7, 147.4, 1

128.1, 127.9

MALDI-MS:

(4-(1,2,2-triph

e solid (yield

CDCl3, δ): 7.

.37 (d, 1H, J

, δ): 156.7, 1

132.6, 131.6

126.1, 124

2N2S+ 490.150

,2-triphenylvw solid (yield

CDCl3, δ): 1

), 7.43 (d, 2H

, δ): 192.1, 1

131.7, 131.6

126.8. MA

654.

1,2,2-triphenyw solid (yield

CDCl3, δ): 9.

.15-7.03 (m,

, δ): 177.3, 1

131.6, 131.5

DI-MS: m/z c

1,2,2-triphenyw solid (yield

CDCl3, δ): 9.

.34 (d, 1H, J

, δ): 183.0, 1

132.4, 131.6

125.9, 124.

442.1098.

l(4-(1,2,2-tripess liquid (y

, δ): 7.21 (d,

z), 1.58-1.47

4

46.9, 143.5,

9, 127.1, 127.

m/z calcd for

henylvinyl)ph

d 22 %). Rf =

.76 (s, 1H), 7

J = 4.1 Hz),

150.8, 146.5,

6, 131.6, 131.

.7, 114.5, 1

04, found 490

vinyl)biphenyl 50 %). Rf =

0.04 (s, 1H),

H, J = 8.6 Hz

146.9, 144.5,

6, 131.6, 130.

ALDI-MS: m

ylvinyl)pheny 62 %). Rf =

.61 (s, 1H), 7

17H), 6.75

159.7, 152.1,

, 128.1, 128.

alcd for C31H

ylvinyl)pheny 76 %). Rf =

.87 (s, 1H), 7

J = 4.0 Hz),

154.4, 145.5,

6, 131.6, 131.

.1. MALDI-M

phenylvinyl)pyield 28 %).

, 2H, J = 8.0

(m, 6H), 1.3

143.3, 142.6

0, 127.0, 126

r C34H22N2O+

henyl)thiophe

= 0.52 (Hex :

.67 (d, 1H, J

7.17-7.04 (m

, 143.5, 143.

5, 130.2, 128

113.7, 76.5.

0.1055.

l-4-carbaldeh 0.60 (Hex :

7.93 (d, 2H,

z), 7.19-7.07 (

, 143.8, 143.

5, 128.1, 128

m/z calcd for

yl)furan-2-car 0.31 (Hex :

.57 (d, 2H, J

(d, 1H, J =

, 145.8, 143.

1, 128.0, 127

H22O2+ 426.16

yl)thiophene-2 0.40 (Hex :

.70 (d, 1H, J

7.17-7.03 (m

, 143.7, 143.

5, 131.1, 128

MS: m/z cal

phenyl)stanna. Rf = 0.19

Hz), 7.13-7.

6-1.29 (m, 6

6, 140.2, 132

6.1, 125.3, 11+ 474.1732, fo

n-2-yl)methy

DCM = 1 : 3

= 4.1 Hz), 7.

m, 17H). 13C

5, 143.4, 142

8.2, 128.2, 12

MALDI-MS

hyde (2a). DCM = 1 : 2

, J = 8.5 Hz)

(m, 17H). 13C

8, 141.9, 140

8.1, 128.0, 12

r C33H24O+

rbaldehyde (2DCM = 1 : 2

= 8.7 Hz), 7.

3.7 Hz). 13C

6, 143.4, 142

7.1, 127.0, 12

620, found 42

2-carbaldehydDCM = 1 : 2

= 4.0 Hz), 7.

m, 17H). 13C

6, 143.5, 142

8.2, 128.1, 12

lcd for C31H

ane (2d). (Hex). 1H-N

04 (m, 15H)

6H), 1.02 (t, 6

2.5, 131.6, 1

14.8, 113.8, 1

found 474.166

ylene)malonon

3). 1H-NMR

.44 (d, 2H, J

C-NMR (75 M

2.6, 140.4, 1

28.0, 127.2, 1

S: m/z calcd

2). 1H-NMR

), 7.72 (d, 2H

C-NMR (75 M

0.4, 137.5, 1

27.6, 127.0, 1

436.1827, f

2b). 2). 1H-NMR

.28 (d, 1H, J

C-NMR (75 M

2.3, 140.3, 1

26.9, 124.9, 1

26.1465.

yde (2c). 2). 1H-NMR

.43 (d, 2H, J

C-NMR (75 M

2.3, 142.2, 1

27.9, 127.1, 1

H22OS+ 442.1

NMR (300 M

, 6.99 (d, 2H

6H), 0.90 (t,

31.5,

09.8,

64.

nitril

(300

= 8.4

MHz,

40.0,

27.1,

d for

(300

H, J =

MHz,

35.3,

26.9,

found

(300

= 3.7

MHz,

32.2,

07.9.

(300

= 8.6

MHz,

40.2,

27.0,

1391,

MHz,

H, J =

9H).


2d

4

6

13C-NM

140.2,

27.6, 1

620.08

(2-(4-bWhite

MHz, C

J = 8.6

141.9,

127.0,

410.05

2-(4-brWhite

MHz, C

Hz). 13

133.7,

found 2

MR (75 MHz

135.9, 131.6

14.0, 9.8. M

860.

bromophenyl)solid (yield 3

CDCl3, δ): 7.

6 Hz). 13C-N

140.0, 133.4

127.0, 120.8

52.

romobenzylidsolid (yield

CDCl3, δ): 7.3C-NMR (75

112.6, 83.7

231.9223.

5

z, CDCl3, δ)

6, 130.9, 129

MALDI-MS: m

)ethene-1,1,2-37 %). Rf =

.31 (d, 2H, J =

NMR (75 MH

4, 131.7, 131.

. MALDI-MS

dene)malonon83 %). Rf =

.77 (d, 2H, J =

5 MHz, CDC

7. MALDI-M

: 144.1, 144.

.2, 128.7, 12

m/z calcd fo

-triyl)tribenze0.56 (Hex :

= 8.5 Hz), 7.2

Hz, CDCl3, δ

6, 131.6, 131

S: m/z calcd f

nitrile (6). 0.23 (Hex :

= 8.6 Hz), 7.7

Cl3, δ): 158.7

MS: m/z calc

1, 144.0, 143

7.8, 127.8, 12

or C38H44Sn-

ene (4). DCM = 2 : 1

22-7.11 (m, 1

δ): 143.8, 143

.2, 128.2, 12

for C26H19Br+

DCM = 1 : 1

72 (s, 1H), 7.

7, 133.3, 132

cd for C10H5

3.4, 141.4, 1

26.6, 126.5,

620.2621, f

1). 1H-NMR

15H), 7.01 (d

3.7, 143.6, 1

28.1, 128.0, 1+ 410.0670, f

1). 1H-NMR

.68 (d, 2H, J

2.1, 130.2, 1

5BrN2- 231.9

41.0,

29.3,

found

(300

d, 2H,

43.0,

27.1,

found

(300

= 8.7

29.9,

9636,


2. A

Figu

472

CdT

bsorption an

ure S1. Norm

nm, green, ▼

Te solar cell (m

nd emission s

malized absor

▼) associated

magenta).

spectra of Y0

rption (solid

d with AM1.5

6

083 in LDS f

lines) and em

5G solar spect

film

mission (dash

trum (dark ye

h lines) spectr

ellow) and sp

tra of Y083 (

pectral respon

(λex =

nse of


7

3. Transition dipole moment change

The dipole moment change was calculated by linear Lippert-Mataga equation:

− ≅ − + 2 −ℎ

= − 12 + 1 − − 12 + 1

Where ν is the wavenumber (cm-1); the superscript ICT and vac mean ICT and gas states,

respectively; the subscript abs and flu mean absorption and emission processes, respectively; μe

and μg are dipole moment (1 D = 10-18 esu cm) of the excited and ground state, respectively; h is

the Planck’s constant (6.63×10-27 erg·s); c is the speed of light (3×1010 cm·s-1) and a0 (cm) is the

cavity radius of Onsagar’s reaction field. The Δf value was tuned by different mixtures of

1,4-dioxane and acetonitrile. It is calculated by: ϵ = χ ϵ + χ ϵ n = χ n + χ n

Table S1. Calculation of transition dipole moment change (ue – ug) of fluorophores 1a-c.

Fluorophorea slope, cm-1 r2 ue – ug, D

1a 11545 ± 1156 0.9251 24.2 ± 1.2

1b 9186 ± 1123 0.8799 21.6 ± 1.3

1c 10537 ± 1306 0.8769 23.2 ± 1.4 a average value of the longest axis for fluorophores 1a-c is 2 nm.


8

4. Theoretical computations

Table S2. Calculated charge contribution (%) on molecular orbitals of ground (S0) and excited (S1)

states on donor (TPE) group. The difference indicates ICT rate (%).

Absorption Emission

S0 S1* ICT rate S1 S0* ICT rate

1a 94 % 11 % 83 % 12 % 96 % 84 %

1b 82 % 17 % 65 % 19 % 92 % 73 %

1c 86 % 16 % 70 % 21 % 91 % 70 %

* Non-equilibrium state.


5. Fl

Figu

= 95

D

D

W

fluor

Th

C

luorescence

ure S2. Fluor

5 %) (right). T

Data in Figure

Data in Figure

Where α is th

rescence lifet

he fitting resu

Compd

1a

1b

1c

lifetime mea

rescent lifetim

The fluoropho

S2 left was f

e S2 right was

he represent

time.

ults are:

single-expon

τf (ns)

1.92

1.05

1.01

asurements

mes of fluorop

ore concentra

fitted by singl

s fitted by twI =τthe amplitud

nential

9

phores 1a-c i

ation is 15μM

le-exponentiaI = αewo-exponentiaα e + α= α τ + αα τ + αdes of the co

in acetonitrile

M.

al decay equa

al decay equae ττ

omponents at

t

τ1 (ns)

2.19

1.75

1.38

e (fw = 0) (lef

ation:

ation:

t t = 0 and

two-exponent

τ2 (ns)

9.43

5.98

4.32

ft) and mixtur

τf is the ave

ntial

) τf (n

5.7

2.3

1.7

re (fw

erage

ns)

70

5

72


6. Im

Figu

aceto

the a

mage of aggr

ure S3. TEM

onitrile soluti

aggregated na

regated nano

M image of

ion with 95 %

anoparticles i

oparticles

f aggregated

% of water fra

in TEM adhes

10

nanoparticle

action. Due to

sive onto the

es of fluoro

o the hydroph

polymer edg

ophore 1a p

hobic nature o

ge of the samp

prepared from

of fluorophor

ple substrate.

m its

re 1a,


11

7. Thermal stability measurements

Figure S4. Results of TGA and DSC measurements. Decomposition temperature: 1a, 132 °C, 1b,

291 °C and 1c, 245 °C. Melting point: 1a, n/a (decomposed first), 1b, 239 °C and 1c, n/a.


12

8. LDS measurements

The measurements of LDS effect on the CdTe solar cell is based on the definition of cell EQE

and the output short circuit current density (Jsc): J = e EQE λ ϕ λ dλ = dIdA

Where ϕ λ is the output light profile of the solar simulator and A is the active area of the

CdTe solar cell, which is 0.5 cm2.

Both the short circuit current (Isc) with and without the LDS film were measured. Assuming A is

proportional to Isc, the change of Isc is equal to the change of Jsc: I , − I , I , = J , − J , J , = JJ

A CdTe solar cell was used as reference in the LDS film EQE measurement. This solar cell was

fabricated with a thin CdS layer (about 70 nm) and it shows short-wavelength response (300 – 500

nm). It is active area is 0.5 cm2. The EQE of a CdTe solar cell with LDS film was calculated by

the following equation: I , λI , λ = EQE λEQE λ

The output Isc at each individual wavelength was directly measured by a multimeter. The

individual wavelength light was selected by connecting a monochromator to the solar simulator.


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