Supplementary Information (SI) for Energy & Environmental Science.

This journal is © The Royal Society of Chemistry 2025

Supplementary Information (SI) for Energy & Environmental Science.

This journal is © The Royal Society of Chemistry 2025

Supplementary Information

Reducing Energy Loss by Developing Luminescent

Triphenylamine Functionalized Electron Acceptor for High-

Performance Organic Solar Cells

Yue Chen+a,b, Xiaopeng Duan+a, Junjie Zhangb, Zhongwei Geb, Haisheng Maa, Xiaobo Sun*a,b, Huotian

Zhang*c, Jiaxin Gaod, Xuelin Wangd, Xunchang Wange, Zheng Tangd, Renqiang Yange, Feng Gaoc, and

Yanming Sun*

aHangzhou International Innovation Institute, Beihang University, 311115 Hangzhou, P. R. China

E-mail: [email protected]; [email protected]

bSchool of Chemistry, Beihang University, Beijing 100191, P. R. China
cDepartment of Physics Chemistry and Biology (IFM), Linköping University, Linköping 58183,

Sweden

E-mail: [email protected]
dState Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Center for

Advanced Low-dimension Materials, College of Materials Science and Engineering, Donghua

University, Shanghai 201620, P. R. China

eKey Laboratory of Flexible Optoelectronic Materials and Technology (Ministry of Education),

School of Optoelectronic Materials &Technology, Jianghan University, Wuhan 430056, P. R. China

+ These authors contributed equally: Yue Chen, Xiaopeng Duan

1
1.Experiment section
1.1 Materials

PM6 was purchased from Solarmer Materials (Beijing, China). Compound 1(2-(5-bromo-3-oxo-2,3-

dihydro-1H-inden-1-ylidene) malononitrile) was purchased from Hyper Chemical Company. L8-BO

and L8-BO-CHO (3,9-bis(2-butyloctyl)-12,13-bis(2-ethylhexyl)-12,13-dihydro-

[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo

[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-dicarbald-ehyde) were meticulously prepared

according to established literature methods.[1] 1,3-dibromo-5-chlorobenzene (DBCl) was purchased

from Leyan.com. Compound 2(4-(Diphenylamine)phenylboronic acid) and Pd(Pph3)4 were purchased

from Energy Chemical. [2-(9H-Carbazol-9-yl)ethyl] phosphonic acid (2PACz) was purchased from

Aladdin. All purchased materials were used without further purification. The detailed synthetic

procedures and characterizations of the Z-Tri were described in the following sections.

1.2 Synthesis of Z-Tri

Compound 3: Compound 1 (273 mg, 1.00 mmol) and compound 2 (1446 mg, 5.00 mmol) were

dissolved into tetrahydrofuran (45 ml) in a three-neck flask. K2CO3 (484 mg, 3.50 mmol) dissolved in

water (6 ml) was added to the three-neck flask. The solution was flushed with nitrogen for 10 min.

Then, add Pd (Pph3)4 (110 mg) to the solution, then let the solution temperature to 95°C for 5 h.

Washed with saturated salt water and ethyl acetate. The solvent was removed under reduced pressure.

The crude product was subsequently purified by column chromatography on silica gel to afford

compound 3 as an orange solid (417 mg, 93% yield). 1H NMR (500 MHz, CD2Cl2) δ 8.63 (d, J = 8.3

Hz, 1H), 8.19 – 8.00 (m, 2H), 7.60 (d, J = 8.8 Hz, 2H), 7.33 (dd, J = 8.5, 7.3 Hz, 4H), 7.22 – 7.07 (m,

8H), 3.72 (s, 2H).

Z-Tri: Compound 4 (L8-BO-CHO, 120 mg, 0.113 mmol) and compound 3 (396 mg, 0.904 mmol)

were dissolved into dry chloroform (40 mL) in a three-neck flask. The solution was flushed with

nitrogen for 15 min. After 0.6 mL pyridine was added, the mixture was stirred at 65°C overnight. After

cooling to room temperature, the reaction mixture was poured into water and extracted several times

with chloroform. Then the solvent was removed under reduced pressure, and the crude product was
2
purified by column chromatography on silica gel to yield Z-Tri as a black solid (187 mg, 87% yield)

.1H NMR (400 MHz, Chloroform-d) δ 9.15 (s, 2H), 8.73 (d, J = 8.4 Hz, 2H), 8.14 (d, J = 1.8 Hz, 2H),

7.97 (dd, J = 8.4, 1.9 Hz, 2H), 7.61 (d, J = 8.8 Hz, 4H), 7.34 (t, J = 8.5 Hz, 8H), 7.19 (m, 10H), 7.16 –

7.10 (m, 4H), 4.78 (t, J = 7.8 Hz, 2H), 3.19 (d, J = 7.5 Hz, 2H), 2.11 (m, 4H), 1.39 (m, 4H), 1.24 (m,

32H), 1.03 (m, 10H), 0.85 (dt, J = 13.8, 6.9 Hz, 12H), 0.76 (td, J = 7.5, 3.8 Hz, 6H), 0.64 (td, J = 7.2,

4.0 Hz, 6H); 13C NMR (126 MHz, CDCl3, δ): 188.49, 160.60, 152.31, 149.18, 147.60, 147.09, 146.45,

144.94, 137.99, 137.76, 137.74, 134.96, 134.09, 133.54, 132.23, 131.02, 129.70, 129.57, 127.92,

125.64, 125.33, 123.97, 122.48, 121.58, 120.26, 115.90, 115.39, 113.35, 67.22, 55.73, 40.35, 39.85,

34.52, 33.56, 33.30, 31.84, 29.73, 29.66, 28.87, 28.85, 27.67, 26.61, 26.59, 23.36, 23.33, 23.01, 22.88,

22.86, 22.67, 14.11, 14.07, 13.79, 13.77, 10.40; MS (MALDI-TOF) m/z: [M + H]+ calcd for

C120H120N10O2S5, 1892.82, found: 1892.97.

S
HO OH N N
CN
B C 4H 9 C 4H 9
NC CN NC S S
90℃ C6H13 C6H13
N
＋ N Pd(Pph3)4,THF, O ＋ OHC S
C 4H 9
N N
S
C 4H 9
CHO
O
C 2H 5 C 2H 5
Br Na2CO3

1 2 3 4

S
N N
C 4H 9 C 4H 9
S S
C6H13 C6H13
CN N N NC
S S
60℃ NC
C 4H 9 C 4H 9 CN
O C 2H 5 C 2H 5 O

CHCl3, pyridine

N N

Z-Tri

Scheme S1. Synthetic routes of Z-Tri.

1.3 Device fabrication

All the OSCs devices were fabricated by using a conventional structure of ITO/2PACz/active

layer/PNDIT-F3N/Ag. The ITO-coated substrates were sequentially cleaned by detergent deionized

water, acetone, and isopropyl alcohol for 20 min in an ultrasonic cleaning machine. The cleaned ITO-

3
coated substrates were dried in an oven at 100 °C overnight. Before use, the ITO-coated substrates

were pretreated by a plasma cleaner for 1 min under a vacuum condition below 10 Pa. Then a

monolayer of 2PACz (0.3 mg ml-1 in ethanol) was firstly deposited on the top of the ITO substrates at

a rate of 3000 rpm for 30 s, followed by thermal annealing at 100 oC for 10 min under ambient

conditions. The PM6:L8-BO (1:1.2 w/w) was dissolved in chloroform at the donor concentration of

7.3mg/mL with 165 wt% DBCl as the solid additive. The PM6:Z-Tri (1:1.2 w/w) was dissolved in

chloroform at the donor concentration of 7.3mg/mL with 165 wt% DBCl as the solid additive. The

PM6:L8-BO: Z-Tri (1:1:0.2 w/w/w) was dissolved in chloroform at the donor concentration of

7.3mg/mL with 165 wt% DBCl as the solid additive. Then the active layers with different amounts of

Z-Tri were spin-cast on the 2PACz layer surface in an N2-filled glove box at 2800 rpm for 40 s with a

total concentration of 16 mg mL−1 in chloroform (CF). The active layer solutions were stirred at 80 oC

for 4h before used. Then, the active layers were thermally annealed at 80 °C for 8 min. Subsequently,

a thin layer of PNDIT-F3N (1.2 mg ml-1 in methanol with 0.5% acetic acid, v/v) was spin-coated onto

the active layer at a rate of 4200 rpm for 30 s. Finally, a 120 nm-thick silver layer was thermally

deposited under a vacuum condition of 2×10-4 Pa. The active area of devices is 5.12 mm2.

1.4 Device characterization

J-V and EQE Measurements

The devices were tested through a mask with an area of 3.15 mm2. The device performance was

measured by using a 510 Air Mass 1.5 Global (AM1.5G) solar simulator (SS-F5-3A, Enlitech) with

an irradiation intensity of 100 mW cm-2, which was determined by using a calibrated silicon solar cell

(SRC2020, Enlitech). The J-V characteristics were measured by using a Keithley 2400 Source

Measure Unit. EQE spectra were performed by using a QE-R3011 Solar Cell EQE measurement

system (Enlitech).

Time-dependent density functional theory (TD-DFT) calculations

All calculations were optimized using the ORCA 5.0.4 program package. The R2SCAN-3c composite

method proposed by S.Grimme was used to optimize the structure and ωB97X-D3 hybrid functional

combined with Def2-TZVP was used for single point calculations. The solvent effect of chloroform

4
was considered, using the continuum polarizable continuum model (CPCM). All post-calculation

analysis was carried out using the Multiwfn 3.8.4 Dev software package and the results were visualized

using visual molecular dynamics (VMD) 1.8.4. .

Ultraviolet-visible (UV-vis) spectroscopy measurements

UV-vis absorption spectra of the pristine and blend films were acquired with a UV-vis

spectrophotometer (Shimadzu UV-3600).

Cyclic Voltammogram (CV) Measurements

Cyclic voltammogram (CV) measurement was carried out on a CHI660E electrochemical workstation

with three electrodes, employing glassy carbon discs as the working electrode, Pt wire as the counter

electrode, and Ag/AgCl electrode as the reference electrode at a scanning rate of 100 mV s-1 under a

nitrogen atmosphere. Tetrabutylammonium hexafluorophosphate (Bu4NPF6, 0.1 mol/L) dissolved in

acetonitrile (HPLC grade) was adopted as the supporting electrolyte. PBDF-NS was drop-cast the

electrode from chloroform solutions to form thin films. Potentials were referenced to the

ferrocene/ferrocenium (Fc/Fc+) redox couple by using ferrocene as the external standard in acetonitrile

solutions (EFc/Fc+=0.42 eV). EHOMO =−[(4.8− EFc/Fc+) +Eox] (eV); ELUMO =−[(4.8− EFc/Fc+) +Ered] (eV).

Space-charge-limit current (SCLC)

The SCLC method was used to study the charge transport properties of neat film and blend films. The

hole-only and electron-only devices were fabricated with a structure of

ITO/2PACz/PM6:NFA/MoO3/Ag and ITO/ZnO/PM6:NFA/PNDIT-F3N/Ag, respectively. The

charge carrier mobility was determined by fitting the corresponding J-V characteristics by using the

equation of J=9ε0εrµV2/8L3, where J is the current density, ε0 is the permittivity of free space, εr is the

permittivity of the active layer, µ is the charge carrier mobility (μh and μe), V is the effective voltage

(V=Vappl-Vbi-VR, in which Vappl is the applied voltage, Vbi is the built-in potential and VR is the voltage

loss from series resistance of the device) and L is the film thickness of the neat film or blend film.

Steady state photoluminescence (PL) measurements

PL spectra were collected by a spectrometer (DU420A-OE, ANDOR). Fluorescence decay dynamics

were recorded by TCSPC (Becker&Hickl, SPC-150).

5
sEQE measurements.

The sEQE measurements were conducted using a halogen lamp light source, a monochromator

(Newport CS260), a Stanford SR830 lock-in amplifier, and a Stanford SR570 current amplifier. The

lamp intensity was calibrated by a Si detector (Hamamatsu s1337-1010BQ).

EL measurements

The EL spectra were measured by using a source meter (Keithley 2400) to inject electric current, and

recorded by a Kymera-328I spectrograph and a Si EMCCD purchased from Andor Technology

(DU970P), and a InGaAs CCD camera (DU491A-1.7, Andor Technology).

EQEEL measurements

EQEEL was determined by a homebuilt setup using a Keithley 2400 to inject current into the solar

cells. The Si detector (Hamamatsu s1337-1010BQ) and a Keithley 6482 picoammete were used to

determine the emission photon-flux of the solar cells.

Contact angle measurements

The water and glycerol contact angle images of neat films were recorded by using a KRÜSS DSA 100

instrument under atmospheric condition.

Grazing Incidence Wide-Angle X-ray Scattering (GIWAXS)

GIWAXS measurements were conducted at beamline 7.3.3 of the Advanced Light Source. Samples

were prepared on Si substrates utilizing blend solutions identical to those employed in the fabrication

of devices. A 10 keV X-ray beam was incident at a grazing angle ranging from 0.12° to 0.16°, chosen

to optimize the scattering intensity from the samples. The scattered X-rays were captured by a Dectris

Pilatus 2M photon counting detector.

Atomic Force Microscopy (AFM) measurement

AFM measurement was performed on a Dimension Icon AFM (Bruker) in a tapping mode under

ambient conditions. (GIWAXS) patterns were acquired by detector Pilatus3R 1M, Dectris (X-ray

Source: MetalJet-D2, Excillum).

Photo-induced Force Microscopy (PiFM)

6
PiFM is a multimodal Atomic Force Microscopy (AFM) technique that integrates the high resolution

of AFM with infrared spectroscopy to acquire topographical and molecular information with sub-10

nanometer resolution. All measurements were conducted using Molecular Vista's Visascope

microscope and Block Engineering's Laser Tune QCL, with an adjustable range from 775 to 1885 cm-1

and a spectral linewidth of 2 cm-1. PiFM images were created with a resolution of 256×256 pixels, line

speed of 0.89 lines/s, and a size of 1 µm2, using wavenumbers 1648 cm-1, 1278 cm-1, and 1539 cm-1

to emphasize the PM6, L8-BO, and Z-Tri.

Transient absorption spectroscopy (TAS) measurement

Femtosecond transient absorption spectroscopy measurements were performed on an Ultrafast Helios

pump-probe system in collaboration with a regenerative amplified laser system from Coherent. An

800 nm pulse with a repetition rate of 1kHz, a length of 100 fs, and an energy of 7 mJ/pluse, was

generated by an Ti:sapphire amplifier (Astrella, Coherent). The time delay between pump and probe

was controlled by a motorized optical delay line with a maximum delay time of 8 ns. The samples

films were spin-coated onto the 1 mm-thick quartz plates and are encapsulated by epoxy resin in

nitrogen-filled glove box to resist water and oxygen in the air. The pump pulse is chopped by a

mechanical chopper with 500 Hz and then focused on to the mounted sample with probe beams. The

probe beam was collimated and focused into a fiber-coupled multichannel spectrometer with CCD

sensor. The energy of pump pulse was measured and calibrated by a power meter (PM400, Thorlabs)

Estimation of glass-transition temperature (Tg)

The glass transition temperature (Tg) was determined using ultraviolet-visible spectroscopy.

Absorption spectra measurements were conducted on the receptor thin film, with the annealing

temperature ranging from 20°C to 240°C. Then, the deviation metric (DMT) of the each absorption

spectra was calculated, following the method from Samuel E. Root et al. DMT= ∑λmax λmin [IRT (λ) -

IT (λ)]2where λ is the wavelength, λmax and λmin are the upper and lower bounds of the optical sweep,

respectively, IRT(λ) and IT(λ) are the normalized absorption intensities of the as-cast (room

temperature) and annealed films, respectively. Then, Tgs were determined to points where the two

interpolated lines in low- and high-temperature regions intersect.

7
8
2.Figures and Tables

CF CB

Fig. S1. Photograph of Z-Tri dissolved in chloroform and chlorobenzene solutions.

9
(b)

L8-BO
Z-Tri
Deviation Metric

Tg= 106 ℃
Tg= 139 ℃

0 50 100 150 200

Temperature (℃ )

Fig. S2. UV-Vis deviation metric results of L8-BO and Z-Tri.

10
Fig. S3. UV-vis absorption spectra of blend films (a) in the solutions and (b) in the films.

11
(a) (b)
——PM6 ——L8-BO
LUMO=-3.48 eV LUMO=-3.88 eV
HUMO=-5.44 eV HUMO=-5.69 eV
Current

Current
-0.50 1.31
-0.90 1.06

-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5

Potential (V) Potential (V)

(c)
——Z-Tri

LUMO=-3.52 eV
HUMO=-5.45 eV
Current

-0.86 1.07

-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5

Potential (V)

Fig. S4. Cyclic voltammetry curves of (a) PM6, (b) L8-BO, and (c) Z-Tri.

12
 (a) (b)
4
10 Hole-only device Electron-only device
104
Current Density (mA cm-2)

Current Density (mA cm-2)

PM6:L8-BO PM6:L8-BO
103 PM6:L8-BO:Z-Tri PM6:L8-BO:Z-Tri
PM6:Z-Tri 103 PM6:Z-Tri

102
102

101
101

100
100

0.1 0.2 0.5 1 2 5 0.1 0.2 0.5 1 2 5

Voltage (V) Voltage (V)

Fig. S5. (a) SCLC curves of hole-only devices based on binary and ternary devices. (b) SCLC curves of

electron-only devices based on binary and ternary devices.

13
 v(a)

1.0
Normalized PCE

0.8

PM6:L8-BO
0.6 PM6:Z-Tri
PM6:L8-BO:Z-Tri
0.4

0.2

0.0
0 150 300 450 600 750 900
Time (h)

Figure S6. The photostability of the solar cells under continuous 100 mW/cm² illumination in air.

14
 v(a)

1.0

0.8
Normalized PCE

0.6
PM6:L8-BO
PM6:Z-Tri
0.4 PM6:L8-BO:Z-Tri

0.2

0.0
0 100 200 300 400 500
Time (h)

Figure S7. The thermal stability of the solar cells under continuous heating at 80°C.

15
 L8-BO Z-Tri
LUMO=-3.45 eV LUMO=-3.24 eV

HUMO=-5.31eV HUMO=-5.25 eV

Fig. S8. The HOMO/LUMO structures of L8-BO and Z-Tri are based on DFT (B3LYP/6-31G level)

calculation. (Alkyl side chains were replaced with methyl groups for simplifying calculation.)

16
Heat Maps Calculation

In the donor-acceptor (D-A) interface of OSCs, heat maps are crucial for demonstrating the charge

transfer process. They vividly display the electron transfer from the donor to the acceptor and the hole

accumulation in the donor. On the heat map, the electron concentration gradually increases on the acceptor

side, indicating successful electron migration from the donor material, which is a key step in the charge-

separation process of OSCs. Meanwhile, the hole concentration rises on the donor side as electrons leave,

leaving behind holes that accumulate in this region. Such visualization by heat maps directly reflects the

charge transfer direction. The movement of electrons and the corresponding hole accumulation define the

charge-transfer pathway. Additionally, the degree of change in electron and hole concentrations on the

heat map can be used to infer the charge transfer efficiency. A steeper increase in electron concentration

on the acceptor side and a more significant rise in hole concentration on the donor side may imply a more

efficient process, whereas a less pronounced change may suggest barriers or inefficiencies in the

interface's charge-transfer mechanism. Overall, heat maps are powerful tools for understanding the

charge-transfer behavior at the D-A interface, essential for improving device.

17
 (a)
PM6:L8-BO

LE

CT

(b)
PM6:Z-Tri

LE

CT

Fig. S9. Optimized geometry of the PM6:L8-BO and PM6:Z-Tri complexes, electron-hole distribution

diagram.

18
Luminescence Lifetime Calculation

The formula for calculating the luminescence lifetime is expressed as:

1.5
𝜏=
𝑓·∆𝐸2

(1)

This formula plays a crucial role in the field of luminescence research, enabling us to quantitatively

determine the duration for which a luminescent material emits light. In this formula, the variable 𝜏

represents the luminescence lifetime, and its unit is seconds. The luminescence lifetime is a key parameter

that characterizes the decay behavior of the excited - state population in a luminescent system. It provides

valuable information about the stability and efficiency of the luminescence process. On the other hand,

ΔE is the energy gap. It is measured in the unit of cm-1, which is a commonly used unit in spectroscopy

to describe energy differences between energy levels. This energy gap is related to the electronic or

vibrational transitions within the luminescent material. Based on the mathematical form of the formula 1,

we can clearly observe an inverse - square relationship between the luminescence lifetime 𝜏 and the energy
2
gap ΔE. As the value of the energy gap ΔE becomes smaller, the denominator 𝑓·∆𝐸 of the formula

decreases. Since the numerator is a constant value of 1.5, a decrease in the denominator leads to an

increase in the value of the entire fraction. Consequently, the luminescence lifetime 𝜏 becomes longer.

This relationship is of great significance in understanding the fundamental mechanisms of luminescence

and in the design and optimization of luminescent materials.

19
 (a)
PM6:L8-BO

ΔE=0.519 eV

E=2.399 eV PM6:L8-BO

(b)
PM6-Z-Tri

ΔE=0.362 eV
PM6:Z-Tri
E=2.283 eV

Fig. S10. Optimized geometry of the (a) PM6:L8-BO and (b) PM6:Z-Tri excitation process diagram, and

diagram of corresponding energy states.

20
Fig. S11. Contact angles of PM6, L8-BO, and Z-Tri neat films based on water and glycerol drops.

21
Energy Loss Calculation

As shown in equation 2, Eloss can be segmented into three distinct components: the radiative

recombination loss from absorption above the bandgap (ΔE1), the additional radiative recombination loss

from the absorption below the bandgap (ΔE2), and the non-radiative recombination loss (ΔEnr). ΔE1

SQ SQ
defined as Eg - qV oc (qV oc is maximum Voc predicted by the Shockley–Queisser limit) strongly

depends on the Eg, which is considered as unavoidable loss in any types of solar cells. ΔE2 can be obtained

SQ rad rad
from the equation of qV oc - qV oc , where V oc is V when only considering radiative recombination.
oc

rad
By fitting sEQE and EL spectra, we determined the V oc of the device.

SQ SQ rad rad
Eloss = Eg - qVoc = ( Eg - qV oc )＋(qV oc - qV oc )＋(qV oc - qVoc)

SQ rad,belowgap non - rad

= ( Eg - qV oc )＋(q∆V oc )＋(q∆V oc )

= ∆𝐸1＋∆𝐸2＋ΔEnr

(2)

ΔEnr has been recognized as the key factor to limit the Voc of OSCs, which can be calculated from the

quation 3:

ΔEnr = - KT ln(EQEEL)

(3)

where K is the Boltzmann constant, T is the Kelvin temperature. The Eg is determined by identifying the

intersection points of EL and absorption spectra of the blend film.

22
 (a) 1.2 (b) 1.2
PM6:L8-BO PL PM6:L8-BO:Z-Tri PL
Absorption Absorption
1.0 1.0

Normalized PL/Abs

Normalized PL/Abs
0.8 0.8

0.6 0.6

0.4 Eg = 1.486 eV 0.4 Eg =1.498 eV

0.2 0.2

0.0 0.0

1.0 1.2 1.4 1.6 1.8 2.0 1.0 1.2 1.4 1.6 1.8 2.0

Energy (eV) Energy (eV)

(c) 1.2
PM6:Z-Tri PL
Absorption
1.0
Normalized PL/Abs

0.8

0.6

0.4 Eg =1.546 eV

0.2

0.0

1.0 1.2 1.4 1.6 1.8 2.0

Energy (eV)

Fig. S12. Normalized reduced PL and absorption spectra of (a) PM6:L8-BO (b)PM6:L8-BO: Z-Tri, and

(c) PM6: Z-Tri films.

23
(i)
102

101

100

10-1

10-2
EQE

10-3

10-4

10-5 PM6:L8-BO:Z-Tri (Eu=21.2 meV)

PM6:Z-Tri (Eu=23.8 meV)
10-6
PM6:L8-BO (Eu=22.4 meV)
10-7

10-8
1.0 1.5 2.0 2.5 3.0 3.5
Energy (eV)

Fig. S13. EQE of the binary and ternary devices.

24
 (a) (b)
1010 1010
Blank Blank
109 L8-BO on 109 Z-Tri on
L8-BO off Z-Tri off
108 108

107

Count
107
Count

106 106

105 105

104 104

103 103
700 800 900 1000 1100 700 800 900 1000 1100

Wavelength (nm) Wavelength (nm)

(c)
1010
Blank
109 L8-BO:Z-Tri on
L8-BO:Z-Tri off
108

107
Count

106

105

104

103
700 800 900 1000 1100
Wavelength (nm)

Fig. S14. Schematic for a PLQY measurement of (a) L8-BO, (b) Z-Tri, and (c) L8-BO:Z-Tri. (The red

line is the light on the sample, directly exciting the sample, blank substrate beside; The blue line is the

light hitting the blank substrate, scattering the light to excite the sample; The black lines are only two

blank substrates inside the integrating sphere.)

25
 (e)

1.0

Linear summation
0.8 PM6:L8-BO:Z-Tri PM6:Z-Tri

Normalized EL
+
PM6:L8-BO
0.6

0.4

0.2

800 900 1000 1100

Wavelength (nm)

Fig. S15. The EL spectra of PM6:L8-BO:Z-Tri and binary blends (16.7% PM6:L8-BO+83.3% PM6:Z-

Tri).

26
 (a) (b)
1000 1000
ΔA (mOD) ΔA (mOD)
L8-BO:Z-Tri L8-BO
Pump @ 650 nm -2.0 -0.50 1.0
Pump @ 650 nm
-2.0 -0.50 1.0

100 100

Delay time (ps)

Delay time (ps)

10 10

1 1

0.1 0.1
600 700 800 900 600 700 800 900
Wavelength (nm) Wavelength (nm)

(c)
1000
ΔA (mOD)
Z-Tri
-2.0 -0.50 1.0
Pump @ 650 nm
100
Delay time (ps)

10

0.1
600 700 800 900
Wavelength (nm)

Fig. S16. 2D TAS images of (a) L8-BO:Z-Tri, (b) L8-BO, and (c) Z-Tri films with 650 nm excitation.

27
Fig. S17. TA spectra of the Z-Tri pumped at 900 nm.

28
Fig. S18. TA spectra of the L8-BO pumped at 900 nm.

29
Fig. S19. TA spectra of the L8-BO:Z-Tri blends pumped at 900 nm.

30
Fig. S20. TA spectra of the PM6:L8-BO:Z-Tri blends pumped at 900 nm.

31
Fig. S21. TA spectra of the PM6:L8-BO blends pumped at 900 nm.

32
Fig. S22. TA spectra of the PM6:Z-Tri blends pumped at 900 nm.

33
(c)

1.0 L8-BO
Z-Tri
Normalized Absorption (a.u.)

L8-BO:Z-Tri
0.8

0.6

0.4

0.2

0.0
400 500 600 700 800 900 1000
Wavelength(nm)

Fig. S23. UV-vis absorption spectra of L8-BO, Z-Tri, and L8-BO:Z-Tri.

34
 (a) (b)
PM6:L8-BO PM6:Z-Tri

(c)
PM6:L8-BO:Z-Tri

Fig. S24. AFM height images of (a) PM6:L8-BO, (b) PM6:Z-Tri, and (c) PM6:L8-BO:Z-Tri blend films.

35
(a) (b) (c)

PM6 (d)

L8-BO (e)

Z-Tri
OOP

IP

(d) (e)
10-2 PM6 PM6
IP OOP
L8-BO L8-BO
Z-Tri Z-Tri
10-3

Intensity
10-3
Intensity

10-4
10-4

0.2 0.4 0.6 1 1.5 2

-1
qxy (Å ) qz (Å ) -1

Fig. S25. The GIWAXS patterns of neat films of donor and acceptors. (a-c) The 2D GIWAXS patterns

of the films; (d) In-plane and (e) out-of-plane cuts of the films with GIWAXS patterns.

36
Fig. S26. 1H-NMR spectrum of compound 3 in CD2Cl2.

37
 1892.978

Z-Tri

Fig. S27. MS (MALDI-TOF) spectrum of Z-Tri.

38
 Z-Tri

Fig. S28. 1H-NMR spectrum of T Z-Tri in CDCl3.

39
 Z-Tri

Fig. S29. 13C-NMR spectrum of T Z-Tri in CDCl3.

40
Table S1. Optical and electrochemical properties of the photoactive materials.

𝜆𝑚𝑎𝑥solution a 𝜆𝑚𝑎𝑥film b 𝜆𝑜𝑛𝑠𝑒𝑡film c 𝐸𝑜𝑝𝑡

𝑔 d Tg e EHOMO f ELUMO g
Materials
(nm) (nm) (nm) (eV) (℃) (eV) (eV)

L8-BO 728 805 885 1.40 106 -5.69 -3.88

Z-Tri 726 778 855 1.45 139 -5.45 -3.52

a) The maximum absorption in solutions; b) The maximum absorption in thin films; c) Absorption onsets

in thin films; d) Optical band gap (Eg) was calculated through the onset of the thin-film absorption edge;

e) Obtained by UV/Vis DMT results; f) Calculated by EHOMO = -4.80 eV - Eox; g) ELUMO = -Ered - 4.80

eV.

41
Table S2. Summary of photovoltaic parameters of the ternary devices with different Z-Tri contents.

Active Layer Voc (V) Jsc (mA cm-2) FF (%) PCE (%)a

PM6:L8-BO (1:1.2) 0.894 26.51 80.1 18.98

PM6:L8-BO:Z-Tri (1:1.1:0.1) 0.901 26.83 80.0 19.34

PM6:L8-BO:Z-Tri (1:1:0.2) 0.927 27.30 80.3 20.32

PM6:L8-BO:Z-Tri (1:0.8:0.4) 0.948 20.17 75.0 14.34

PM6:L8-BO:Z-Tri (1:0.7:0.5) 0.950 19.98 69.2 13.13

PM6:L8-BO:Z-Tri (1:0.5:0.7) 0.954 17.99 59.8 10.26

PM6:L8-BO:Z-Tri (1:0.2:1) 0.958 15.62 47.5 7.11

PM6:Z-Tri (1:1.2) 1.001 9.22 43.0 3.97

a) Average values obtained from 30 devices.

42
Table S3. The hole mobilities and electron mobilities of the binary and ternary devices.

μ ha μe a
Active Layer μh/μe
(10−4 cm2 V−1 s −1) (10−4 cm2 V−1 s −1)

PM6:L8-BO 2.91 ± 0.35 2.34 ± 0.19 1.24

PM6:Z-Tri 2.68 ± 0.21 1.94 ± 0.14 1.38

PM6:L8-BO:Z-Tri 4.79 ± 0.15 4.21 ± 0.11 1.13

a) Average values obtained from 30 devices.

43
Table S4. Contact angle and surface tension data of PM6, L8-BO, and Z-Tri neat films.

Materials θwater (°) θglycerol (°) γ (mN m-1) χ

PM6 101.8 90.7 17.2

L8-BO 92.7 78.4 26.1 0.93

Z-Tri 93.6 80.3 24.2 0.60

44
Table S5. Crystal coherence length and the d-spacings of (010) peaks in OOP direction and (100) peaks

in IP direction of neat and blend films.

Materials 010 (OOP) 100 (IP)

q d-spacing a FWHM CCL b q d-spacing a FWHM CCL b

(Å-1) (Å) (Å-1) (Å) (Å-1) (Å) (Å-1) (Å)

PM6 1.579 3.977 0.3794 14.73 0.288 21.80 0.1089 51.32

L8-BO 1.614 3.890 0.3821 14.63 0.409 15.35 0.1548 36.11

Z-Tri 1.530 4.104 0.4321 12.93 0.436 14.41 0.1911 29.25

PM6:L8-BO 1.618 3.881 0.3570 15.66 0.296 21.21 0.1021 54.74

PM6:Z-Tri 1.587 3.957 0.4162 13.43 0.308 20.38 0.0837 66.78

PM6:L8-BO:Z-Tri 1.621 3.874 0.3478 16.07 0.303 20.72 0.0929 60.16

a) Obtained by the equation of d = 2π/q, in which q corresponds to the diffraction peak positions; b)

Calculated using the equation: CCL = 2 πK/FWHM, in which w is the full width at half maxima and K is

a form factor (0.89 here).

45
Table S6. The photovoltaic performance for PM6:L8-BO:Z-Tri (1:1:0.2) based OSCs with different

active layer thicknesses.

Thickness (nm) Voc (V) Jsc (mA cm-2) FF (%) PCE (%)

100 0.929 26.88 78.7 19.65

110 0.928 26.98 79.1 19.80

120 0.927 27.30 80.3 20.32

130 0.917 27.01 79.7 19.74

140 0.911 26.97 79.7 19.58

46
Table S7. Summary of photovoltaic parameters for PM6:L8-BO:Z-Tri (1:1:0.2) devices with different

annealing temperatures.

Temperature
Voc (V) Jsc (mA cm-2) FF (%) PCE (%)
(℃)

80 0.928 26.49 79.1 19.44

100 0.927 27.30 80.3 20.32

120 0.924 26.85 79.3 19.67

47
Table S8. Comparison of efficiency and energy loss between this work and earlier references.

ΔEnr Voc Eloss PCE

Active Layer Ref.
(eV) (V) (eV) (%)

PM6:CH17:F-2F 0.190 0.889 0.490 18.13 2

PM6:BTP-eC9:ZH2 0.241 0.862 0.514 18.75 3

D18:Y6:IDTT-SiO-IC 0.212 0.896 0.531 18.77 4

PM6:CH-ThCl:CH-6F 0.208 0.932 0.508 18.80 5

PM6:L8-BO:BTP-S9 0.189 0.872 0.540 18.84 6

PBQx-TF:eC9-2Cl:F-BTA3 0.219 0.879 0.551 19.00 7

PM1:L8-BO:BTP-F3Cl 0.186 0.885 0.549 19.10 8

D18:Aqx-18:L8-BO 0.198 0.928 0.543 19.10 9

PM1:L8-BO:BTP-2F2Cl 0.197 0.881 0.547 19.17 10

PM6:L8-BO:BTP-H2 0.196 0.892 0.558 19.20 11

PM6:D18-Cl:L8-BO 0.208 0.910 0.546 19.22 12

PM6:L8-BO-X:Tri-V 0.212 0.892 0.539 19.86 13

PM6:BTP-eC9:o-BTP-eC9 0.190 0.860 0.525 19.88 14

PM6:BO-4Cl:BO-5Cl 0.198 0.872 0.498 18.56 15

PNTB-2T:Y6:PC71BM 0.217 0.875 0.533 17.35 16

PM6:BTP-4F-12:MeIC 0.227 0.863 0.526 17.40 17

PM6:Y6:S3 0.223 0.856 0.579 17.53 18

PM6:Y6:C8-DTC 0.215 0.873 0.537 17.52 19

PM6:Y6:3TP3T-4F 0.220 0.85 0.560 16.70 20

PM6:BTP-eC9:L8-BO-F 0.199 0.853 0.519 18.66 21

48
 PM6:Y6:ZY-4Cl 0.198 0.863 0.520 18.69 22

PM6:L8-BO-X:Y-C10ch 0.223 0.886 0.544 19.10 23

PM6:BTP-eC9:PhC6-IC-F 0.140 0.835 0.545 18.33 24

PM6:BTP-eC9:5BDDBDT-Cl 0.220 0.854 0.540 18.43 25

D18:N3-BO:F-BTA3 0.183 0.924 0.534 20.25 26

PM6:PY-1S1Se:PY-2Cl 0.184 0.914 0.523 18.20 27

PM6:IDTR:L8-BO 0.234 0.902 0.550 19.12 28

PM6:BTP-BO4Cl:5BDTBDD 0.224 0.843 0.545 17.54 29

PM6:BTP-eC9:MOIT-M 0.210 0.87 0.520 18.50 30

D18:Z8:L8-BO 0.190 0.92 0.510 20.20 31

D18:BTP-eC9-4F:DM-F 0.180 0.89 0.540 19.49 32

PM6:L8-BO:Z-Tri 0.196 0.927 0.571 20.32 This work

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