Tuning Performance Of Organic

Thermoelectrics (OTEs) By Dopant

Control
Jalu Setiya Pradana, Irene Santambrogio, Job De Leener
TA: Tzu-Yi (Thomas) Yu

Materials Physics and Technologies for Nanoelectronics

 Content

 Introduction

 Organic Semiconductors

 Dopants

 Doping methods

2 Materials Physics and Technologies for Nanoelectronics

 Introduction

Why OTE?

OTE usage

Performance tuning Flexible thermoelectric generator

DOI: 10.1016/j.mser.2018.09.001
3 DOI: 10.1038/srep18805 Materials Physics and Technologies for Nanoelectronics
 OTE properties

4 Materials Physics and Technologies for Nanoelectronics

 Organic Semiconductors
• Conjugated molecules:
 π-bonding between sp2 C atoms results in delocalized molecular orbitals
 Charges can be delocalized due to resonance structures 

• Organic Thermoelectric molecular structures

Poly(4-ethyleneoxythiophene) Poly(3-hexylthiophene) Poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)

(PEDOT) (P3HT) (PBTTT)

Nat. Rev. Mater., 2016, 1, 16050 ACS Appl. Mater. Interfaces, 2019, 11, 4942−4953

5 Materials Physics and Technologies for Nanoelectronics

 Effect of Alkyl Side Chain Length
SIDE CHAINS
CRYSTALLIZATION

SIDE CHAINS
MELTING

UV-vis-NIR polarized optical spectroscopy Differential Scanning Calorimetry

ACS Appl. Mater. Interfaces, 2019, 11, 4942−4953

6 Materials Physics and Technologies for Nanoelectronics

 Effect of Alkyl Side Chain Length: C12-PBTTT
Figure of merit Electrical conductivity Seebeck coefficient

( )
𝟐 /𝟑
𝝈𝑺 𝑻 𝟐
𝟏
𝒛𝑻 = 𝝈 =𝒒𝒏 𝝁 𝑺∝
𝜿 𝒏

SIDE CHAINS CRYSTALLINITY AFFECTS DOPANT DIFFUSION, THUS n

Side [Anion] σ// S// PF

chain (%) (S cm ) -1
(μV K ) -1 (μW m-2 K-1)

C8 7.6 15 48 2.5 C12-PBTTT shows the

C12 14 193 77 100 best TE properties!
C14 6.9 39 80 33
C18 3.3 6 240 22
ACS Appl. Mater. Interfaces, 2019, 11, 4942−4953

7 Materials Physics and Technologies for Nanoelectronics

 Effect of Single Ether-Based Side Chains

Chemical structures and measured Differential Scanning Calorimetry

energy levels of polymers and dopant
Adv. Energy Mater., 2022, 12, 2103049

8 Materials Physics and Technologies for Nanoelectronics

 Effect of Single Ether-Based Side Chains
PBTTT-C12

PBTTT-8O

UV-vis-NIR polarized optical spectroscopy

Polymer σ// S// PF
(S cm-1) (μV K-1) (μW m-2 K-1)
PBTTT-C12 2430 47 530
PBTTT-8O 5∙104 24 2900
DFT calculation
PBTTT-8O shows the best TE properties!
Adv. Energy Mater., 2022, 12, 2103049

9 Materials Physics and Technologies for Nanoelectronics

 Side Chains: summary
Alkyl Side Chain Length
✘ Disordered side chains hamper
efficient dopant diffusion
✘ Crystalline side chains hamper
efficient dopant diffusion
✔ Loosely packed side chains allow
efficient dopant diffusion
Single Ether-Based Side Chain
✘ OEG side chains adversely affect
structure and stability
✔ Single ether-based side chains
preserve structure and stability
✔ Single ether-based side chains
improve doping efficiency

Single Ether-Based Side Chains shows the best TE performance!

ACS Appl. Mater. Interfaces, 2019, 11, 4942−4953 Adv. Energy Mater., 2022, 12, 2103049

10 Materials Physics and Technologies for Nanoelectronics

 Molecular design of dopants

• Compatible energy offset

 right EA (LUMO)
 e--deficient cores delocalize -bonds
 electron-withdrawing groups (–CN and –CF3)

• Size/configuration
 distortions
 doping efficiency
 volume in the microstructure

Chem. Soc. Rev., 2020, 49, 7210

11 Materials Physics and Technologies for Nanoelectronics
 F6TCNQ vs F4TCNQ in PBTTT

J. Mater. Chem. C, 2020, 8, 16470

Materials Physics and Technologies for Nanoelectronics 12
 F2TCNQ vs F4TCNQ in PBTTT
 Changing the Seebeck coefficient
 OCL
 --stacking
Out-of-plane In-plane

Neat

F4TCNQ
F2TCNQ

Sci. Adv., 2017, 3, e1700434

13 Materials Physics and Technologies for Nanoelectronics

 Doping Methods

• Mixed doping
 Mixing host materials and
dopants

• Sequential doping
 diffusion of dopant to host
material thin film

• Electrochemical doping
 Host materials are doped directly
through electrochemical reactions
Chem. Soc. Rev., 2020, 49, 7210

14 Materials Physics and Technologies for Nanoelectronics

Mixed Doping vs Sequential Doping

Sci. Adv., 2017, 3, e1700434

Vapor doping has higher σ and PF while solution doping has higher S

Materials Physics and Technologies for Nanoelectronics

Crystalline Structure
Out-of-plane In-plane

Neat Solution F4TCNQ Vapor F4TCNQ

Sci. Adv., 2017, 3, e1700434

• Both doping methods have the same lamella-stacked side chains ()

• Vapor doping () has smaller π-π–stacking distance than solution doping ()

Materials Physics and Technologies for Nanoelectronics

 Effect of Positional Distribution
Solution Sequential Vapor Doping
Doping

𝜎 =𝑞𝑛 𝜇

Adv. Electron. Mater., 2022, 8, 2101142

Dopant in crystalline domains led to high which will increase the PF

17 Materials Physics and Technologies for Nanoelectronics

 Doping methods: summary
Doping methods Sequential doping Sequential doping

Vapor doping Vapor doping

Mixed doping Sequential doping

Solution Sequential
Solution doping doping

Chem. Soc. Rev., 2020, 49, 7210 Sci. Adv., 2017, 3, e1700434 Adv. Electron. Mater., 2022, 8, 2101142

18 Materials Physics and Technologies for Nanoelectronics

 Conclusion

• Side chain crystallinity affects dopant diffusion, thus n and TE parameters,

and the best performance are given by single-ether side chain
• Job’s conclusion
• Doping methods affect OTE performance and sequential (vapor) doping is
shown better TE performance so far

19 Materials Physics and Technologies for Nanoelectronics