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Zuo, Guangzheng
Publications (5 of 5) Show all publications
Zuo, G. (2018). Doping and Density of States Engineering for Organic Thermoelectrics. (Doctoral dissertation). Linköping: Linköping University Electronic Press
Open this publication in new window or tab >>Doping and Density of States Engineering for Organic Thermoelectrics
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Thermoelectric materials can turn temperature differences directly into electricity. To use this to harvest e.g. waste heat with an efficiency that approaches the Carnot efficiency requires a figure of merit ZT larger than 1. Compared with their inorganic counterparts, organic thermoelectrics (OTE) have numerous advantages, such as low cost, large-area compatibility, flexibility, material abundance and an inherently low thermal conductivity. Therefore, organic thermoelectrics are considered by many to be a promising candidate material system to be used in lower cost and higher efficiency thermoelectric energy conversion, despite record ZT values for OTE currently lying around 0.25.

A complete organic thermoelectric generator (TEG) normally needs both p-type and n-type materials to form its electric circuit. Molecular doping is an effective way to achieve p- and ntype materials using different dopants, and it is necessary to fundamentally understand the doping mechanism. We developed a simple yet quantitative analytical model and compare it with numerical kinetic Monte Carlo simulations to reveal the nature of the doping effect. The results show the formation of a deep tail in the Gaussian density of states (DOS) resulting from the Coulomb potentials of ionized dopants. It is this deep trap tail that negatively influences the charge carrier mobility with increasing doping concentration. The trends in mobilities and conductivities observed from experiments are in good agreement with the modeling results, for a large range of materials and doping concentrations.

Having a high power factor PF is necessary for efficient TEG. We demonstrate that the doping method can heavily impact the thermoelectric properties of OTE. In comparison to conventional bulk doping, sequential doping can achieve higher conductivity by preserving the morphology, such that the power factor can improve over 100 times. To achieve TEG with high output power, not only a high PF is needed, but also having a significant active layer thickness is very important. We demonstrate a simple way to fabricate multi-layer devices by sequential doping without significantly sacrificing PF.

In addition to the application discussed above, harvesting large amounts of heat at maximum efficiency, organic thermoelectrics may also find use in low-power applications like autonomous sensors where voltage is more important than power. A large output voltage requires a high Seebeck coefficient. We demonstrate that density of states (DOS) engineering is an effective tool to increase the Seebeck coefficient by tailoring the positions of the Fermi energy and the transport energy in n- and p-type doped blends of conjugated polymers and small molecules.

In general, morphology heavily impacts the performance of organic electronic devices based on mixtures of two (or more) materials, and organic thermoelectrics are no exception. We experimentally find that the charge and energy transport is distinctly different in well-mixed and phase separated morphologies, which we interpreted in terms of a variable range hopping model. The experimentally observed trends in conductivity and Seebeck coefficient are reproduced by kinetic Monte Carlo simulations in which the morphology is accounted for.  

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2018. p. 67
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1934
National Category
Condensed Matter Physics
urn:nbn:se:liu:diva-147778 (URN)10.3384/diss.diva-147778 (DOI)9789176853115 (ISBN)
Public defence
2018-06-04, Planck, Fysikhuset, Campus Valla, Linköping, 10:00 (English)
Available from: 2018-05-14 Created: 2018-05-14 Last updated: 2019-12-11Bibliographically approved
Zuo, G., Li, Z., Wang, E. & Kemerink, M. (2018). High Seebeck Coefficient and Power Factor in n-Type Organic Thermoelectrics. Advanced Electronic Materials, 4(1), Article ID 1700501.
Open this publication in new window or tab >>High Seebeck Coefficient and Power Factor in n-Type Organic Thermoelectrics
2018 (English)In: Advanced Electronic Materials, E-ISSN 2199-160X, Vol. 4, no 1, article id 1700501Article in journal (Refereed) Published
Abstract [en]

The n-type thermoelectric properties of [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) are investigated for different solution-based doping methods. A novel inverse-sequential doping method where the semiconductor (PCBM) is deposited on a previously cast dopant 4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)-N,N-diphenylaniline film to achieve a very high power factor PF approximate to 35 mu W m(-1) K-2 with a conductivity sigma approximate to 40 S m(-1) is introduced. It is also shown that n-type organic semiconductors obey the -1/4 power law relation between Seebeck coefficient S and sigma that are previously found for p-type materials. An analytical model on basis of variable range hopping unifies these results. The power law for n-type materials is shifted toward higher conductivities by two orders of magnitude with respect to that of p-type, suggesting strongly that n-type organic semiconductors can eventually become superior to their p-type counterparts. Adding a small fraction lower lowest unoccupied molecular orbital material (core-cyanated naphthalene diimide) into PCBM leads to a higher S for inverse-sequential doping but not for bulk doping due to different morphologies.

Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2018
n-type doping; organic thermoelectrics; power factor; Seebeck coefficient
National Category
Other Materials Engineering
urn:nbn:se:liu:diva-144566 (URN)10.1002/aelm.201700501 (DOI)000419670400026 ()

Funding Agencies|Chinese Scholarship Council (CSC)

Available from: 2018-01-29 Created: 2018-01-29 Last updated: 2021-06-11
Zuo, G., Liu, X., Fahlman, M. & Kemerink, M. (2018). High Seebeck Coefficient in Mixtures of Conjugated Polymers. Paper presented at 2018/05/14. Advanced Functional Materials, 28(15), Article ID 1703280.
Open this publication in new window or tab >>High Seebeck Coefficient in Mixtures of Conjugated Polymers
2018 (English)In: Advanced Functional Materials, ISSN 1616-301X, E-ISSN 1616-3028, Vol. 28, no 15, article id 1703280Article in journal (Refereed) Published
Abstract [en]

A universal method to obtain record?high electronic Seebeck coefficients is demonstrated while preserving reasonable conductivities in doped blends of organic semiconductors through rational design of the density of states (DOSs). A polymer semiconductor with a shallow highest occupied molecular orbital (HOMO) level?poly(3?hexylthiophene) (P3HT) is mixed with materials with a deeper HOMO (PTB7, TQ1) to form binary blends of the type P3HTx:B1?x (0 ≤ x ≤ 1) that is p?type doped by F4TCNQ. For B = PTB7, a Seebeck coefficient S = 1100 µV K?1 with conductivity σ = 0.3 S m?1 at x = 0.10 is achieved, while for B = TQ1, S = 2000 µV K?1 and σ = 0.03 S m?1 at x = 0.05 is found. Kinetic Monte Carlo simulations with parameters based on experiments show good agreement with the experimental results, confirming the intended mechanism. The simulations are used to derive a design rule for parameter tuning. These results can become relevant for low?power, low?cost applications like (providing power to) autonomous sensors, in which a high Seebeck coefficient translates directly to a proportionally reduced number of legs in the thermogenerator, and hence in reduced fabrication cost and complexity.

Place, publisher, year, edition, pages
Wiley-Blackwell, 2018
conjugated polymers, doping, kinetic Monte Carlo simulations, organic thermoelectrics, Seebeck coefficients
National Category
Materials Engineering Physical Sciences
urn:nbn:se:liu:diva-147779 (URN)10.1002/adfm.201703280 (DOI)000430101100004 ()

Funding Agencies: Chinese Scholarship Council (CSC)

Available from: 2018-05-14 Created: 2018-05-14 Last updated: 2018-05-31Bibliographically approved
Zuo, G., Andersson, O., Abdalla, H. & Kemerink, M. (2018). High thermoelectric power factor from multilayer solution-processed organic films. Applied Physics Letters, 112(8), Article ID 083303.
Open this publication in new window or tab >>High thermoelectric power factor from multilayer solution-processed organic films
2018 (English)In: Applied Physics Letters, ISSN 0003-6951, E-ISSN 1077-3118, Vol. 112, no 8, article id 083303Article in journal (Refereed) Published
Abstract [en]

We investigate the suitability of the "sequential doping" method of organic semiconductors for thermoelectric applications. The method consists of depositing a dopant (F4TCNQ) containing solution on a previously cast semiconductor (P3HT) thin film to achieve high conductivity, while preserving the morphology. For very thin films (similar to 25 nm), we achieve a high power factor around 8 mu W/mK(-2) with a conductivity over 500 S/m. For the increasing film thickness, conductivity and power factor show a decreasing trend, which we attribute to the inability to dope the deeper parts of the film. Since thick films are required to extract significant power from thermoelectric generators, we developed a simple additive technique that allows the deposition of an arbitrary number of layers without significant loss in conductivity or power factor that, for 5 subsequent layers, remain at similar to 300 S/m and similar to 5 mu W/mK(-2), respectively, whereas the power output increases almost one order of magnitude as compared to a single layer. The efficient doping in multilayers is further confirmed by an increased intensity of (bi)polaronic features in the UV-Vis spectra. Published by AIP Publishing.

Place, publisher, year, edition, pages
National Category
Materials Chemistry
urn:nbn:se:liu:diva-145764 (URN)10.1063/1.5016908 (DOI)000425977500021 ()

Funding Agencies|China Scholarship Council (CSC); Knut och Alice Wallenbergs stiftelse (Project "Tail of the Sun")

Available from: 2018-03-22 Created: 2018-03-22 Last updated: 2018-05-14
Zuo, G., Abdalla, H. & Kemerink, M. (2016). Impact of doping on the density of states and the mobility in organic semiconductors. PHYSICAL REVIEW B, 93(23), 235203
Open this publication in new window or tab >>Impact of doping on the density of states and the mobility in organic semiconductors
2016 (English)In: PHYSICAL REVIEW B, ISSN 2469-9950, Vol. 93, no 23, p. 235203-Article in journal (Refereed) Published
Abstract [en]

We experimentally investigated conductivity and mobility of poly(3-hexylthiophene) (P3HT) doped with tetrafluorotetracyanoquinodimethane (F(4)TCNQ) for various relative doping concentrations ranging from ultralow (10(-5)) to high (10(-1)) and various active layer thicknesses. Although the measured conductivity monotonously increases with increasing doping concentration, the mobilities decrease, in agreement with previously published work. Additionally, we developed a simple yet quantitative model to rationalize the results on basis of a modification of the density of states (DOS) by the Coulomb potentials of ionized dopants. The DOS was integrated in a three-dimensional (3D) hopping formalism in which parameters such as energetic disorder, intersite distance, energy level difference, and temperature were varied. We compared predictions of our model as well as those of a previously developed model to kinetic Monte Carlo (MC) modeling and found that only the former model accurately reproduces the mobility of MC modeling in a large part of the parameter space. Importantly, both our model and MC simulations are in good agreement with experiments; the crucial ingredient to both is the formation of a deep trap tail in the Gaussian DOS with increasing doping concentration.

Place, publisher, year, edition, pages
National Category
Other Physics Topics
urn:nbn:se:liu:diva-130276 (URN)10.1103/PhysRevB.93.235203 (DOI)000378813800009 ()

Funding Agencies|Chinese Scholarship Council (CSC)

Available from: 2016-08-01 Created: 2016-07-28 Last updated: 2018-08-29

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