Obtained parameters based on theoretical simulation.
Abstract
We have systematically investigated thermoelectric properties by a series of doping in layered cobaltites Bi2Sr2Co2Oy, verifying the contribution of narrow band. In particular, Sommerfeld coefficient is dependent on charge carriers’ density and as function of density of states (DOS) at Fermi level, which is responsible for the persistent enhancement of large thermoelectric power. Especially for Bi2Sr1.9Ca0.1Co2Oy, it may provide an excellent platform to be a promising candidate of thermoelectric materials. On the other hand, high‐performance thermoelectric materials require elaborate doping and synthesis procedures, particularly the essential thermoelectric mechanism still remains extremely challenging to resolve. In this chapter, we show evidence that thermoelectricity can be directly generated by a natural chalcopyrite mineral Cu1+xFe1−xS2 from a deep‐sea hydrothermal vent, wherein the resistivity displays an excellent semiconducting character, while the large thermoelectric power and high power factor emerge in the low x region where the electron‐magnon scattering and large effective mass manifest, indicative of the strong coupling between doped carriers and localized antiferromagnetic spins, adding a new dimension to realizing the charge dynamics. The present findings advance our understanding of basic behaviors of exotic states and demonstrate that low‐cost thermoelectric energy generation and electron/hole carrier modulation in naturally abundant materials is feasible.
Keywords
- layered cobalt oxides
- narrow band contribution
- natural chalcopyrite mineral
- thermoelectricity generation
- electron‐magnon scattering
1. Introduction
Layered cobaltites with CdI2‐type CoO2 block provide an excellent platform for investigating thermoelectric properties. A key to unveil mysterious thermoelectric properties lies in the two‐dimensional (2D) conducting CoO2 layer. For layered Bi‐
On the other hand, ternary chalcogenides serve as an ideal platform for investigating intricate physical and chemical characteristics controlling the efficiency of thermoelectric materials, and also are promising materials for potential applications in photovoltaics, luminescence, as well as thermoelectric and spintronic devices [10–13]. Ternary chalcopyrite‐structured chalcogenides, such as CuFeS2, have attracted particular attention owing to their unique optical, electrical, magnetic, and thermal properties [14–28]. Studies on chalcopyrite (CuFeS2) have primarily focused on its electronic states [14, 15, 29–31]. However, the microscopic mechanism of electronic structure and thermoelectric character in CuFeS2, which presumably arises from some scenarios such as delocalization of the Fe 3
In this chapter, we confirm that an unexpected thermoelectricity can directly be generated in a natural chalcopyrite mineral Cu1+
2. Thermoelectric properties and narrow band contribution of Bi2Sr1.9M 0.1Co2Oy and Bi2Sr2Co1.9X 0.1Oy
2.1. Crystal structure and valence states of Co ions
The crystal structure of Bi2Sr2Co2O
2.2. Resistivity and transport mechanism
Figure 2a and d shows temperature dependence of resistivity
To get insight into the conduction mechanism below
2.3. Thermoelectric power and narrow band model
Figure 3a and b shows temperature dependence of thermoelectric power
In general,
Actually, activation energy
2.4. X‐ray photoemission spectroscopy and thermal conductivity
In order to further verify the narrow band model, we carried out XPS spectra for Bi2Sr1.9Ca0.1Co2O
Temperature dependence of total thermal conductivity
3. Exotic reinforcement of thermoelectric power in layered Bi2Sr2−x Cax Co2Oy
3.1. XRD patterns and electrical transport properties
The crystal structure of Bi2Sr2Co2O
Figure 7a and b shows resistivity
To discern conduction mechanism below
3.2. Enhancement of thermoelectric power driven by Ca doping
Figure 8a shows thermoelectric power
As we know,
3.3. Specific heat and Sommerfeld coefficient
Next we will check whether the enhanced
Now we discuss the underlying implications of enhanced
4. Thermoelectricity generation and electron‐magnon scattering in a natural chalcopyrite mineral
4.1. Crystal structure and SEM characterization
A series of natural chalcopyrite minerals, Cu1+
To probe the microstructures of natural Cu1+
4.2. Thermoelectricity generation and electronic states
To examine the functional properties of natural Cu1+
In order to track the evolution of electronic states, we carried out thermoelectric power (
4.3. Electron‐magnon scattering and large effective mass
The matter of imperative concern is how to understand the origin of
To better discern intrinsic transport mechanism of Cu1+
Parameter | Δ | ||||
---|---|---|---|---|---|
186 | −6.21 | 0.03 | −3.84×10−8 | 60.1 | |
68 | −75.45 | −0.08 | −5.47×10−8 | 4.9 | |
38 | −10.61 | −0.04 | −3.95×10−8 | 11.8 |
To gain more insight into the correlation between magnon drag, doped carriers, and
In terms of thermal conductivity
5. Conclusions
Our results of layered cobaltites Bi2Sr2Co2O
In addition, we demonstrated direct thermoelectricity generation in natural chalcogenides, Cu1+
Acknowledgments
The author gratefully thanks L. H. Yin, W. H. Song, Y. P. Sun, A. U. Khan, N. Tsujii, K. Takai, R. Nakamura, and T. Mori for their fruitful collaboration in the study of layered cobaltites and natural chalcogenides for thermoelectrics. This work was supported by the National Natural Science Foundation of China under Contract No. 10904151, the Fund of Chinese Academy of Sciences for Excellent Graduates, and the NIMS Open Innovation Center (NOIC) of Japan. The author thanks the Sichuan University Talent Introduction Research Funding (grant No. YJ201537) and Sichuan University Outstanding Young Scholars Research Funding (grant No. 2015SCU04A20) of China for financial support.
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