P-type Material Research Articles

Tuning conduction properties and clarifying thermoelectric performance of P-type half-Heusler alloys TiNi1−xCoxSn (0 ≤ x ≤ 0.15)

TiNiSn is an N-type thermoelectric material with a high-power factor composed of low toxicity and abundant elements. TiNiSn also shows P-type electrical conduction by hole doping. In this study, we tune the conduction properties of TiNi1−xCoxSn (0 ≤ x ≤ 0.15) with Co substitution at the Ni site. The samples were prepared by the arc melting method, and thermoelectric properties were investigated up to 800 K. The results of the Hall effect and the Seebeck coefficient measurements indicate that the majority of charge carriers changes from electrons to holes at x ≥ 0.03, suggesting that Co acts as an acceptor. We report for the first time that Ti0.994Ni1.00Co0.051Sn1.01 exhibits ZT = 0.12 at 675 K. This work reveals that Ti0.994Ni1.00Co0.051Sn1.01 could be a potential P-type thermoelectric material operating at high temperatures.

Phonon-charge carrier dynamics via grain-boundary phase in equilibrium reaction of higher manganese silicide/CNF hybrid composites

Higher manganese (TE) silicide (HMS), an eco-friendly, low-cost, and earth-abundant p-type thermoelectric material, exposes a Nowotny chimney-ladder crystal structure, obeying the 14th-electron rule. Here, a hybrid composite of a carbon nanofiber (CNF) and HMS was synthesized by vacuum melting followed by spark plasma sintering, and its thermoelectric performance were demonstrated. The incorporation of CNF with HMS notably enhances the Seebeck coefficient and decline the thermal conductivity without significantly affecting the carrier concentration and electrical conductivity due to the interfacial energy filtering effect. A maximum Seebeck coefficient of 307 μV/K was recorded for the 0.5% CNF composite with HMS, leading to accomplish a high-power factor of 1755.63 μW/mK2 at 803 K. Also, interfaces, grain boundaries, and dislocations leading to the high magnitude of strain, confirmed from HR-TEM and strain analysis, leads to decrease in lattice thermal conductivity to 1.95 W/mK. As a result, HMS attains the peak zT value of 0.64, suggesting that carbon-based composites are a promising way to boost the thermoelectric performance of HMS-based compounds.

Two-component heterojunction-based ambipolar field effect transistors for improved sensitivity of ammonia sensor

To improve the sensing response of ammonia (NH3) sensors, a two-dimensional configuration molecule 5,11-di-naphthalen-2-yl-6,12-dihydro-indolocarbazole (ICZ-NA) was designed and synthesized as the p-channel organic semiconductor material. Bilayer organic field-effect transistor (OFET) was constructed with ICZ-NA and N,N’-bis(n-octyl)-2,6-dicyanonaphthalene-1,4,5,8-bis(dicarboximide (NDI-8CN2) as p-type and n-type active semiconductor materials respectively, and the two-component devices exhibits excellent ambipolar FET performance. The thin film transistors based on single-component and two-component were further used as sensors for ammonia detection. Compared with the sensors based on NDI-8CN2, the sensitivity and selectivity of ammonia detection based on two-component sensors have been greatly improved, and the ratio of current change can still be maintained over 3.65 %, when the gas concentration lower to 10 ppb level. The higher sensing response and low limit of detection demonstrate that the two-component ambipolar configuration is a highly effective method for improving sensing response capability.

Significantly Enhanced Thermoelectric Performance of p-Type Mg3Sb2 via Zn Substitution on Mg(2) Site: Optimization of Hole Concentration Through Ag Doping.

n-Type Mg3Sb2-based thermoelectric materials have recently garnered significant interest due to their superior thermoelectric efficiency. Yet, the advancement of p-type Mg3Sb2 for thermoelectric applications is impeded by its lower dimensionless figure of merit (zT). In this study, we demonstrate the improved thermoelectric performance of p-type Mg3Sb2 through the strategic optimization of Zn content and Ag doping on the Mg/Zn(2) site. Initially, samples of Mg3-xZnxSb2 (x = 0, 0.5, 1.0, and 1.5) were synthesized via elemental reactions within a Pyrex tube, followed by densification through hot pressing. X-ray diffraction analysis confirmed that the Mg3-xZnxSb2 phases retain the same Pm1 space group as the pristine Mg3Sb2 phase. The strategic substitution of Zn improved the power factor via band convergence and reduced lattice thermal conductivity by introducing point defect phonon scattering. This led to a peak zT of 0.5 at 725 K, with an average zT of 0.25 across the 325-725 K range. Enhancement in carrier concentration was achieved by doping Ag onto the Zn site, culminating in a peak zT of 0.95 at 725 K and an average zT of 0.46 between 325 and 725 K for the Mg2Zn0.97Ag0.03Sb2 sample. This performance surpasses that of most p-type Mg3Sb2-based materials, markedly advancing the potential for Mg3Sb2-based materials in midtemperature heat recovery thermoelectric generators.

Insight into Carrier and Phonon Transports of PbSnS2 Crystals.

The simultaneous optimization of n-type and p-type thermoelectric materials is advantageous to the practical application of the device. As an emerging thermoelectric material, PbSnS2 exhibits highly competitive thermoelectric properties due to its unique carrier and phonon transport characteristics. To promote the utilization of this low-cost thermoelectric material, p-type PbSnS2 crystals are synthesized and optimized through Na doping and Se alloying. The resulting thermoelectric transport properties differ significantly from those reported for n-type crystals, prompting us to compare and analyze both n-type (Cl-doped) and p-type (Na-doped) PbSnS2 crystals from various perspectives. Cl doping is subject to weaker "Fermi pinning" and lower impurity ionization energy compared with Na doping, leading to higher doping efficiency. The different optimal performance directions in n-type and p-type crystals can be attributed to the distinct charge density distributions near the conduction band minimum (CBM) and the valence band maximum (VBM). Additionally, both n-type and p-type crystals exhibit ultralow lattice thermal conductivity due to the low symmetry of their twisted NaCl structure combined with the strong anharmonicity. This comprehensive analysis of PbSnS2 crystals provides a solid foundation for further performance optimization and device assembly, while also sheds light on the investigation of layered thermoelectric materials.

Trinuclear iron-oxo cocatalyst regulating new electron transfer pathway in Pt loaded bismuth oxychloride for efficient photocatalytic hydrogen production

BiOCl, a traditional p-type semiconductor, finds extensive application in photocatalytic oxidation and degradation, whereas it is less common in photocatalytic water splitting and hydrogen production. Here, the photocatalytic hydrogen production performance of black BiOCl has been examined by the introduction of noble metal platinum and cocatalyst trinuclear iron-oxo cluster. During the 5-h photocatalytic process, the established system significantly augments the hydrogen production efficiency of black BiOCl by an estimated factor of 8.53. Under illumination, trinuclear iron-oxo clusters provide electron recombination with holes in the valence band of the catalyst, thereby increasing the utilization of photogenerated electrons. Additionally, since the specific energy level structure has a significant impact on the cocatalyst function, trinuclear iron-oxo clusters can be suitable in a variety of photocatalytic systems. This new endeavor might present creative design approaches and low-cost cocatalyst alternatives for the photocatalytic hydrogen evolution from the water splitting of conventional p-type semiconductor materials.

Atomistic oxidation mechanism of Bi0.5Sb1.5Te3 (0001) surface

Surface oxidation can potentially influence transport properties of thermoelectric materials and service performance of thermoelectric devices. Here, the oxidation mechanism of the (0001) surface of a widely used p-type TE material, Bi0.5Sb1.5Te3 (BST), was investigated using spherical aberration corrected scanning transmission electron microscopy (STEM). Combining atomic resolution STEM and density function theory (DFT), it was revealed that oxidation occurs at room temperature in the dry air through O diffusion into the surface quintuple layer, facilitating formation of both cation and anion vacancies, weakening the Bi-Te and Sb-Te bonds, leading to oxidation product Sb2O3, amorphous Te, and Bi-rich Bi2Te3. Formation of a thin O-rich cation-deficient quintuple layer on the surface and the Bi-rich BST region can significantly reduce the interfacial reaction between BST and Ni electrode, as the reaction layer thickness is reduced by 75% after the surface oxidation. This work provides essential structural information on surface oxidation mechanism and its influence on properties and performance of TE materials and devices.

Optical and optoelectrical characterizations of Cu2ZnSn3S8: A potential nominee for optoelectronic and photovoltaic applications

A successful trial has been accomplished in synthesizing a stable phase of Cu2ZnSn3S8 (CZTS8). The deposited thin films have been obtained by utilizing the chemical bath deposition (CBD) process. Basic characterizations have been applied to check the formation of our new stable material. The formed CZTS8 films disclose the amorphous nature as presented in the x-ray diffraction (XRD) patterns. Also, an enhancement in film morphology has been obtained by expanding the film thickness. Moreover, optoelectrical and linear/nonlinear optical features have been studied for the as-deposited films. Our material has interesting characteristics to be a promising window sheet for thin film solar cells. It reveals a tendency to be an n-type semiconductor material. Further, it shows high optical absorption as well as high optical conductivity. Moreover, it has a direct optical transition, and its energy gap is varied in the range (3.89 eV - 3.94 eV). Additionally, the dispersion and optoelectrical indices were affected by the variation in both film thickness and film roughness. Furthermore, the nonlinear optical indices χ(1),χ(3) and n2 were improved via the increase in film thickness. A satisfactory correlation has been performed between all of the evaluated parameters. The main goal of this study has been achieved by obtaining n-type material by increasing the Tin and Sulfur contents in the CZTS8 as compared with the known p-type material (Cu2ZnSnS4) CZTS4. The revealed findings acknowledge that CZTS8 could be a promising nominee for either optoelectronic or photovoltaic applications.

Evaluation of the Polypyrrole Coupling Mode for High-Performance Dual-Ion Batteries.

Due to the advantages of large interstitial sites, antisolubility, and reversible insertion and extraction of anions, polypyrrole (PPy) has become an excellent P-type electrode material for dual-ion batteries. Unfortunately, PPy electrodes inevitably suffer from low specific capacity and poor cycle stability because of structural disintegration during repeated cycling as well as poor doping ability brought on by aggregation or cross-linking within the PPy chain. In this work, PPy with different proportions of coupling mode (α-α, α-β, or β-β coupling) was derived from different preparation methods. Among them, PPy derived from the interfacial frozen polymerization method (I-PPy) is dominated by the α-α coupling mode and possesses the best anion doping ability and the highest specific capacity of 119 mAh g-1 at 100 mA g-1 compared with PPy derived from electrochemical deposition (E-PPy) and chemical oxidation method (C-PPy) (both less than 40 mAh g-1). This work verifies that increasing the proportion of the α-α coupling mode in the PPy electrode is a useful strategy to enhance the anion doping ability and capacity of dual-ion batteries.

Rational composition engineering toward high thermoelectric performance in p-type EuMg2Sb2-based materials

Mg-based compounds are emerging materials for efficient thermoelectric conversion, as exemplified by n-type Mg3Sb2-based materials, while a high performing p-type Mg3Sb2 material is lacking. EuMg2Sb2, a derivative of Mg3Sb2, has revealed potential as a high-performance alternative to p-type Mg3Sb2-based materials, while pristine EuMg2Sb2 suffers from low carrier concentration. Herein, we reveal that both Zn substitution for Mg and Yb substitution for Eu not only boost the carrier concentration and mobility of p-type EuMg2Sb2-based materials, but also sharply diminish the lattice thermal conductivity via enhancing phonon scattering. Band structure calculation shows that Zn substitution minimizes the energy difference between different bands at the valence band maximum and reduces the band effective mass, leading to optimized band structure. Combined with the role of Ag doping in increasing the carrier concentration and power factor, p-type Eu0.5Yb0.5Mg1.0975Zn0.9975Ag0.005Sb2 sample obtains a maximal dimensionless figure of merit (zT) value of 1.18 at 823 K, which compares favorably to those of EuMg2Sb2 and other p-type Mg–Sb-based Zintl materials. This study demonstrates the efficacy and importance of delicate composition engineering in boosting the thermoelectric performance of p-type EuMg2Sb2.

Long-term carrier lifetime instabilities in n-type FZ- and Cz-silicon under illumination at elevated temperature

Even though n-type Si wafers show a lower extent of light-induced degradation, similar degradation and regeneration behavior as in p-type Si materials has been observed for various n-type Si monocrystalline materials. In this work, the long-term behavior of minority charge carrier lifetime in non-diffused n-type FZ-Si and Cz-Si wafers during illumination at elevated temperatures is investigated. Thereby, various influencing factors such as peak firing temperature and treatment temperature are considered. Degradation and a very strong regeneration effect, which exceeds the initial effective lifetime value, can be observed in the samples. Since surface-related saturation current density remains almost constant during degradation and regeneration, the effect seems to be bulk related. The extent of degradation and regeneration could be shown to be firing temperature-dependent. It could also be shown for n-type FZ-Si wafers that higher firing temperatures result in an increased H2 content within the silicon bulk. Investigations of the injection-dependent defect density revealed that the defect formed during degradation is not a deep level Shockley-Read-Hall defect. Observations at different treatment temperatures and constant illumination of 0.9(1) sun photon flux equivalent have shown that a higher treatment temperature leads to faster degradation and regeneration kinetics. Similarly, higher injection rates also speed up regeneration kinetics. Since degradation also occurs in darkness, the bulk related degradation effect in n-type FZ-Si is charge carrier-induced and not necessarily light-induced.

Origin of Enhanced Photoelectrochemical Activity of the n-CdS/p-type Semiconductor Interface: Homojunction or Heterojunction?

Surface engineering of photoelectrodes is considered critical for achieving efficient photoelectrochemical (PEC) cells, and various p-type materials have been investigated for use as photoelectrodes. Among these, the p-type semiconductor/n-type CdS heterojunction is the most successful photocathode structure because of its enhanced onset potential and photocurrent. However, it is determined that the main contributor to the enhanced activity is the Cd-doped layer and not the CdS layer. In this study, a Cd-doped n+p-buried homojunction of a CuInS2 photocathode is first demonstrated without a CdS layer. The homojunction exhibited a more active and stable PEC performance than the CdS/CuInS2 heterojunction. Moreover, it is confirmed that Cd doping is effective for other p-type materials. These results strongly suggest that the effects of Cd doping on photocathodes should be carefully investigated when designing CdS/p-semiconductor heterojunction photoelectrodes. They also indicate that the Cd-doped layer has great potential to replace the CdS layer in future photoelectrode designs.

P-Type Organic Cathode Materials with Oxygen Atoms as Active Sites for High-Performance Organic Batteries

p-Type Organic Cathode Materials with Oxygen Atoms as Active Sites for High-Performance Organic Batteries

A High Capacity p-Type Organic Cathode Material for Aqueous Zinc Batteries.

P-type organic cathode materials typically exhibit high redox potentials and fast redox kinetics, presenting broad application prospects in aqueous zinc batteries (AZBs). However, most of the reported P-type organic cathode materials exhibit limited capacity (< 100 mAh g-1), which is attributable to the low mass content ratio of oxidation-reduction active functional groups in these materials. Herein, we report a high-capacity p-type organic material, 5,12-dihydro-5,6,11,12-tetraazatetracene (DHTAT), for aqueous zinc batteries. Both experiments and calculation indicate the charge storage of DHTAT involves the adsorption/ desorption of ClO4- on the -NH- group. Benefitting from the high mass content ratio of the -NH- group in DHATA molecule, the DHATA electrode demonstrates a remarkable capacity of 224 mAh g-1 at a current density of 50 mA g-1 with a stable voltage of 1.2 V. Notably, after 5000 cycles at a high current density of 5 A g-1, DHTAT retains 73% of its initial capacity, showing a promising cycling stability. In addition, DHTAT also has good low-temperature performance and can stably cycle at -40 °C for 4000 cycles at 1 A g-1, making it a competitive candidates cathode material for low-temperature batteries.

Small signal analysis for the characterization of organic electrochemical transistors

A method for the characterization of organic electrochemical transistors (OECTs) based on small signal analysis is presented that allows to determine the electronic mobility as a function of continuous gate potential using a standard two-channel AC potentiostat. Vector analysis in the frequency domain allows to exclude parasitic components in both ionic and electronic conduction regardless of film thickness, thus resulting in a standard deviation as low as 4%. Besides the electronic mobility, small signal analysis of OECTs also provides information about a wide range of other parameters including the conductance, transconductance, conductivity and volumetric capacitance through a single measurement. General applicability of small signal analysis is demonstrated by characterizing devices based on n-type, p-type, and ambipolar materials operating in accumulation or depletion modes. Accurate benchmarking of organic mixed ionic-electronic conductors through small signal analysis can be anticipated to guide both materials development and the design of bioelectronic devices.

High-Performance p-type organic electrode materials with oxygen atoms as active centers enabled by molecular design and in situ electropolymerization

Redox-active organic molecules are considered to be one type of promising electrode materials for next generation lithium-ion batteries (LIBs), among which p-type electrode materials with higher voltage and outstanding reaction kinetics receive much attention. However, it is a great challenge to develop p-type materials with oxygen atom as the active center and the electrochemical performance of the few reported examples needs significant improvement. Herein, 1,3,5-tri(benzofuran-2-yl)benzene (TBFB) was elaborately designed and facilely synthesized through one-step Suzuki coupling reaction from commercially available raw reagents. When used as p-type electrode material for LIBs, it was found that TBFB with poor solubility can be effectively in situ electropolymerized during the charging process, forming more insoluble polymers. Experimental results demonstrate that TBFB electrode achieves a high specific capacity of 179.1 mAh g−1 and an ultralong cycle life of 8000 cycles. This work manifests the electrochemical performance of p-type organic electrode materials with oxygen atom as active center can be effectively enhanced by rational molecular design and in situ electropolymerization method.

Colloidal synthetic environmental design towards high-density twin boundaries and boosted thermoelectric performance in Cu5FeS4 icosahedrons

High-density twin boundaries can significantly influence materials’ functional and mechanical properties. In thermoelectrics, twin engineering is able to manipulate the carrier and phonon transport in semiconductors, leading to improved dimensionless figure of merit (zT). However, obtaining twin boundaries with tunable density and uniform distribution in thermoelectric semiconductors is rather challenging. Here, by precisely controlling the temperature of sulfur precursor, the particle size of synthesized Cu5FeS4 icosahedrons can be decreased to produce higher-density twin boundaries. Accordingly, the optimized average distance between two adjacent twin boundaries matches the mean free path of phonons but is much larger than that of carriers, thereby efficiently lowering the lattice thermal conductivity without affecting the carrier mobility significantly. In combination with the enhanced power factor caused by increased carrier concentration, a maximal zT of 0.95 is achieved at 773 K in a p-type Cu5FeS4 derivative material, which is one of the highest values among those in Earth-abundant, environmentally-friendly thermoelectric sulfides. This work uncovers the crucial role of high-density twin boundaries in decoupling the carrier and phonon transport for improved thermoelectric performance in Cu5FeS4-based materials.

Developing advanced CrSi coatings for combatting surface degradation of N-type (Zr,Ti)Ni(Sn,Sb) and P-type (Zr,Ti)Co(Sn,Sb) half Heusler thermoelectric materials

In this study, advanced oxidation-protective CrSi coatings were developed and deposited on N-type (Zr,Ti)Ni(Sn,Sb) and P-type (Zr,Ti)Co(Sn,Sb) thermoelectric (TE) materials using an environmentally friendly closed field unbalanced magnetron sputtering PVD system. The oxidation behaviour of the CrSi-coated and uncoated samples was evaluated through static oxidation tests at 500 °C and 600 °C for 10h and 50 h, respectively. In addition, the samples were exposed to cyclic oxidation tests between 25 °C and 500 °C for 10, 30 and 50 cycles, with each cycle consisting of 1h of oxidation at 500 °C, to examine the coating ability to withstand thermal shock, which is involved in the service of TE devices. The surface morphology, cross-section layer structure, elemental distribution and phase constitution were analysed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and X-ray diffraction (XRD). The mass gain after the oxidation tests was measured and calculated for each sample to study the oxidation kinetics. The uncoated samples exhibited a considerable amount of oxidation, leading to change in the surface morphologies, and the formation of alternated layers including oxide products (Zr(Ti)O2, SnO2) and Ni3Sn4 compound for the N-type and (Zr(Ti)O2, SnO2, Sb2O4) and CoSb compound for the P-type material, after static and cyclic oxidation tests. The experimental work in this study has, for the first time, demonstrated that the CrSi coatings developed with very high thermal stability and oxidation resistance can effectively protect both the N-type and P-type materials from oxidation and sublimation even during cyclic oxidation tests. The strong affinity of Cr and Si to oxygen can trap oxygen, retard its inward diffusion and thus protect the TE material substrate from oxidation. This finding could pave the way towards the further development of long-life high-performance TE generators and devices, thus contributing to the net zero target.

Ohmic Contact Resistance in SiC Diodes with Ti and NiSi P&lt;sup&gt;+&lt;/sup&gt; Contacts

Ohmic contacts play a major role in the signal transfer between the semiconductor device and the external circuitry. One of the main technological issues to develop high-performance SiC-based devices is the control of metal/SiC contact properties to fabricate low resistance and high stability SiC Ohmic contacts to p-type SiC. This is mostly due to intrinsic SiC characteristics like large work function, low dopant activation for p-type materials and low hole mobility. These limits are even more emphasized in SiC JBS or MPS diodes, where Schottky and Ohmic contacts on the P doped regions embedded in the active area to improve surge ruggedness are usually formed by using the same metallization process. This naturally results either in a high Schottky barrier height in the Schottky contact with consequent increase of the conduction loss at low currents or in a poorly conductive Ohmic contact, leading to reduced IFSM capability. Therefore, the optimization and control of the process parameters like for example the P+ doping concentration peak underneath the metallization layer and the annealing process temperatures is crucial to obtain a good Ohmic contact and enhance the device´s robustness against surge current.

Excellent thermoelectric performance of Fe2NbAl alloy induced by strong crystal anharmonicity and high band degeneracy

Full-Heusler alloys with earth-abundant elements exhibit high mechanical strength and favorable electrical transport behavior, but their high intrinsic lattice thermal conductivity limits potential thermoelectric application. Here, the thermoelectric transport properties of Fe-based Full-Heusler Fe2MAl (M = V, Nb, Ta) alloys are comprehensively investigated utilizing density functional theory. The results suggest that Fe2NbAl exhibits exceptionally low lattice thermal conductivity due to low phonon velocities and weakly bound Nb atoms. In Fe2NbAl, the underbonding of the Nb atoms leads large Grüneisen parameters and high anharmonic scattering rates of low-frequency acoustic phonon. Meanwhile, the high band degeneracy and large electrical conductivity lead to a maximum p-type power factor of 255.6 μW·K−2·cm−1 at 900 K. The combination of low lattice thermal conductivity and favorable electrical transport properties leads a maximum p-type dimensionless figure of merit of 1.7. Our work indicates Fe2NbAl, as a low-cost, environmentally friendly, is a potential high-performance p-type thermoelectric material.