N-type Single-walled Carbon Nanotube Research Articles

Unusual Electrical Conductivity Enhancement in Stable n-Type Carbon Nanotube Networks.

Organic molecule-doped n-type single-walled carbon nanotube (SWCNT) networks are promising candidates for advanced energy applications, such as flexible thermoelectrics and photovoltaics. Yet charge transport in n-type SWCNTs is limited by two factors: i) charge localization impeding inter-tube transport caused by disordered mesostructure of randomly oriented SWCNTs and ii) reduction of charge carrier concentration driven by oxidation. Herein, studied the relationship between the mesostructure and thermoelectric properties of n-type SWCNTs obtained by surfactant-functionalization and polymer-dopant grafting. Surprisingly, the electrical conductivity of the polymer-doped SWCNTs keeps increasing with increasing polymer content, even after the saturation of carrier concentration, resulting in 12x higher conductivity on polymer-doping compared to surfactant-functionalization. While hopping transport typically dominates in disordered systems, it is shown that a bridging effect from the polymer causes unusual band-like conduction in polymer-doped SWCNTs. Additionally, since surfactants are essential to prevent oxidation and retain n-type over a long duration, shows that SWCNTs obtained through a dual-functionalization strategy using both polymer-dopant and surfactant, demonstrates a long-term stable high n-type thermoelectric power factor, when the surfactant amount is carefully controlled. Besides thermoelectrics, the findings are of general interest to developing stable and conductive n-type SWCNTs for various energy and electronic applications.

Elevating Thermoelectric Performance by Compositing Dibromo-Substituted Thienoacene with SWCNTs.

Composites of organic small molecules (OSMs) and single-walled carbon nanotubes (SWCNTs) have drawn great attention as flexible thermoelectric (TE) materials in recent years. Here, we synthesized thieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]thiophene (TTA) and 2,6-dibromothieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]thiophene (TTA-2Br) and compounded them with SWCNTs, obtaining thermoelectric TTA/SWCNT and TTA-2Br/SWCNT composites. The introduction of the electron-withdrawing Br group was found to decrease the highest molecular orbital energy level and bandgap (Eg) of TTA-2Br. As a result, the Seebeck coefficient (S) and power factor (PF) of the OSM/SWCNT composite films were significantly improved. Moreover, suitable energy barrier between TTA-2Br and SWCNTs facilitates the energy filtering effect, which further enhances thermoelectric properties of the 40 wt % TTA-2Br/SWCNT composite film with optimum thermoelectric properties (PF = 242.59 ± 9.42 μW m-1 K-2 at room temperature), good thermal stability, and mechanical flexibility. In addition, the thermoelectric generator (TEG) prepared using 40 wt % TTA-2Br/SWCNT composite films and n-type SWCNT films can generate an output power of 102.8 ± 7.4 nW at a temperature difference of 20 °C. This work provides new insights into the preparation of OSM/SWCNT composites with significantly enhanced thermoelectric properties.

Stretchable and Flexible Painted Thermoelectric Generators on Japanese Paper Using Inks Dispersed with P- and N-Type Single-Walled Carbon Nanotubes.

As power sources for Internet-of-Things sensors, thermoelectric generators must exhibit compactness, flexibility, and low manufacturing costs. Stretchable and flexible painted thermoelectric generators were fabricated on Japanese paper using inks with dispersed p- and n-type single-walled carbon nanotubes (SWCNTs). The p- and n-type SWCNT inks were dispersed using the anionic surfactant of sodium dodecylbenzene sulfonate and the cationic surfactant of dimethyldioctadecylammonium chloride, respectively. The bundle diameters of the p- and n-type SWCNT layers painted on Japanese paper differed significantly; however, the crystallinities of both types of layers were almost the same. The thermoelectric properties of both types of layers exhibited mostly the same values at 30 °C; however, the properties, particularly the electrical conductivity, of the n-type layer increased linearly, and of the p-type layer decreased as the temperature increased. The p- and n-type SWCNT inks were used to paint striped patterns on Japanese paper. By folding at the boundaries of the patterns, painted generators can shrink and expand, even on curved surfaces. The painted generator (length: 145 mm, height: 13 mm) exhibited an output voltage of 10.4 mV and a maximum power of 0.21 μW with a temperature difference of 64 K at 120 °C on the hot side.

Vertically designed high-performance and flexible thermoelectric generator based on optimized PEDOT:PSS/SWCNTs composite films

To solve the long-lasting challenge of low thermoelectric performance of flexible thermoelectric device (F-TEG), in this work, we report a three-dimensional vertically structured F-TEG composed of flexible, stable, and high-performing p- and n-type single-walled carbon nanotube (SWCNT)-based composite films. The p-type SWCNT-based composite film exhibits a high room-temperature power factor of >500 μW m−1 K−2, benefiting from the effective de-doping of the hybridized poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT:PSS) using a binary co-doping agent composed of NaHCO3 and the polar solvent ethylene glycol (EG). Simultaneously, the n-type SWCNT-based film doped with the amine-rich electron donor polyethyleneimine (PEI) is prepared, exhibiting a high room-temperature power factor of 185.4 μW m−1 K−2 and excellent air stability. By employing flexible supporting foam, vertical p-n thermoelectric legs are realized, and the F-TEG based on these legs exhibits a maximum open-circuit voltage of 23.2 mV and a maximum output power of 2.6 μW at a temperature difference of 48 K, demonstrating a competitive normalized power density of >2.5 μW cm−2 K−2, which advances the low-power flexible wearable field.

All-Automated Fabrication of Freestanding and Scalable Photo-Thermoelectric Devices with High Performance.

Flexible photo-thermoelectric (PTE) devices have great application prospects in the fields of solar energy conversion, ultrabroadband light detection, etc. A suitable manufacturing process to avoid the substrate effects as well as to create a narrow transition area between p-n modules for high-performance freestanding flexible PTE devices is highly desired. Herein, an automated laser fabrication (ALF) method is reported to construct the PTE devices with rylene-diimide-doped n-type single-walled carbon nanotube (SWCNT) films. Thewet-compressing approach is developed to improve the thermoelectric power factors and figure of merit (ZT) of the SWCNT hybrid films. Then, the films are cut and patterned automatically to make PTE devices with various structures by the proposed ALF method. The freestanding PTE device with a narrow transition area of ≈2-3 µm between the p and n modules exhibits a high-power density of 0.32 µW cm-2 under the light of 200 mW cm-2, which is among the highest level for freestanding-film-based PTE devices. The results pave the way for the automatic production process of PTE devices for green power generation and ultrabroadband light detection.

Stable photothermal conversion in single-walled carbon nanotube device with pn-junction under uniform sunlight irradiation

N-type single-walled carbon nanotube (SWCNT) films with high air stabilities have attracted significant attention for their potential application in SWCNT devices featuring pn-junctions for power generation. However, SWCNT devices must be locally heated or formed into suspended structures to generate a temperature difference and produce output power. In this study, pn-junction SWCNT films were fabricated via vacuum filtration and subsequently attached to a polyimide substrate, enabling the creation of SWCNT devices without the need for suspended structures. Upon uniform irradiation with artificial sunlight, the SWCNT device produced a stable output voltage and short-circuit photocurrent. A thermographic image showed the emergence of a temperature gradient originating from the center of the SWCNT film and extending to the edge of the polyimide substrate. This phenomenon can be attributed to the higher optical absorption of SWCNT films compared to that of polyimide substrates. Consequently, the diffusion of carriers within the device generated an electric potential difference. Therefore, the SWCNT device generated a temperature gradient and yielded output power under uniform sunlight irradiation. These findings may aid in the development of facile and flexible optical devices, including photodetectors and hybrid devices integrating solar cells.

N-Type PVP/SWCNT Composite Films with Improved Stability for Thermoelectric Power Generation.

Single-walled carbon nanotubes (SWCNTs) are one of the promising thermoelectric materials in applications of powering wearable electronics. However, the electrical performance of n-type SWCNTs quickly decreases in air, showing a low stability, and low-cost and effective solutions to improving its stability are also lacking, all of which limit practical applications. In this study, we studied the stability of PVP/SWCNT composite films, where oxygen and moisture from air should be responsible for the decreased stability due to oxidation and hydration. In this case, we found that coating with a 0.20 g mL-1 PVP/0.002 g mL-1 PVDF layer on the surface of PVP/SWCNTs can prevent the penetration of oxygen and moisture from air, improving film stability, where there is almost no reduction in thermoelectric performance after they are exposed to air for 60 days. Based on the stable n-type PVP/SWCNT films, a thermoelectric generator was fabricated, where poly(dimethylsiloxane) (PDMS) was used to coat the surface of the thermoelectric leg to further improve its stability. This generator showed high output performance, which achieved an open-circuit voltage of 10.6 mV and a power density of 312.2 μW cm-2 at a temperature difference of 50 K. Particularly, it exhibited high stability, where the output performance kept almost unchanged after exposure to high-humidity air for 30 days. This coating technology is also applicable to other air-sensitive materials and promotes the development and application of thermoelectric materials and devices.

Study of the electron-doping mechanism in single-walled carbon nanotubes using dimethylbenzimidazole.

Single-walled carbon nanotubes (SWCNTs) exhibit p-type properties in air, necessitating electron doping using n-dopants (e.g., reducing agents) for the development of SWCNT-based electronic devices. Dimethylbenzimidazole (DMBI-H) derivatives serve as effective electron dopants, not only for SWCNTs, but also for various organic semiconducting materials. However, the doping reaction is still a subject of debate. In this study, the electron-doping reactions of ortho-methoxy-substituted DMBI-H for SWCNTs were analyzed in protic and aprotic solvents in the presence and absence of dioxygen (O2). The presence of O2 was found to cause the reduction of O2 on the SWCNT surface in the protic solvent, resulting in the production of DMBI cations and water through proton-coupled electron transfer (PCET) from the n-doped SWCNT and ethanol. This work elucidates the mechanism behind the air-stability of n-type SWCNTs.

Pyridine-mediated B–B bond cleavage of tetrahydroxydiboron to synthesize n-doped SWCNTs with long-term air stability

Neutral radicals, including carbon radicals, are highly useful chemical species for the functionalization of semiconducting materials to change their electrical and optical properties owing to their high reactivity. However, boron radicals have been limited to synthetic and reaction chemistry, with rare utilization in materials science. In this study, a mixture of tetrahydroxydiboron (B2(OH)4) and pyridine derivatives was found to act as an electron dopant for single-walled carbon nanotubes (SWCNTs) because of the electron transfer from pyridine-mediated boron radicals generated by B–B bond dissociation to neutral radicals. In particular, the radical formed from a mixture of B2(OH)4 and 4-phenylpyridine ((4-Phpy)B(OH)2·) efficiently doped electrons into the SWCNT films; thus, n-type SWCNTs with long-term air stability for more than 50 days at room temperature were prepared. Furthermore, the experimental and theoretical surface analyses revealed that the formation of stable cations from ((4-Phpy)B(OH)2·) and the efficient interaction with SWCNTs due to their high planarity served as the mechanism for their stable doping.

Long-Term Stable Thermal Emission Modulator Based on Single-Walled Carbon Nanotubes.

Dynamic control of a material's thermal emission could enable many emerging applications, such as thermal camouflage and infrared (IR) display. Low-dimensional carbon nanomaterials have shown great potential in these applications because of their tuneability in charge density via static gating or ionic intercalation. Herein, a thermal emission modulator based on single-walled carbon nanotubes (SWCNTs) is realized by ionic gating. The Fermi energy of the SWCNTs is shifted via the adsorption of ions on the surface, and the highest emissivity is observed at the neutral state while both P-type and N-type SWCNTs have a reduced emissivity. An emissivity modulation range is achieved approximately from 0.45 to 0.95 within the electrochemical window of the used ionic liquid. Thermal camouflage and IR display applications are then demonstrated by utilizing the tuneable thermal emissivity of the fabricated SWNCT films. More importantly, a single-layer structure allows effective dynamic control purely by static gating, without involving any ion interaction process that may cause structural damage, as observed in graphene and multi-walled nanotubes. Therefore, the SWCNT-based IR modulators exhibit long-term stability, with nearly identical modulation range and response time after 6000 dynamic tuning cycles, indicating great potential for practical applications.

High-performance g-C3N4 coated single-walled carbon nanotube composite films for flexible thermoelectric generators

Thermoelectric (TE) devices consisting of p-type and n-type single-walled carbon nanotubes (SWCNTs) based films, which can gather waste heat and turn it into electrical power, show potential application in supplying power for wearable electronic devices. In this study, graphitic carbon nitride (g-C3N4) has been prepared by high temperature pyrolysis of melamine and confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction pattern (XRD), respectively. Then the prepared g-C3N4 is composited with SWCNTs via mechanical mixing and vacuum-filtering method to obtain free-standing flexible g-C3N4/SWCNT thermoelectric composite films. The results demonstrate that g-C3N4 is efficiently covered on the surface of SWCNTs via interfacial π-π interaction, and g-C3N4 layer with several nanometers coated on SWCNTs simultaneously improves the electrical conductivity (σ) and the Seebeck coefficient (S) of g-C3N4/SWCNT. At a mass ratio of 2.5 % for g-C3N4/SWCNT, an optimal power factor value of 163.0 ± 1.0 μW m−1 K−2 is obtained for g-C3N4/SWCNT with the σ of 702.6 ± 1.6 S cm−1 and the S of 48.2 ± 0.2 μV K−1 at room temperature. Finally, a self-powering TE device composed of three pairs of p-n junctions is manufactured, and the actual output power is about 1.13 μW at the temperature difference of 50 K. As a result, this study offers a straightforward way to enhance the thermoelectric performance of single-walled carbon nanotubes, which can be utilized in flexible power generators.

Fully-Solution-Processed Enhancement-Mode Complementary Metal-Oxide-Semiconductor Carbon Nanotube Thin Film Transistors Based on BiI3 -Doped Crosslinked Poly(4-Vinylphenol) Dielectrics for Ultralow-Power Flexible Electronics.

The threshold voltage (Vth ) adjustment of complementary metal-oxide-semiconductor (CMOS) thin film transistors (TFTs) is one of the research hotspotsdue to its key role in energy consumption control of CMOS circuits. Here, ultralow-power flexible CMOS circuits based on well-matched enhancement-mode (E-mode) CMOS single-walled carbon nanotube (SWCNT) TFTs are successfully achieved through tuning the work function of gate electrodes, electron doping, and printing techniques. E-mode P-type CMOS SWCNT TFTs with the full-solution procedure are first obtained through decreasing the work function ofAg gate electrodes directly caused by the deposition of bismuth iodide(BiI3 )-doped solid-state electrolyte dielectrics. After synthetic optimization of dielectric compositions and semiconductor printing process, the flexible printed E-mode SWCNT TFTs show the high Ion /Ioff ratios of ≈106 , small subthreshold swing (SS) of 70-85mV dec-1 ,lowoperating voltages of ≈0.5 to -1.5V, good stabilityand excellent mechanical flexibility during 10000 bending cycles. E-mode N-type SWCNT TFTs are then selectively achieved via printing the polarity conversion ink (2-Amino-2-methyl-1-propanol (AMP) aselectron dopingagent) in P- type TFT channels. Last, printed SWCNT CMOS invertersare successfully constructed with full rail-to-rail output characteristics and the record unit static power consumption of 6.75 fW µm-1 at VDD of 0.2V.

Dual-Type Flexible-Film Thermoelectric Generators Using All-Carbon Nanotube Films

The long-term stability of n-type single-walled carbon nanotubes (SWCNTs) in air makes all-carbon thermoelectric generators (TEGs) viable. To increase the performance of TEGs, we developed a dual-type flexible-film thermoelectric generator (DFTEG). The vacuum filtering was used to form p- and n-type SWCNT films from ethanol-based dispersion and water-based solutions with cationic surfactant, respectively. DFTEGs were fabricated as follows: strip-shaped p- and n-type SWCNT films were attached on the top and back sides of a polyimide substrate, respectively, and were connected alternately in series by bending copper tapes on the edge of the polyimide substrate. The thermoelectric performance was measured after attaching the DFTEG outside a beaker full of water, where the water surface reached the center of the DFTEG. For a 10 mm long film and 15 p-n pairs, the DFTEG had an output voltage of 40 mV and a maximum power of 891 nW at a temperature difference of 25 K. The measured thermoelectric performance was significantly higher than that of the single-type TEG for almost the same SWCNT films. This result demonstrates that thermoelectric performance can be improved by using DFTEGs that are fabricated with optimum structural designs.

Influence of Polyvinylpyrrolidone on Thermoelectric Properties of Melt-Mixed Polymer/Carbon Nanotube Composites.

For thermoelectric applications, both p- and n-type semi-conductive materials are combined. In melt-mixed composites based on thermoplastic polymers and carbon nanotubes, usually the p-type with a positive Seebeck coefficient (S) is present. One way to produce composites with a negative Seebeck coefficient is to add further additives. In the present study, for the first time, the combination of single-walled carbon nanotubes (SWCNTs) with polyvinylpyrrolidone (PVP) in melt-mixed composites is investigated. Polycarbonate (PC), poly(butylene terephthalate) (PBT), and poly(ether ether ketone) (PEEK) filled with SWCNTs and PVP were melt-mixed in small scales and thermoelectric properties of compression moulded plates were studied. It could be shown that a switch in the S-value from positive to negative values was only possible for PC composites. The addition of 5 wt% PVP shifted the S-value from 37.8 µV/K to -31.5 µV/K (2 wt% SWCNT). For PBT as a matrix, a decrease in the Seebeck coefficient from 59.4 µV/K to 8.0 µV/K (8 wt% PVP, 2 wt% SWCNT) could be found. In PEEK-based composites, the S-value increased slightly with the PVP content from 48.0 µV/K up to 54.3 µV/K (3 wt% PVP, 1 wt% SWCNT). In addition, the long-term stability of the composites was studied. Unfortunately, the achieved properties were not stable over a storage time of 6 or 18 months. Thus, in summary, PVP is not suitable for producing long-term stable, melt-mixed n-type SWCNT composites.

Ultra-long air-stability of n-type carbon nanotube films with low thermal conductivity and all-carbon thermoelectric generators

This report presents n-type single-walled carbon nanotubes (SWCNT) films with ultra-long air stability using a cationic surfactant and demonstrates that the n-type Seebeck coefficient can be maintained for more than two years, which is the highest stability reported thus far to the best of our knowledge. Furthermore, the SWCNT films exhibit an extremely low thermal conductivity of 0.62 ± 0.08 W/(m·K) in the in-plane direction, which is very useful for thin-film TEGs. We fabricated all-carbon-nanotube TEGs, which use p-type SWCNT films and the n-type SWCNT films developed, and their air-stability was investigated. The TEGs did not degrade for 160 days and exhibited an output voltage of 24 mV, with a maximum power of 0.4 µW at a temperature difference of 60 K. These results open a pathway to enable the widespread use of carbon nanotube TEGs as power sources in IoT sensors.

Enhancement Effect of the C60 Derivative on the Thermoelectric Properties of n-Type Single-Walled Carbon Nanotube-Based Films.

Obtaining air-stable and high-performance flexible n-type single-walled carbon nanotube (SWCNT)-based thermoelectric films used in wearable electronic devices is a challenge. In this work, the microstructure and thermoelectric properties of n-type SWCNT-based films have been optimized via doping C60 and its derivative into polyethylenimine/single-walled carbon nanotube (PEI/SWCNT) films. The result demonstrated that the dispersity of triethylene glycol-modified C60 (TEG-C60) was better in PEI/SWCNT films than that of pure C60. Among the prepared composite films, TEG-C60-doped PEI/SWCNT (TEG-C60/PEI/SWCNT) films exhibited the highest TE performance, achieving a peak electrical conductivity of 923 S cm-1 with a Seebeck coefficient of -42 μV K-1 at a TEG-C60/SWCNT mass ratio of 1:100. Compared to that of PEI/SWCNT, the power factor was increased significantly from 40 to 162 μW m-1 K-2 after the addition of TEG-C60, which was higher than that of films after the addition of C60. In addition, the n-type doped SWCNT films had good air stability at high temperatures, and the Seebeck coefficients of C60/PEI/SWCNT and TEG-C60/PEI/SWCNT at 120 °C were still negative and remained at 92% and 85%, respectively, after 20 days. Furthermore, a flexible TE device consisting of five pairs of p-n junctions was assembled using the optimum hybrid film, which generated a maximum output power of 3.6 μW at a temperature gradient of 50.2 K. Therefore, this study provides a facile way to enhance the thermoelectric properties of n-type carbon nanotube-based materials, which have potential application in flexible power generators.

Poly(ionic liquid) dielectric for high performing P- and N-type single walled carbon nanotube transistors

There is an increasing demand for low-cost and high-performance electronics which has stimulated a need for new high-performance dielectric materials. We have developed a facile synthesis of poly(2-(methacryloyloxy)ethyl trimethylammonium bis(trifluoromethylsulfonyl)azanide-ran-methyl methacrylate) (P(METATFSI-MMA)), a polymeric ionic liquid that can be used as a high-performance dielectric for semiconducting single walled carbon nanotube (SWCNTs) thin film transistors (TFTs). The P(METATFSI-MMA) polymer was synthesized at both 35 and 62 mol% of 2-(methacryloyloxy)ethyl trimethylammonium bis(trifluoromethylsulfonyl)azanide and produced p- and n-type devices that functioned under ambient conditions. These TFTs were then used to study the impact of electrochemical doping on the performance of SWCNT TFTs when switching from n-type, where an electrical double layer is formed, to p-type, where the TFSI− anions are free to interact with the SWCNTs. The TFTs operating in p-type had higher current on/off ratios and a larger transconductance than those operating in n-type, which is characteristic of electrochemically doped transistors. Furthermore, we tested the impact of operating frequency on device performance and discovered that decreasing the operating frequency of the TFTs resulted in a decreased hysteresis. The decrease in hysteresis was also observed to be more significant for the 35 mol% polymer.

Simultaneously Achieving Green p- and n-Type Single-Walled Carbon Nanotube Composites by Natural Amino Acids with High Performance for Thermoelectrics

Simultaneously Achieving Green p- and n-Type Single-Walled Carbon Nanotube Composites by Natural Amino Acids with High Performance for Thermoelectrics

Understanding the solvent effects on polarity switching and thermoelectric properties changing of solution-processable n-type single-walled carbon nanotube films

Developing high performance solution-processable n-type thermoelectric materials is challenging. In this paper, we report that single-walled carbon nanotubes (SWCNTs) prepared in dimethyl sulfoxide (DMSO) (SWCNTs/DMSO) exhibit a high n-type electrical conductivity of 2298 S/cm at room temperature, which is superior to that of previously reported n-type solution-processable SWCNTs. The maximum n-type electrical conductivity was 3490 S/cm at 373 K. The great electrical conductivity results in a high n-type power factor of 195 μW/m-K2 for SWCNTs/DMSO films at 373 K which is larger than most of the n-type solution-processable SWCNTs. The theoretical calculation indicates that the wrapping morphology of the surfactant on SWCNTs is strongly affected by different solvent polarities which lead to different packing densities of the SWCNT films as demonstrated in the scanning electron microscope images, subsequently affecting the n-type doping efficiency and the n-type electrical conductivity. The electrical conductivity affected by the mixed p- and n-type carriers in the film were discussed. A full SWCNT thermoelectric generator has been fabricated to show the heat-to-electricity conversion ability of the materials. This work reveals a potential method to prepare highly conductive n-type SWCNTs by choosing the proper solvent for optimized thermoelectric performance.

Hf-Contacted High-Performance Air-Stable n-Type Carbon Nanotube Transistors

We have demonstrated air-stable n-type single-walled carbon nanotube (SWCNT)-based field-effect transistors (FETs) with hafnium (Hf) contacts. Unlike previously reported p-type characteristics for ...