We report a synthesis procedure for dodecanethiol capped wurtzite ZnO nanocrystals with an average diameter of 4 nm that are monodisperse, highly soluble, and shelf-stable for many months. Compared to previous ZnO ink recipes, we demonstrate improved particle solubility and excellent ink stability, resulting in ZnO nanocrystal inks that are optimized for printed electronics applications. The ZnO nanocrystal solution exhibits an absorption peak at 341 nm (3.63 eV), which represents a blue-shift of approximately 0.3 eV from the bulk ZnO bandgap (∼3.3 eV). This blue shift is consistent with previously reported models for an increased bandgap due to quantum confinement. We used variable-angle spectroscopic ellipsometry (VASE) to determine the optical properties of solution-processed thin films of ZnO nanocrystals, which provides valuable insight into the changes in film composition and morphology that occur during thermal annealing treatments ranging from 150–300 °C. The ZnO nanocrystals maintain their quantum confinement when deposited into a thin film, and the degree of quantum confinement is gradually reduced as the thermal annealing temperature increases. Using infrared absorption measurements (FTIR) and X-ray photoelectron spectroscopy (XPS), we show that the dodecanethiol ligands are removed from the ZnO films during annealing, resulting in a high-purity semiconductor film with very low carbon contamination. Furthermore, we show that annealing at 300 °C results in complete ligand removal with only a slight increase in grain size. Thin-film transistors (TFT) using ZnO nanocrystals as the channel material annealed at 300 °C show moderate mobility (∼0.002 cm 2 V −1 s −1 ) and good on/off ratio >10 4 . These results demonstrate the distinct advantages of colloidal nanocrystals for printed electronics applications: the composition and morphology of the solution-processed film can be carefully tuned by controlling the size and surface coating of the nanocrystals in the ink.
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Inkjet-printed p-type CuBI : wearable thin-film transistors
Printing enabled solution processing of semiconductors, especially Cu-based films, is an inexpensive and low-energy fabrication route for p-type thin-film transistors that are critical components of printed electronics. The state-of-the-art route is limited by a gap between ink compositions that are printable and ink compositions that enable high electrical performance at low processing temperatures. We overcome this gap based on the insight that the hole density of CuI can be tuned by alloying with CuBr while achieving a higher on/off ratio due to the lower formation energy of copper vacancies in CuBr than in CuI. We develop stable and printable precursor inks from binary metal halides that undergo post-printing recrystallization into a dense CuBrI thin film at temperatures as low as 60 °C. Adjusting the CuI/CuBr ratio affects the electrical properties. CuBr 0.2 I 0.8 films achieve the highest field-effect mobility among CuI based thin-film transistors (9.06 ± 1.94 cm 2 V −1 s −1 ) and an average on/off ratio of 10 2 –10 5 at a temperature of 150 °C. This performance is comparable to printed n-type Cu-based TFT that needs temperatures as high as 400 °C. (mobility = 0.22 cm 2 V −1 s −1 , on/off ratio = 10 3 ). The developed low-temperature processing capability is used to inkjet print textile-based CuBrI thin-film transistors at a low temperature of 60 °C to demonstrate the potential for printing complementary circuits in wearable electronic textiles.
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- Award ID(s):
- 2001081
- NSF-PAR ID:
- 10373883
- Date Published:
- Journal Name:
- Materials Advances
- ISSN:
- 2633-5409
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Additive patterning of transparent conducting metal oxides at low temperatures is a critical step in realizing low‐cost transparent electronics for display technology and photovoltaics. In this work, inkjet‐printed metal oxide transistors based on pure aqueous chemistries are presented. These inks readily convert to functional thin films at lower processing temperatures (
T ≤ 250 °C) relative to organic solvent‐based oxide inks, facilitating the fabrication of high‐performance transistors with both inkjet‐printed transparent electrodes of aluminum‐doped cadmium oxide (ACO) and semiconductor (InOx ). The intrinsic fluid properties of these water‐based solutions enable the printing of fine features with coffee‐ring free line profiles and smoother line edges than those formed from organic solvent‐based inks. The influence of low‐temperature annealing on the optical, electrical, and crystallographic properties of the ACO electrodes is investigated, as well as the role of aluminum doping in improving these properties. Finally, the all‐aqueous‐printed thin film transistors (TFTs) with inkjet‐patterned semiconductor (InOx ) and source/drain (ACO) layers are characterized, which show ideal low contact resistance (R c< 160 Ω cm) and competitive transistor performance (µ linup to 19 cm2V−1s−1, Subthreshold Slope (SS) ≤150 mV dec−1) with only low‐temperature processing (T ≤ 250 °C). -
High-throughput printing-based fabrication has emerged as a key enabler of flexible electronics given its unique capability for low-cost integration of circuits based on printed thin film transistors (TFTs). Research in printing inorganic metal oxides has revealed the potential for fabricating oxide TFTs with an unmatched combination of high electron mobility and optical transparency. Here, we highlight recent developments in ink chemistry, printing physics, and material design for high-mobility metal oxide transistors. We consider ongoing challenges for this field that include lowering process temperatures, achieving high speed and high resolution printing, and balancing device performance with the need for high mechanical flexibility. Finally, we provide a roadmap for overcoming these challenges with emerging synthetic strategies for fabricating 2D oxides and complementary TFT circuits for flexible electronics.more » « less
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Abstract The demand of cost‐effective fabrication of printed flexible transistors has dramatically increased in recent years due to the need for flexible interface devices for various application including e‐skins, wearables, and medical patches. In this study, electrohydrodynamic (EHD) printing processes are developed to fabricate all the components of polymer‐based organic thin film transistors (OTFTs), including source/drain and gate electrodes, semiconductor channel, and gate dielectrics, which streamline the fabrication procedure for flexible OTFTs. The flexible transistors with top‐gate‐bottom‐contact configuration are fabricated by integrating organic semiconductor (i.e., poly(3‐hexylthiophene‐2,5‐diyl) blended with small molecule 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene), conductive polymer (i.e., poly (3,4‐ethylenedioxythiophene) polystyrene sulfonate), and ion‐gel dielectric. These functional inks are carefully designed with orthogonal solvents to enable their compatible printing into multilayered flexible OTFTs. The EHD printing process of each functional component is experimentally characterized and optimized. The fully EHD‐printed OTFTs show good electrical performance with mobility of 2.86 × 10−1cm2V−1s−1and on/off ratio of 104, and great mechanical flexibility with small mobility change at bending radius of 6 mm and stable transistor response under hundreds of bending cycles. The demonstrated all printing‐based fabrication process provides a cost‐effective route toward flexible electronics with OTFTs.
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Flexible electronics with highly thermal stability and mechanical strength are highly needed in advanced transportation systems. Semiconducting single‐walled carbon nanotubes are one of the leading active materials for such thin film transistors because they are printable, flexible, thermally stable, and mechanically strong. Dielectrics with large capacitance are another major component, and polymer electrolytes are printed for flexible electronics, but they suffer from poor mechanical strength and low operating temperature. Here, a transparent, mechanically flexible, and thermally stable polyfluorinated electrolyte (PFE) is developed with high capacitance by curing printed polyfluorinated resin (PFR) and ionic liquid composite at high temperature. PFE inherits the mechanical flexibility and thermal stability from PFR. The immobilized ionic liquid inside the porous structures of PFE accounts for the high capacitance. With top‐gated PFE, fully printed electronically pure single‐chirality (6,5) single‐walled carbon nanotube (SWCNT) thin‐film transistors (TFTs) exhibit air stable, consistent, and reliable ambipolar characteristics with high transconductance (1 mS) and small subthreshold swing (<0.15 V dec−1) at low voltage in ambient air for p‐type and n‐type carriers, and >105ON/OFF current ratio for both carriers under low operation voltage.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2MA00425A
