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 (
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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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In recent years, oxide electronics has emerged as one of the most promising new technologies for a variety of electrical and optoelectronic applications, including next-generation displays, solar cells, batteries, and photodetectors. Oxide electronics have a lot of potential because of their high carrier mobilities and ability to be manufactured at low temperatures. However, the preponderance of oxide semiconductors is n-type oxides, limiting present applications to unipolar devices and stifling the development of oxide-based bipolar devices like p-n diodes and complementary metal-oxide–semiconductors. We have contributed to oxide electronics, particularly on transition metal oxide semiconductors of which the cations include In, Zn, Sn and Ga. We have integrated these oxide semiconductors into thin film transistors (TFTs) as active channel layer in light of the unique combination of electronic and optical properties such as high carrier mobility (5-10 cm2/Vs), optical transparency in the visible regime (>~90%) and mild thermal budget processing (200-400°C). In this study, we achieved four different results. The first result is that unlike several previous reports on oxide p-n junctions fabricated exploiting a thin film epitaxial growth technique (known as molecular beam epitaxy, MBE) or a high-powered laser beam process (known as pulsed laser deposition, PLD) that requires ultra-high vacuum conditions, a large amount of power, and is limited for large-area processing, we demonstrate oxide-based heterojunction p-n diodes that consist of sputter-synthesized p-SnOx and n-IGZO of which the manufacturing routes are in-line with current manufacturing requirements. The second result is that the synthesized p-SnOx films are devoid of metallic Sn phases (i.e., Sn0 state) with carrier density tuneability and high carrier mobility (> 2 cm2/Vs). The third result is that the charge blocking performance of the metallurgical junction is significantly enhanced by the engineering of trap/defect density of n-IGZO, which is identified using photoelectron microscopy and valence band measurements. The last result is that the resulting oxide-based p-n heterojunction exhibits a high rectification ratio greater than 103 at ±3 V (highest among the sputter-processed oxide junctions), a low saturation current of ~2×10-10 A, and a small turn-on voltage of ~0.5 V. The outcomes of the current study are expected to contribute to the development of p-type oxides and their industrial device applications such as p-n diodes of which the manufacturing routes are in-line with the current processing requirements.more » « less
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Abstract Printed electronics have made remarkable progress in recent years and inkjet printing (IJP) has emerged as one of the leading methods for fabricating printed electronic devices. However, challenges such as nozzle clogging, and strict ink formulation constraints have limited their widespread use. To address this issue, a novel nozzle‐free printing technology is explored, which is enabled by laser‐generated focused ultrasound, as a potential alternative printing modality called Shock‐wave Jet Printing (SJP). Specifically, the performance of SJP‐printed and IJP‐printed bottom‐gated carbon nanotube (CNT) thin film transistors (TFTs) is compared. While IJP required ten print passes to achieve fully functional devices with channel dimensions ranging from tens to hundreds of micrometers, SJP achieved comparable performance with just a single pass. For optimized devices, SJP demonstrated six times higher maximum mobility than IJP‐printed devices. Furthermore, the advantages of nozzle‐free printing are evident, as SJP successfully printed stored and unsonicated inks, delivering moderate electrical performance, whereas IJP suffered from nozzle clogging due to CNT agglomeration. Moreover, SJP can print significantly longer CNTs, spanning the entire range of tube lengths of commercially available CNT ink. The findings from this study contribute to the advancement of nanomaterial printing, ink formulation, and the development of cost‐effective printable electronics.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2MA00425A
