Saleem
Anwar‡
ab,
Beomjin
Jeong‡
a,
Mohammad Mahdi
Abolhasani
ac,
Wojciech
Zajaczkowski
a,
Morteza
Hassanpour Amiri
a and
Kamal
Asadi
*a
aMax Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany. E-mail: asadi@mpip-mainz.mpg.de
bSchool of Chemical & Materials Engineering, National University of Sciences & Technology, Sector H–12, Islamabad, Pakistan
cChemical Engineering Department, University of Kashan, 8731753153, Kashan, Iran
First published on 25th February 2020
Nylons are one of the most successful commercialized polymers and can also be made to have ferroelectric properties. However, use of nylons in microelectronic devices like ferroelectric field-effect transistors has proven to be challenging due to the difficulty in achieving ferroelectric thin films by solution processing. In this work, we present ferroelectric field-effect transistor (FeFET) memory with a ferroelectric nylon-11 gate. Water quenching allows for the fabrication of ultra-smooth ferroelectric nylon-11 thin films. A bottom-gate top-contact (BGTC) FeFET is successfully demonstrated with a p-type semiconducting polymer, poly(triaryl amine) (PTAA), as a channel. The nylon-11 FeFET shows reliable memory functionality. The demonstration of nylon-11 based FeFETs makes nylons a promising material for applications in organic electronics, such as flexible devices, electronic textiles and biomedical devices.
Polyamides, or nylons, are one of the most successful commercialized polymers and are extensively used in textiles and structural and high performance applications. The polymer chain in nylons is composed of amide units that are separated by CH2 units. Odd nylons that have an even number of CH2 units between the amide bonds exhibit ferroelectric properties i.e. remanent polarization, Pr, and coercive field, Ec, that are on par with fluorinated polymers.11 Despite their significant potential, microelectronic devices employing odd nylons have rarely been demonstrated, mainly because of the difficulty in thin film fabrication of ferroelectric nylons. The exploitation of ferroelectric odd-nylons is hindered due to difficulties associated with (i) solution processing of nylons into thin films, and (ii) arriving at the crystalline ferroelectric δ′-phase, which is characterized by a metastable mesophase with randomly oriented hydrogen bonds along the backbone and between the adjacent chains.12–14
Solution processing of nylon thin films is challenging because of the excellent solvent resistance of nylons to most common organic solvents. Thin films processed from the limited number of applicable solvents such as formic acid, m-cresol, or trifluoroacetic acid (TFA)15,16 produce films with porous structure, which is unsuitable for microelectronic applications.17–19 A previous attempt to develop a nylon-11 gate insulator using a high boiling point solvent, m-cresol, has resulted in poor memory operation of the resulting FeFETs due to the uncontrolled high roughness of the nylon-11 film.20 Therefore, nylon-based functional microelectronic devices such as ferroelectric field effect transistors (FeFETs) have hardly been realized.
Recently, we have demonstrated ferroelectricity in solution processed thin films of odd-nylons using a solvent mixture of TFA:acetone [60:40 mole percent (mol%)].21 The ferroelectric phase is realized by placing the wet spin-coated film in a vacuum chamber to quickly extract the solvent and provide fast crystallization conditions. The resulting vacuum-quenched thin films show small crystallites and the absence of spherulitic superstructures. The solvent-quenching process using a vacuum, to some degree, imitates the supercooling process from a melt, which is known to yield the pseudohexagonal non-spherulitic δ′-phase.21 However, thin films produced by vacuum quenching have a roughness of around 5 nm, which is not suited for applications in devices such as FeFETs.22 We hypothesize that the roughness is due to the extended solvent-quenching time, since the vacuum is not strong enough to quickly extract solvent molecules. To exactly imitate supercooling, the solvent extraction process should be done much quicker. The δ′-phase crystallites are then much smaller and the film roughness would reduce, rendering nylon-11 suitable for FeFET applications.
Here, we report FeFETs based on ultra-smooth nylon-11 thin films that are realized by a solvent quenching method using a non-solvent, water. The resulting nylon-11 films are non-porous and show dielectric and ferroelectric properties similar to the vacuum-quenched ones. The resultant nylon FeFETs show excellent memory functionality with a high ON–OFF ratio, good retention time and excellent cycle endurance. Our demonstration of nylon FeFETs offers a great opportunity for technological utilization of nylons in microelectronics.
Fig. 1 Tapping mode AFM height and phase images, respectively, of a nylon-11 thin film obtained by (a and b) vacuum quenching and (c and d) water quenching. |
For solvents that are miscible with water, placing the solvent-wet film in a water bath leads to liquid–liquid (L–L) demixing, resulting in polymer-rich and polymer-poor phases. As a result, a porous and rough morphology is obtained for the solidified film. From this point of view, achieving ultra-smooth nylon-11 thin-films is counterintuitive because TFA:acetone is miscible with water. However, L–L demixing does not seem to play a role during the water-quenching process. Here we tentatively explain the film formation mechanism. TFA is a strong acid, which by protonating the amide bond weakens the hydrogen bonds and solubilizes nylon-11. Addition of acetone (by 40 to 50 mol%) increases the acidity due to the deshielding of the acidic proton.21 On the other hand, water has a strong tendency to dissociate a proton from TFA:acetone and to form hydronium ions (H3O+). The formation of H3O+ deprotonates the amides along the polymer chains, leading to solidification of the nylon-11 film. The kinetics of H3O+ formation is much faster than the L–L demixing, such that before L–L demixing sets in, all the solvent molecules are depleted from the film. To support this claim, a mixture of TFA:acetone (60:40 mol%) with water (50:50 mol%) has been prepared. In sharp contrast with TFA:acetone, the mixture with water does not dissolve nylon-11, as shown in Fig. S1 (ESI†), under the same room-temperature conditions. The mixing with water renders TFA:acetone a non-solvent for nylon-11, due to the unavailability of protons to attack hydrogen bonded amides.
Crystallization at high solvent depletion rates is governed by homogeneous nucleation, where the number of nucleation sites upon solidification is several orders of magnitude larger in comparison with crystallization at low solvent depletion rates, such as conventional spin coating. Due to the large number of crystallites, lateral growth of crystalline lamellae into spherulites is hindered, and therefore the ferroelectric δ′-phase is obtained.21,23 The quick depletion of TFA:acetone from the film mimics supercooling of nylon-11 from melts, which yields the crystalline ferroelectric δ′-phase.21Fig. 2 shows the WAXD patterns of the water-quenched thin film and, as a reference, that of the melt-quenched-stretched (MQS) thick film. The MQS film shows the (001) diffraction peak at 4.79 nm−1, corresponding to a d-spacing of 1.311 nm in perfect agreement with the literature values of the δ′-phase.13,24–26 The (001) reflection gives the length of repeat units in the crystalline structure along the polymer chain. A second diffraction peak at 15.10 nm−1 (a d-spacing of 0.416 nm) is a superposition of the (100) and (010) peaks and gives the inter-chain distance along the hydrogen bonds and the inter-sheet distance between the hydrogen bonded sheets, respectively. The presence of a single diffraction peak around 15 nm−1 indicates the low inter-molecular arrangement of the chains with random orientation of hydrogen bonds along the backbone and between adjacent chains.13,14
Fig. 2 WAXD pattern for the water-quenched thin film compared with a melt-quenched stretched thick film. |
The diffraction peaks of the water-quenched thin film show similar reflections to those of the MQS thick film, as well as the vacuum quenched one.21 The (001) and (100/010) reflection peaks for the water-quenched thin film are exactly at the same position. Therefore, the WAXD measurement unambiguously indicates that water quenching allows one to readily produce thin films of nylon-11 with the ferroelectric δ′-phase.
The electrical displacement (D) vs. electrical field (E) hysteresis loops (top) and switching current (bottom) of the reference vacuum-quenched and the water-quenched capacitors are given in Fig. 3a. Pr and Ec of both samples are 4.5 ± 0.2 μC cm−2 and 200 ± 10 MV m−1, respectively, and are similar to literature values, indicating the effectiveness of the water quenching process.11,13,14,27 To show the robustness and applicability of the films for microelectronic applications, we have measured the retention time of the polarization and cycle endurance as shown in Fig. 3b. The capacitor does not show any sign of depolarization, and Pr remains stable for nearly 105 seconds. Moreover, the water-quenched thin films show excellent performance upon repeated polarization switching processes, and the polarization is stable for more than one million switching cycles. A slight increase in the Pr value is observed upon cycling, which is attributed to electric field induced polarization or electroforming.28,29 It has been shown that nylon-11 films show fatigue-free performance that can even exceed that of PVDF and P(VDF–TrFE) capacitors.28
We note that nylons are known for their water uptake. The presence of water molecules inside the film would jeopardize the ferroelectric performance of the nylon-11 capacitor. To investigate whether water uptake takes place during water quenching, we have studied the dielectric response of the nylon-11 thin films. Fig. 4 shows the relative permittivity ε′ (top) and loss ε′′ (bottom) spectra of both the vacuum- and water-quenched samples. ε′ or the dielectric constant exhibits a very weak frequency dependence at the low frequency limit (<1 Hz), which is about 4 and reduces to 3.5 at 1 MHz. The lack of strong frequency dependence particularly at low frequencies could be assigned to the lack of ions (water or solvent molecules) in the films. The loss for both films is about the same and again shows only weak frequency dependence. The impedance spectra indicate a lack of ions, including water molecules, in both films, in particular in the water-quenched nylon-11 film. Therefore, the water quenching process has no effect on the performance of the nylon-11 capacitors and does not hinder the application of nylon-11 for microelectronic devices.
Fig. 4 Frequency dependence of the relative permittivity (ε′) (top) and loss (ε′′) (bottom) of the nylon-11 thin film processed via vacuum quenching (black) and water quenching (red). |
Achieving low roughness with minimized dielectric losses renders water-quenched nylon-11 thin films suitable for a gate insulator in FeFETs. To that end, nylon-11 FeFETs with BGTC architecture and p-type semiconductor polytriarylamide, PTAA, have been fabricated. The device schematic and chemical structure of PTAA are shown in Fig. 5a. The p-type PTAA FeFET exhibits large hysteresis in the IDS–VGS transfer characteristic, arising from the ferroelectric polarization of the nylon-11 gate as shown in Fig. 5b. Upon application of a negative gate bias, holes in PTAA accumulate at the interface between nylon-11 and PTAA. The coercive gate bias at which the nylon-11 polarizes is about −30 V. The negative polarization of nylon-11 is compensated by hole carriers in PTAA, giving rise to a significant increase in channel conductance (ON-state). When the positive gate voltage is biased above +30 V, nylon-11 reverses polarization. The positively polarized nylon-11 ferroelectric at the interface with PTAA cannot be compensated and the ferroelectric is depolarized, and thus the channel becomes depleted (OFF-state).30 The nylon-11 FeFET has bistable current states at zero gate bias with an ON–OFF ratio that is larger than 103 and operates as a ferroelectric memory. A gate current level of 10−8 A was observed at programming and erasing voltages. We note that microelectronic devices are typically encapsulated against ambient conditions for operational stability. Therefore, water uptake in nylon-11 will not be of concern in applications when the devices are properly encapsulated.
The data retention and cycle endurance of the nylon-11 FeFET are presented in Fig. 5c and d. The ON- and OFF-states are programmed by applying −50 V and +50 V gate bias, respectively, and then the channel conductance is probed at 0 V gate bias. The current for both the ON- and OFF-states has remained constant in time and remained around 10−7 and 10−10 A, respectively, as shown in Fig. 5c. We have demonstrated, in Fig. 3b, superior polarization stability of nylon-11 in time. Therefore, long term stability of the ON-state for the PTAA based FeFET is expected due to the presence of the compensation charges. The slight reduction in the ON-state current however could originate from the aging of the PTAA since organic semiconductors are known to be prone to degradation under electrical biasing.31 The cycle endurance of the nylon-11 FeFET is explored for repetitive data programing and erasing cycles. Fig. 5d shows the current level in the PTAA channel at a read gate voltage of VGS = 0 V repetitively changed upon programming at VGS = −50 V (ON-state) and erasing at VGS = +50 V (OFF-state). The ON–OFF ratio of the PTAA channel current remained around 30 after switching over 60 times. The switching time for the nylon-11 FeFET is set to 100 ms to provide a longer time for polarization at a switching field of 167 MV m−1 (VGS = 50 V), which is lower than the 250 MV m−1 used in the capacitor. We note that nylon-11 has shown excellent endurance under repetitive polarization switching cycles for more than 106 cycles (Fig. 3b). Therefore, upon further switching of the nylon-11 gate, the same ON/OFF ratio is expected.
Footnotes |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c9tc06868f |
‡ These authors contributed equally to this work. |
This journal is © The Royal Society of Chemistry 2020 |