Wei
Zhang
a,
Sagar
Shrestha
b,
Sajjan
Parajuli
a,
Bijendra Bishow
Maskey
a,
Jinhwa
Park
a,
Hao
Yang
a,
Younsu
Jung
*a and
Gyoujin
Cho
*ab
aDepartment of Biophysics, Institute of Quantum Biophysics, Research Engineering Center for R2R-Printed Flexible Computer, Sungkyunkwan University, Suwon-si, 16419, Republic of Korea. E-mail: isinu7@skku.edu; gcho1004@skku.edu
bDepartment of Intelligent Healthcare Convergence, Sungkyunkwan University, Suwon-si, 16419, Republic of Korea
First published on 6th June 2023
Charge carrier polarity tuning in printed thin film transistors (TFTs) is a crucial step in order to obtain complementary printed devices. In this work, we studied the effect of an Al2O3 passivation layer on printed single-walled carbon nanotube (SWCNT) based TFTs to tune the charge carrier polarity. By varying the atomic layer deposition (ALD) temperature and Al2O3 layer thickness, we can tune the doping degree of Al2O3 to tailor the polarity of printed SWCNT-based TFTs (SWCNT-TFTs). The precise control of threshold voltage (Vth) and polarity from p-type to well-balanced ambipolar, and n-type SWCNT-TFTs is successfully demonstrated with high repeatability by optimizing the ALD temperature and Al2O3 layer thickness based on 20 printed samples per test. As a proof-of-concept, inverter logic circuits using the SWCNT-TFT with different polarity types are demonstrated. The ambipolar device-based inverter exhibits a voltage gain of 3.9 and the CMOS-based inverter exhibits a gain of approximately 4.3, which is comparable to the current roll-to-roll (R2R) printed inverter circuits. Different thicknesses of Al2O3 layer, coated by the ALD at different temperatures and thicknesses, provide a deep understanding of the device fabrication and control process to implement the tailored doping method to efficiently realize R2R printed SWCNT-TFT-based complementary electronic devices.
In general, p-type SWCNT-TFTs are mostly observed under ambient printing conditions because the SWCNTs are vulnerable to adsorb water and oxygen. However, for integrating logic circuits such as CMOS (complementary metal oxide semiconductor) inverters, n-type SWCNT-TFTs are highly desirable as the counterpart of p-type devices.10–12 Many methods for converting the polarity of SWCNT-TFTs have been reported based on addition of chemical dopants,13 organic reducing reagents,14 or metal oxides for electrostatic doping15 on active materials. However, few studies reported on printed n-type SWCNT-TFTs. Recently, we reported the conversion method from p-type to n-type SWCNT-TFTs through an additional n-doping printing process using n-doping ink via a roll-to-roll (R2R) or roll-to-plate (R2P) gravure printing method.16,17 However, without an additional passivation layer, the n-type SWCNT-TFT can easily return to p-type SWCNT-TFT under ambient conditions, causing device failure. Furthermore, an extra printing step for printing both the n-type doping layer and the passivation layer would be inconvenient and problematic because adding an extra printing process would increase the production cost and the possibility of damaging the previously printed layers in printing the SWCNT-TFT-based devices. Thus, a simple and efficient way of achieving both n-doping and passivation simultaneously to realize stable n-type TFT based printed devices will be attractive because then only p-type SWCNT-TFTs will be required to be printed.16,18
To achieve both n-doping and stability on the printed SWCNT-TFTs at the same time, various techniques have been reported over the past few decades, including atomic layer deposition (ALD).12,19–21 ALD is well known for its ability to produce high-quality and uniform thin films with outstanding conformality even on complex geometries with high aspect ratios due to its self-terminating reaction property of each cycle in the growth process.22,23 Aluminum oxide (Al2O3), as one of the most extensively studied high-k material used as a precursor of ALD, possesses a high dielectric constant (∼9) combined with a large band gap (8.9 eV), low interfacial trap density, capability of processing at low temperatures, high breakdown electric field, and high chemical stability.24,25 Therefore, in the field of flexible electronic devices, Al2O3 layers, fabricated by ALD, are often used as passivation and dielectric layers.21,26 For example, an ambipolar SWCNT-TFT on silicon and polyimide substrates was realized by depositing an Al2O3 layer via the ALD, and n-type SWCNT-TFTs on a Si-wafer have also been fabricated by depositing Al2O3 using the ALD to demonstrate the potential of Al2O3 as a passivation layer for a pressure sensor to reduce environmental noise. Moreover, in recent years, solution-based Al2O3 dielectrics have been spin coated and cured using far-ultraviolet irradiation to complete flexible TFTs in order to adopt the printing process.27 In addition, high-performance p-type oxide TFTs with high hole mobilities by using solution-based Al2O3 were reported28 for application in developing low-cost flexible and printed electronics using the R2R gravure printing technology. However, there is no report yet regarding the precise control of the charge carrier polarity on fully R2R gravure printed SWCNT-TFTs using Al2O3 deposited by the ALD to achieve both unipolar and ambipolar devices and device stability at the same time.
In this work, we explore the effect of the deposited Al2O3 layer via the ALD on the R2R printed SWCNT-TFTs to understand how a p-type SWCNT-TFT can be converted into the ambipolar and n-type one. The SWCNT-TFTs were fabricated for this study using the R2R gravure printing process, which offers major advantages in mass production ability and low cost over the counterparts of flexible devices fabricated through vacuum deposition and photolithographic processes. Then, Al2O3 was deposited on top of the active layer of the printed SWCNT-TFTs using the ALD method. By adjusting the deposition (ALD) temperature and the thickness of deposited Al2O3, the threshold voltage (Vth) and polarity conversion were successfully controlled for the easy fabrication of p-type, ambipolar, and n-type printed SWCNT-TFTs. As such, we explored the following novel aspects: (1) air-stable n-type and ambipolar SWCNT-TFTs were obtained by coating Al2O3 on the p-type SWCNT-TFTs using the ALD method, (2) a series of designed experiments have been conducted to systematically study the mechanism of carrier type conversion and the factors affecting the conversion process. These experiments investigated the impact of alumina deposition temperature and thickness on the printed SWCNT-FETs, and (3) p-type, n-type, and ambipolar inverters were demonstrated and characterized for the integration of logic circuits. These results highlight the potential of utilizing deposited Al2O3 layers via the ALD as the doping and passivation layers for enhancing the stability and simplifying the R2R printing process to pave the way for commercializing printed electronics. Thus, the importance of this work in fabricating R2R printed SWCNT based complementary devices is that the three printing steps, p-doping, n-doping, and passivation can be simply replaced by one ALD step to save energy and cost.
After fabricating SWCNT-TFTs through the R2R gravure printing process, transfer and output characteristics of the printed SWCNT-TFTs were measured under ambient conditions using a semiconductor parameter analyzer (Keithley 4200A-SCS, USA) with a probe station (MST-4000A, MS-TECH, Korea). Thirty-five TFTs with similar electrical properties were chosen from the R2R printed SWCNT-TFTs as the testing samples for depositing the Al2O3 layer via the ALD (step (v) in Fig. 1a). Five devices were put in one group, and all the prepared devices were divided into 7 groups according to different deposition temperatures and thicknesses. To study the effect of deposition temperature, 50 nm thickness of Al2O3 was coated using the ALD method onto the printed SWCNT-TFT samples at temperatures of 150 °C, 140 °C, 130 °C, and 100 °C, respectively. Then, different thicknesses of 50 nm, 100 nm, 150 nm, and 200 nm of Al2O3 were respectively deposited at a deposition temperature of 140 °C. All the devices were carefully attached onto a 6-inch silicon wafer using polyimide (PI) tape and then the silicon wafers with samples were put into the ALD chamber. For the ALD process, trimethylaluminum (TMA) and water were used as precursors. The pulse time of TMA and water precursors was 0.1 s and 0.2 s, respectively, whereas the running time of TMA and water precursors was 30 s and 60 s, respectively. Under this condition, the steady-state growth per cycle is 0.15 nm. The reaction cycles for growing Al2O3 layers with the thickness of 50 nm, 100 nm, 150 nm, and 200 nm were 312, 624, 936, and 1048 respectively.
It is worth noting that, at the temperature of 100 and 130 °C (Fig. 2a and b), the devices show the typical p-type dominant properties, but as the temperature increases to 140 °C (Fig. 2c), the n-type charge carrier of on-current increases while the p-type charge carrier of on-current decreases, showing ambipolar properties interestingly, while at the temperature of 150 °C (Fig. 2d), the devices show n-type charge carrier-dominant properties. All the experiments were repeated (Fig. S2†). On the one hand, as reported previously, this phenomenon is caused by the different amounts of positive fixed charges generated by the deposited Al2O3 layer.30 When the deposition temperature is increased, the H2O, introduced during the ALD process, vaporizes rapidly. Consequently, fewer oxygen atoms are available during the formation of the Al2O3 layer. This leads to a higher deficiency of oxygen atoms within the oxide layer, resulting in the accumulation of more positive charge at a higher deposition temperature. On the other hand, the different temperatures may have different curing effects on the samples. To investigate the curing effect during the deposition process, a sample was cured for 8 hours at the temperature of 100 °C, 130 °C, 140 °C, and 150 °C, respectively. The results show that higher the curing temperature, more the shift of Vth towards 0 V as shown in Fig. S3.† Moreover, Fig. 2e–h show the transfer characteristics of the printed SWCNT-TFT with Al2O3 coating thicknesses of respectively 50 nm, 100 nm, 150 nm, and 200 nm at 140 °C deposition temperature. When the deposition thickness is 50 nm, the device shows ambipolar properties (Fig. 2e). However, when increasing the Al2O3 layer thickness to 100 nm and 150 nm (Fig. 2f and g), the device shows a slightly n-type dominant property. By increasing the thickness to 200 nm, the devices finally become n-type dominant (Fig. 2h). All the experiments were repeated as shown in Fig. S4† and the key electrical parameters of p-type and n-type devices fabricated under different ALD conditions were comparable as shown in Table S1.† Based on the above experiments and our device properties, there might be two possible reasons for the results obtained: the thickness of the Al2O3 layer and the curing time. On the one hand, the differences in the thickness of the Al2O3 layer may affect the density of the fixed positive charge present in the device. A previous report has suggested that thicker Al2O3 layers may result in a higher density of fixed charge.31 As a result, the increased thickness of the Al2O3 layer could induce more electrons in the interface of SiO2/Al2O3, resulting in an electron-richer situation. We can speculate, based on their study, that the thickness difference in the deposited Al2O3 may cause different densities of fixed positive charge which can influence the polarity of printed SWCNT-TFTs. This is supported by the results shown in Fig. 2e, f and S4.† On the other hand, the curing time might be another reason for the conversion from the pristine p-type SWCNT-TFT to the n-type during the ALD process since higher the thickness, more the deposition time required. To prove this, we additionally cured a pristine sample for 24 hours and measured IV characteristics every 8 hours. The results show that the Vth shifts more toward 0 V at a longer curing time as shown in Fig. S5.† Longer the curing time, more the water and oxygen removed from the SWCNT active channel, indicating that fewer holes will be involved as the carriers in the final device properties. Therefore, a similar number of electrons are induced by the deposited Al2O3 while the number of holes is reduced so that the device n-type will finally dominate the final device's property.
Fig. 3 elucidates the mechanism of different charge carrier polarity types of devices. Intrinsic SWCNTs have the ability to conduct electrons and holes. Firstly, R2R gravure printed SWCNT-TFTs show p-type properties due to their exposure to water and oxygen molecules in the ambient air.31 Therefore, the carriers in the SWCNT channel are holes and the Fermi level is close to the valence band (Fig. 3a). The polarity conversion of SWCNT-TFTs is attributed to the deposited Al2O3 which generated a positive fixed charge and could attract electrons in the SWCNT active layer, resulting in the Fermi level shifting towards the conduction band. When the number of electrons and holes in the channel are comparable, the devices show ambipolar properties in which the corresponding Femi level will be located near the middle between the conduction band and valence band (Fig. 3b). However, when the number of electrons is higher than the holes, the device will show n-type charge carrier dominant performance and the Fermi level of this type of device will move towards the conduction band (Fig. 3c). Usually SWCNT-based TFTs are vulnerable to the humidity in the air. Therefore, stable device development is an important step for practical applications of the device. The transfer characteristic curves for the p-type, ambipolar and n-type SWCNT-TFTs are respectively shown in Fig. 4a, b and c for showing the devices' stability under ambient conditions. From the attained transfer characteristic curves, we confirmed that no significant variations were observed in Vth and on/off ratio values between the initial state and the final state after 48 hours under the exposure of moisture and light. This suggests that the deposited Al2O3 layer can prevent water and oxygen from being adsorbed onto its surface. Furthermore, since the stability of the TFT under the bias stress is a critical point for practical applications, the biasing stress effect was further investigated using the printed devices with the deposition of the Al2O3 layer.28 The p-type, ambipolar device, and n-type devices were tested under the biasing voltage of Vgs = 20 V, and the transfer curves were measured every 10 minutes for 30 minutes. As shown in Fig. S6,† the measured transfer curves showed that all devices were stable under biasing stress, indicating the negligible defect density in the active channel. By using ambipolar SWCNT-TFTs, we further constructed inverter logic gates, the schematic of which is shown in Fig. 4d. Here, the noise margin (NM) is another critical parameter affecting the performance of the device consisting of digital logic circuits. Because it quantifies how much external signal perturbation a logic gate circuit can withstand during device operation, the tolerance ability to variations in the signal level is valuable for the integrated logic gates. The high noise margin (NMH) and low noise margin (NML) of the ambipolar TFT based inverter are 2.8 V and 3.4 V respectively as shown in Fig. 4e. In addition, the maximum gain of the inverter is around 4 (Fig. 4f). For inverters built using CMOS devices consisting of symmetric p-type and n-type SWCNT-TFTs (Fig. 4g), the NMH and NML are 4.7 V and 4.6 V, respectively as shown in Fig. 4h, and the maximum gain of the inverter is around 4.2 (Fig. 4i). The detailed transfer curve and output curve of the ambipolar devices and CMOS devices used in the inverter circuit test are shown in Fig. S7a–c.† The characteristics of the ambipolar charge carrier are clearly shown as a diode in Vds–Ids curves for both p-type and n-type measurements when the gate voltage is zero. Regarding the cut-off frequency of the devices, the calculated theoretical cut-off frequency was 202 kHz for the CMOS inverter based on the simple equation fT = gm/2π(CGS + CGD),8 where gm is the transconductance, CGS and CGD are the parasitic capacitances between the drain–source layer and gate layer. However, the observed cut-off frequency of the CMOS inverter was 100 Hz due to the trapped charges at the interface between the printed SWCNT network structure and dielectric layer, causing the huge parasitic capacitance. Based on the results from our previous logic gate circuits such as fully R2R gravure printed 1 bit ring oscillation,16 full adders,7 and 4 bit code generator,17 a voltage gain of 4 is sufficient for operating a simple type of TFT integrated circuits (within 100 TFT integration) with a reasonable degree of functionality. Thus, the ambipolar SWCNT-TFT based printed devices will be easier to develop the practical printed devices than implementing both n-type and p-type SWCNT-TFTs because complementary devices with environmental stability can be efficiently achieved.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3na00286a |
This journal is © The Royal Society of Chemistry 2023 |