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Preparation and Characterization of Solution-Processed Nanocrystalline p-Type CuAlO2 Thin-Film Transistors
Nanoscale Research Letters volume 13, Article number: 259 (2018)
The development of p-type metal oxide thin-film transistors (TFTs) is far behind the n-type counterparts. Here, p-type CuAlO2 thin films were deposited by spin coating and annealed in nitrogen atmosphere at different temperature. The effect of post-annealing temperature on the microstructure, chemical compositions, morphology, and optical properties of the thin films was investigated systematically. The phase conversion from a mixture of CuAl2O4 and CuO to nanocrystalline CuAlO2 was achieved when annealing temperature was higher than 900 °C, as well as the transmittance, optical energy band gap, grain size, and surface roughness of the films increase with the increase of annealing temperature. Next, bottom-gate p-type TFTs with CuAlO2 channel layer were fabricated on SiO2/Si substrate. It was found that the TFT performance was strongly dependent on the physical properties and the chemical composition of channel layer. The optimized nanocrystalline CuAlO2 TFT exhibits a threshold voltage of − 1.3 V, a mobility of ~ 0.1 cm2 V−1 s−1, and a current on/off ratio of ~ 103. This report on solution-processed p-type CuAlO2 TFTs represents a significant progress towards low-cost complementary metal oxide semiconductor logic circuits.
Over the past decades, metal oxide thin-film transistors (TFTs) have been extensively investigated for the next-generation active-matrix liquid crystal displays, organic light-emitting diode displays, and other emerging electronic circuits applications due to their excellent electrical properties and outstanding optical transparency [1, 2]. However, a majority of the metal oxide TFTs reported to date were focused on n-type materials . The p-type oxide semiconductors are usually characterized with localized oxygen 2p orbitals with large electronegativity, self-compensation from oxygen vacancies, and the incorporation of hydrogen as an unintentional donor. Therefore, it is difficult in achieving effective hole doping . Up to now, only a few p-type oxide materials (Cu2O, CuO, SnO, etc.) were proved to be suitable for TFT application [5, 6], but their performance lags far behind of n-type counterparts. This limits the development of all oxide p-n junctions and complementary metal oxide semiconductor (CMOS) logic circuits.
To obtain a good p-type metal oxide, it is critical to modify the energy band structure and reduce the Coulomb force exerted by the oxygen ions on holes. thus motivating the discovery of a group of p-type delafossite oxides, such as CuMO2 (M=Al, Ga, In) and SrCu2O2 [7, 8]. Among them, CuAlO2 has a wide bandgap of ~ 3.5 eV, and its valence band maximums are dominated by a large hybridization of the oxygen orbitals with 3d10 electrons in the Cu1+ closed shell, which leads to a dispersive valence band. Meanwhile, the cations with closed shells (d10s0) are beneficial to achieve high optical transparency because such an electronic structure can avoid light absorption from the so-called d-d transitions. Therefore, it has attracted considerable attention since the first fabrication in 1997 . However, there are only a few reports focusing on p-type TFTs using CuAlO2 as channel layers. The primary difficulty is poor crystallinity and impurity phases, such as Cu2O, CuO, Al2O3, and CuAl2O4. The first report of a CuAlO2 TFT was fabricated by magnetron sputtering, and the device exhibits a current on/off ratio of 8 × 102 and a hole mobility of 0.97 cm2 V−1 s−1 . However, magnetron sputtering needs a strict high vacuum environment and a sophisticated operation process. In contrast, the solution-processed method offers conspicuous advantages, such as simplicity, low-cost, tunable composition, and atmospheric processing. In this work, we present a solution route to prepare CuAlO2 thin films. The effect of annealing temperature on the microstructure, chemical compositions, morphology, and optical properties of the thin films was investigated systematically. Finally, bottom-gate TFTs using the obtained nanocrystalline CuAlO2 thin films as channel layers were fabricated and they exhibit a mobility of ~ 0.1 cm2V−1 s−1, a threshold voltage of − 1.3 V, and a current on/off ratio of ~ 10 .
Precursor Preparation and Thin-Film Fabrication
The CuAlO2 thin films were prepared by spin coating using copper nitrate trihydrate (Cu(NO3)2·3H2O) and aluminum nitrate nonahydrate (Al(NO3)3·9H2O) as starting materials. The molar ratio of two metal salts is 1:1, and the concentration of each salt in ethylene glycol methylether is 0.2 mol/L; acetylacetone was added to form a stable solution in deep green. The entire mixing process was carried out in 80 °C water bath with stirring. Prior to film deposition, the substrates were ultrasonically cleaned with acetone, ethanol, and deionized water for 5 min in each solution. Then, the final precursor was spin-coated with a low rotating speed of 500 rpm for 9 s and followed by a high rotating speed of 5000 rpm for 30 s. After spin-coating, the substrate was annealed at 350 °C for 20 min. The procedures from coating to annealing were repeated four times until the desired thickness (~ 40 nm) of the films was reached. Finally, the as-deposited films were annealed at 700–1000 °C for 2 h in nitrogen atmosphere and cooled down to room temperature at same atmosphere.
Fabrication of CuAlO2 TFTs
The CuAlO2 TFTs with a bottom-gate structure were fabricated on SiO2/Si substrate. Three hundred-nanometer-thick SiO2 serves as the gate dielectric. After CuAlO2 film deposition, 50 nm gold source/drain electrodes were thermal evaporated on the channel layer through a shadow mask. The evaporation rate was 0.08 nm/s, and the channel width (W) and length (L) were 1000 μm and 100 μm, respectively. Finally, an indium layer was welded to the Si substrate as the back-gate electrode.
Film and TFT Characterization
The CuAlO2 film structure was studied by X-ray diffraction (XRD, DX2500) with CuKα radiation (λ = 0.154 nm). The Raman spectrum was measured by Renishaw-1000 with a solid-state laser (633 nm). Surface morphologies were measured with scanning electron microscopy (SEM, JSM-5600LV, JEOL) and Veeco Dimension Icon atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) was performed on a Thermo Scientific Escalab 250 Xi spectrometer. XPS spectra were collected after etching the film surface for about 3 nm to minimize surface contamination. The optical transmittance was measured by UV-Vis spectrophotometer (Varian Cary 5000). The electrical characteristics were measured by a semiconductor parameter analyzer (Keithley 2612B).
Results and Discussion
Figure 1a shows the XRD patterns of CuAlO2 thin films annealed at a different temperature. For the film annealed at 700 °C, only weak CuO phase diffraction peaks at 35.8° and 38.9° were observed, indicating that 700 °C is not enough for the formation of CuAlO2 phase . Two new peaks at 31.7° and 37.1° assigned to CuAlO2 and CuAl2O4 phases, respectively, were observed after 800 °C annealing. When the temperature reached to 900 °C, the intensity of the CuO peaks decrease and the CuAl2O4 phase peaks disappear. Several new peaks at 36.8°, 42.5°, 48.5°, 57.5°, and 31.7°, assigned to CuAlO2 phase, dominated the film [9, 12]. The temperature was further increased to 1000 °C, the peaks intensity increased, and single CuAlO2 phase were obtained. The enhancement of the crystallinity may be attributed to the fact that more energy absorption accelerated the growth of crystallites at higher annealing temperature.
Figure 1b shows the Raman spectra of CuAlO2 thin films. The four-atom primitive cell of delafossite structure CuAlO2 leads to 12 normal modes, but only the A1g (416 cm−1) and Eg (771 cm−1) modes are Raman active. As shown in Fig. 1b, it is obvious that two Raman vibration modes, A1g and Eg, both are present for all films . Unlike bulk analysis of XRD, Raman scattering originates from the molecular vibration and lattice vibration that can detect Raman active molecule vibrate from a very small amount of concentration. That explains the existence of CuAlO2 phase in the 700 °C annealed film, which is not observable in XRD spectrum. Others peaks at 798 cm−1, 297 cm−1, and 632 cm−1 were also observed which are assigned to the F2g mode of CuAl2O4, Ag, and Bg modes of CuO, respectively . The peaks of CuO and CuAl2O4 phases decrease as the annealing temperature increases from 700 to 1000 °C, and both phases convert to phase CuAlO2 after 1000 °C annealing, which is consistent with XRD results.
To understand the chemical compositions of CuAlO2 thin films annealed at different temperature, XPS measurement was carried out and the Cu 2p core levels spectra are shown in Fig. 2a. The typical Cu 2p3/2 peak can be fitted into two peaks located at ~ 932.8 and ~ 934.2 eV, which can be attributed to Cu+ and Cu2+, respectively. Similarly, fitted Cu 2p1/2 deconvolution two peaks are centered at ~ 952.6 (Cu+) and ~ 954.1 eV (Cu2+), respectively . Since the spin-orbital splitting of Cu 2p is ~ 19.8 eV, the 2p3/2 and 2p1/2 peaks were not constrained for the area ratio during fitting. Nevertheless, the area ratio of the Cu 2p3/2 peak and the Cu 2p1/2 peak is ~ 1.90, being close to the ideal value of 2 determined from electron state densities . The dominated peaks at ~ 932.8 eV (Cu+) and ~ 952.6 eV (Cu+) indicate that Cu cations mainly exist in Cu+ form in CuAlO2 lattice. Note that Cu2+ state is presented in all films, even no CuO peaks were detected in the high temperature annealed samples by XRD. Meanwhile, the satellite peaks observed from 941.2 to 944.4 eV also implied the presence of CuO. However, satellite peaks are almost negligible after high-temperature annealing, which is consistent with the above XRD observations. Quantitative analysis of the XPS spectra gave Cu+/[Cu++Cu2+] atomic ratios of 62.5%, 68.9%, 73.7%, and 78.9% for CuAlO2 thin films annealed at 700, 800, 900, and 1000 °C, respectively, indicating reduction of Cu2+ with the increase of annealing temperature [10, 16]. The XPS O 1s peaks are shown in Fig. 2b. It was interesting that the binding energies exhibit symmetrical dominant peaks centered at ~ 529.8 eV, indicating most of oxygen atom are bonded to nearest neighbor metal ions (Cu+, Al3+, or Cu2+) in the lattice. It should be noted that the peak at ~ 531.3 eV, attributed to oxygen-related defects, can hardly be distinguished. This result can be explained by the introduction of surface etch process and high crystallization quality.
The surface morphologies of the CuAlO2 thin films were observed by SEM, as shown in Fig. 3a. All the films exhibit continuous, smooth, and dense structure morphology without obvious micro-cracks. The grain size is homogeneous and increases with the increase of annealing temperature. The gradually enlarged grain size would lead to the fewer grain boundaries, which act as trapping sites and significantly reduce the mobility for the nanocrystalline CuAlO2 films . Thus, the CuAlO2 thin films annealing at high temperature is beneficial to the charge transport and may result high performance TFTs . Surface roughness is another factor which can seriously influence the electrical performance of oxide TFTs . To obtain the root mean square (RMS) roughness, the CuAlO2 thin films were investigated by AFM, as shown in Fig. 3b. The RMS roughness of films annealed at 700 °C, 800 °C, 900 °C, and 1000 °C were 0.92, 1.82, 2.12, and 2.96 nm, respectively. Obviously, the RMS increases with the increase of annealing temperature. Generally, rough surface would result in presence of electrical defects or trapping sites resulting in inferior device performance . Therefore, it was supposed that there should be a competition relation between grain size and surface roughness to affect the performance of nanocrystalline oxide TFTs.
The optical transmission spectra of the CuAlO2 thin films on fused silica were measured in wavelength range from 200 to 800 nm, as shown in Fig. 4. It was observed that all films have steep absorption edge and strong ultraviolet absorption, which is an indication of the good crystallinity of the films. The average transmittance in the visible light region was calculated from ~ 60 to ~ 80%, increasing with the increase of annealing temperature. Tauc’s relation αhν = A(hν − Eg)1/2 is carried out to calculate the optical band gap, where α is the absorption coefficient, A is the constant for a direct transition, h is the Planck’s constant, and ν is the photon frequency . The value of Eg is given by the linear extrapolation of the plot of (αhν)2 versus hν to the energy axis, as shown in the inset of Fig. 4. The Eg were calculated to be 3.25 eV, 3.40 eV, 3.60 eV, and 3.80 eV for the CuAlO2 thin films annealed at 700 °C, 800 °C, 900 °C, and 1000 °C, respectively.
Finally, we fabricated the bottom-gate top-contact TFTs on SiO2/p-Si substrates to investigate the electrical performance of CuAlO2 as channel layers. The schematic diagram of device is illustrated in Fig. 5a. The output curves of the CuAlO2 TFTs at a gate-source voltage (VGS) of − 50 V are shown in Fig. 5b. It clearly indicates the on-state current (Ion) increases with the increase of annealing temperature. This is mainly attributed to the elimination of insulator-like CuAl2O4 phase and the enhancement of nanocrystalline CuAlO2 phase. The transfer curves are shown in Fig. 5c–f, and the CuAlO2 TFTs exhibit a typical p-type behavior. All the devices show a moderate on/off current ratio (Ion/Ioff) of ~ 103 which perhaps can be further improved by optimizing channel thickness, cation doping, or changing source/drain material [22,23,24]. The threshold voltage (VT) is determined as a horizontal axis intercept of a linear fitting to the IDS1/2-VGS curve. The VT shift towards the positive with the increase of annealing temperature. The filed effect mobility (μFE), the subthreshold slope (SS), and the interface trap density (Nt) can be calculated by the following equations [25, 26]:
where k is the Boltzmann constant, T is the temperature, q is the elementary charge of electron, and Cox is the areal capacitance of the gate insulator . The key electrical parameters of the devices are listed in Table 1. It can be seen the SS values, largely higher than reported n-type devices, decrease with the increase of annealing temperature, which is consistent with the trend of VT. The results can be explained by the reduction of traps at the channel/dielectric interface . The μFE values increase from 0.006 to 0.098 cm2V−1 s−1 as the annealing temperature increased from 700 to 1000 °C, which indicates an improvement of hole transport due to phase conversion from a mixture to nanocrystalline CuAlO2 and enlargement of grain size. The μFE are lower than solution-processed CuCrO2 TFTs reported by Nie et al . The reason may be the delafossite nanocrystalline CuAlO2 structure is lack of Cu-O-Cu lattice content than that of CuCrO2 . In spite of the annealing temperature of the devices is high for practical applications, this is the first report about solution-processed CuAlO2 TFTs. Further reduction of the annealing temperature by UV/ozone photochemical reaction and/or combustion synthesis is now underway [23, 30, 31].
In summary, solution-processed CuAlO2 thin films were fabricated and annealed in nitrogen atmosphere at different temperature. With the temperature increased from 700 to 1000 °C, the film structure phase transforms from a mixture of CuAl2O4 and CuO to nanocrystalline CuAlO2, as well as the optical transmittance, energy band gap, grain size, and surface roughness of the films increase. The p-type CuAlO2 TFTs performance was strongly dependent on the physical properties and the chemical composition of channel layer. The optimized nanocrystalline CuAlO2 TFT exhibits a threshold voltage of − 1.3 V, a mobility of ~ 0.1 cm2V−1 s−1, and a current on/off ratio of ~ 103. Compared to vacuum-based magnetron sputtering, our work demonstrates a low-cost, solution-processed CuAlO2 TFTs, which represents an important advancement towards the development of complementary metal oxide semiconductor logic circuits.
Atomic force microscopy
- C ox :
The areal capacitance of the gate insulator
- I on/I off :
On/off current ratio
- k :
The Boltzmann constant
- L :
The channel length
- N t :
The interface trap density
- q :
The elementary charge of electron
Scanning electron microscopy
The subthreshold slope
- T :
The absolute temperature
- V T :
- W :
The channel width
X-ray photoelectron spectroscopy
- μ FE :
Filed effect mobility
Li Z-Y, Yang H-Z, Chen S-C, Lu Y-B, Xin Y-Q, Yang T-L, Sun H (2018) Impact of active layer thickness of nitrogen-doped In–Sn–Zn–O films on materials and thin film transistor performances. J Phys D Appl Phys 51(17):175101
Yu X, Marks TJ, Facchetti A (2016) Metal oxides for optoelectronic applications. Nat Mater 15(4):383–396
Park JS, Maeng W-J, Kim H-S, Park J-S (2012) Review of recent developments in amorphous oxide semiconductor thin-film transistor devices. Thin Solid Films 520(6):1679–1693
Wang Z, Nayak PK, Caraveo-Frescas JA, Alshareef HN (2016) Recent developments in p-type oxide semiconductor materials and devices. Adv Mater 28(20):3831–3892
Sung S-Y, Kim S-Y, Jo K-M, Lee J-H, Kim J-J, Kim S-G, Chai K-H, Pearton SJ, Norton DP, Heo Y-W (2010) Fabrication of p-channel thin-film transistors using CuO active layers deposited at low temperature. Appl Phys Lett 97(22):222109
Yabuta H, Kaji N, Hayashi R, Kumomi H, Nomura K, Kamiya T, Hirano M, Hosono H (2010) Sputtering formation of p-type SnO thin-film transistors on glass toward oxide complimentary circuits. Appl Phys Lett 97(7):072111
Yanagi H, Hase T, Ibuki S, Ueda K, Hosono H (2001) Bipolarity in electrical conduction of transparent oxide semiconductor CuInO2 with delafossite structure. Appl Phys Lett 78(11):1583–1585
Nagarajan R, Draeseke AD, Sleight AW, Tate J (2001) p-type conductivity in CuCr1−xMgxO2 films and powders. J Appl Phys 89(12):8022–8025
Kawazoe H, Yasukawa M, Hyodo H, Kurita M, Yanagi H, Hosono H (1997) P-type electrical conduction in transparent thin films of CuAlO2. nature 389:939–942
Yao ZQ, He B, Zhang L, Zhuang CQ, Ng TW, Liu SL, Vogel M, Kumar A, Zhang WJ, Lee CS, Lee ST, Jiang X (2012) Energy band engineering and controlled p-type conductivity of CuAlO2 thin films by nonisovalent Cu-O alloying. Appl Phys Lett 100(6):062102
Jiang HF, Lei HC, Zhu XB, Li G, Yang ZR, Song WH, Dai JM, Sun YP, Fu YK (2009) Effects of citric acid on properties of single phase CuAlO2 thin films derived by chemical solution deposition. J Alloys Compd 487(1–2):404–408
Ehara T, Abe H, Iizaka R, Abe K, Sato T (2017) Crystalline orientation control in sol–gel preparation of CuAlO2 thin films. J Sol-Gel Sci Technol 82(2):363–369
Byrne D, Cowley A, Bennett N, McGlynn E (2014) The luminescent properties of CuAlO2. J Mater Chem C 2(37):7859–7868
Liu S, Wu Z, Zhang Y, Yao Z, Fan J, Zhang Y, Hu J, Zhang P, Shao G (2015) Strong temperature-dependent crystallization, phase transition, optical and electrical characteristics of p-type CuAlO2 thin films. Phys Chem Chem Phys 17(1):557–562
Ghosh CK, Popuri SR, Mahesh TU, Chattopadhyay KK (2009) Preparation of nanocrystalline CuAlO2 through sol–gel route. J Sol-Gel Sci Technol 52(1):75–81
Nie S, Liu A, Meng Y, Shin B, Liu G, Shan F (2018) Solution-processed ternary p-type CuCrO2 semiconductor thin films and their application in transistors. J Mater Chem C 6(6):1393–1398
Murali KR, Balasubramanian M (2013) Properties of CuAlO2 thin films deposited by polyacrylamide gel route. Mater Sci Semicond Process 16(1):38–42
Kim MG, Kanatzidis MG, Facchetti A, Marks TJ (2011) Low-temperature fabrication of high-performance metal oxide thin-film electronics via combustion processing. Nat Mater 10(5):382–388
Hou JJ, Wang F, Han N, Zhu H, Fok K, Lam W, Yip S, Hung T, Lee JEY, Ho JC (2013) Diameter dependence of electron mobility in InGaAs nanowires. Appl Phys Lett 102(9):093112
Wang F, Yip S, Han N, Fok K, Lin H, Hou JJ, Dong G, Hung T, Chan KS, Ho JC (2013) Surface roughness induced electron mobility degradation in InAs nanowires. Nanotechnology 24(37):375202
Zhang X, Zhai J, Yu X, Ding L, Zhang W (2013) Fabrication and characterization of flexible Ag/ZnO Schottky diodes on polyimide substrates. Thin Solid Films 548:623–626
Qu Y, Yang J, Li Y, Zhang J, Wang Q, Song A, Xin Q (2018) Organic and inorganic passivation of p-type SnO thin-film transistors with different active layer thicknesses. Semicond Sci Technol 33(7):075001
Liu A, Zhu H, Guo Z, Meng Y, Liu G, Fortunato E, Martins R, Shan F (2017) Solution combustion synthesis: low-temperature processing for p-type Cu:NiO thin films for transparent electronics. Adv Mater 29:1701599
Zhang X, Wang B, Sun X, Zheng H, Li S, Zhang P, Zhang W (2018) Highly transparent and conductive W-doped ZnO/Cu/W-doped ZnO multilayer source/drain electrodes for metal-oxide thin-film transistors. IEEE Electron Device Lett 39(7):967–970
Jiao Y, Zhang X, Zhai J, Yu X, Ding L, Zhang W (2013) Bottom-gate amorphous In2O3 thin film transistors fabricated by magnetron sputtering. Electron Mater Lett 9(3):279–282
Dahiya AS, Opoku C, Poulin-Vittrant G, Camara N, Daumont C, Barbagiovanni EG, Franzo G, Mirabella S, Alquier D (2017) Flexible organic/inorganic hybrid field-effect transistors with high performance and operational stability. ACS Appl Mater Interfaces 9(1):573–584
Liu A, Liu G, Zhu H, Shin B, Fortunato E, Martins R, Shan F (2016) Hole mobility modulation of solution-processed nickel oxide thin-film transistor based on high-k dielectric. Appl Phys Lett 108(23):233506
Ding X, Qin C, Song J, Zhang J, Jiang X, Zhang Z (2017) The influence of hafnium doping on density of states in zinc oxide thin-film transistors deposited via atomic layer deposition. Nanoscale Res Lett 12(1):63
Sanal KC, Jayaraj MK (2014) Room temperature deposited p-channel amorphous Cu 1−x Cr x O 2−δ thin film transistors. Appl Surf Sci 315:274–278
Zhang H, Meng Y, Song L, Luo L, Qin Y, Han N, Yang Z, Liu L, Ho JC, Wang F (2018) High-performance enhancement-mode thin-film transistors based on Mg-doped In2O3 nanofiber networks. Nano Res 11(3):1227–1237
Wang F, Song L, Zhang H, Meng Y, Luo L, Xi Y, Liu L, Han N, Yang Z, Tang J, Shan F, Ho JC (2018) ZnO nanofiber thin-film transistors with low-operating voltages. Adv Electron Mater 4(1):1700336
This work was supported by the National Natural Science Foundation of China (U1504625), Youth Backbone Teacher Training Program in Henan province (2017GGJS021), Program for Innovative Research Team in Science and Technology in University of Henan Province (19IRTSTHN019), and Foundation of Henan Educational Committee (12A510003).
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Li, S., Zhang, X., Zhang, P. et al. Preparation and Characterization of Solution-Processed Nanocrystalline p-Type CuAlO2 Thin-Film Transistors. Nanoscale Res Lett 13, 259 (2018). https://doi.org/10.1186/s11671-018-2680-5
- p-type thin-film transistor
- Nanocrystalline films