Dual active layer a-IGZO TFT via homogeneous conductive layer formation by photochemical H-doping
© Jeong et al.; licensee Springer. 2014
Received: 1 September 2014
Accepted: 24 October 2014
Published: 18 November 2014
In this study, InGaZnO (IGZO) thin film transistors (TFTs) with a dual active layer (DAL) structure are fabricated by inserting a homogeneous embedded conductive layer (HECL) in an amorphous IGZO (a-IGZO) channel with the aim of enhancing the electrical characteristics of conventional bottom-gate-structure TFTs. A highly conductive HECL (carrier concentration at 1.6 × 1013 cm-2, resistivity at 4.6 × 10-3 Ω∙cm, and Hall mobility at 14.6 cm2/Vs at room temperature) is fabricated using photochemical H-doping by irradiating UV light on an a-IGZO film. The electrical properties of the fabricated DAL TFTs are evaluated by varying the HECL length. The results reveal that carrier mobility increased proportionally with the HECL length. Further, a DAL TFT with a 60-μm-long HECL embedded in an 80-μm-long channel exhibits comprehensive and outstanding improvements in its electrical properties: a saturation mobility of 60.2 cm2/Vs, threshold voltage of 2.7 V, and subthreshold slope of 0.25 V/decade against the initial values of 19.9 cm2/Vs, 4.7 V, and 0.45 V/decade, respectively, for a TFT without HECL. This result confirms that the photochemically H-doped HECL significantly improves the electrical properties of DAL IGZO TFTs.
KeywordsTFT UV irradiation Photochemical doping Hydrogen donor a-IGZO Dual active layers
Recently, there has been a growing need in the next-generation display industry for the development of new channel thin film transistors (TFTs) in order to implement active-matrix organic light-emitting diode (AMOLED) displays with a large area, rapid information transmission, high resolution, and high frame rates. Among the various candidates for new channel TFTs, oxide TFTs are receiving great attention owing to their several advantages such as high electron mobility, high on/off ratio, low leakage current, and good uniformity even when deposited at low temperatures. In particular, amorphous InGaZnO (a-IGZO) TFT is emerging as the most viable option among oxide TFTs for use in the next-generation display industry, as it provides good uniformity as an amorphous TFT suitable for large displays and has a relatively high mobility of over 10 cm2/Vs[2–4].
A-IGZO TFT has higher electron mobility than existing silicon-based TFTs, which are less amorphous. However, for OLED pixels that are utilized in large AMOLED TVs, high current is generally required in order to emit light through electrical current injection. In addition, there is a great demand for TFTs with electron mobility higher than 30 cm2/Vs in order to realize the required display resolutions and pixel circuits. To fulfill these requirements, extensive research has been conducted in an attempt to enhance the electron mobility of a-IGZO via different methods, including oxygen vacancy control,[6, 7] hydrogen annealing,[8, 9] use of a Ca capping layer, sputtering power control, and by combining various oxide components[11, 12]. However, oxygen vacancy control - one of the most commonly used methods to enhance the electrical conductivity of oxide semiconductors - may improve their conductivity, but the conductivity range in which this method is applicable is very limited. Hydrogen annealing increases the number of oxygen vacancies by artificially creating a reducing atmosphere and makes it possible to realize high electrical conductivity; however, this method requires a lengthy thermal process carried out above 300°C and is very limited in its applicability as it may damage surrounding devices through rapid hydrogen diffusion. In addition, attempts have been made to enhance the electron mobility of a-IGZO by forming an additional Ca capping layer on top of the active layer to induce the reduction of a-IGZO and increase the number of oxygen vacancies. However, this method encountered problems such as restrictions by the surrounding environment due to vulnerability of Ca to oxygen or moisture in the atmosphere and the complexity of the fabrication process in forming additional layers. Further, sputtering power control and the combination of various oxide materials have reproducibility problems, since target, equipment, and process requirements have not been standardized.
With this background, many researches have been conducted on dual active layer (DAL) TFTs to enhance their mobility by forming additional materials with high electrical conductivity on either the top or bottom of active layers. Kim et al. achieved improvement in mobility by depositing an additional layer of a Mo thin film on the active layer. However, the mobility did not increase noticeably (2.5 to 4.7 cm2/Vs), and the transparency decreased with increasing metal length. In another study, a high electrical conductivity oxide such as ITO was embedded in the channel path of the active layer to enhance both transmittance and mobility. However, in this method, an interface is generated between the active layer and oxide material owing to the formation of a heterojunction, and this interface formation may degrade the electrical properties of the TFTs.
Hence, clearly distinguished from all the above-discussed previous reports, the present study was focused on high-performance DAL TFTs fabricated using a strikingly convenient optical method called ‘permanent photochemical doping,’ which can uniformly enhance electrical properties by the effective H donor incorporation in the channel, in an attempt to resolve the issues encountered by existing DAL TFTs. Among the available oxide semiconductors, a-IGZO with excellent electrical properties was used for fabricating the TFT active layer, and a homogeneous embedded conductive layer (HECL) obtained through photochemical doping at room temperature was embedded in the channel path to enhance electrical mobility. In addition, the electrical characteristics of the fabricated DAL TFTs were evaluated by varying the HECL length within a certain range to be shorter than the length of the active layer to investigate the effect of HECL on the channel path.
Bottom-gate-structure TFTs with an embedded highly conductive a-IGZO path in a-IGZO active layer were fabricated on a glass substrate. A 100-nm-thick Mo gate electrode was deposited using DC sputtering at room temperature and patterned out using wet etching. This was followed by the deposition of a 100-nm-thick SiO2 gate insulator at 300°C using plasma-enhanced chemical vapor deposition. For HECL formation, a 20-nm-thick a-IGZO layer was deposited on PR-patterned SiO2 substrates with a width of 50 μm and lengths of 20, 40, and 60 μm by RF sputtering at room temperature by using a single oxide target. During a-IGZO deposition, an ambient atmosphere of Ar:O2 with a ratio of 90:10 was maintained at 5 mTorr. For HECL formation, after a lift-off process, patterned a-IGZO layers were steadily irradiated by deep-UV light (with main wavelengths of 185 and 254 nm) for 240 min. An additional 20-nm-thick active layer of a-IGZO was then deposited at an RF power of 40 W and room temperature. The 50-μm-wide and 80-μm-long a-IGZO active layer was patterned again using a lift-off process. For fabricating source and drain electrodes, 100-nm-thick Mo layers were deposited using DC sputtering at room temperature.
The electrical properties of the fabricated TFTs were evaluated via current–voltage (I-V) measurements performed using an Agilent E5270B parameter analyzer (Agilent Technologies, Inc., Santa Clara, CA, USA). The electrical properties of the HECL itself were analyzed using the Van der Pauw method by Hall measurement (Ecopia HMS 3000, Ecopia, Anyang, Korea) at room temperature. The chemical compositions of the oxide thin films were analyzed using X-ray photoelectron spectroscopy (XPS; Theta probe base system, Thermo Fisher Scientific Co., Seoul, South Korea). The energy resolution for each point was 0.05 eV, and the peak energy was self-calibrated to C1s and O1s reference peak states. The optical absorption data were measured by a rotating compensator-enhanced SE device with a spectral resolution of 15 meV and were analyzed using a three-phase optical model.
Results and discussion
UV-irradiated a-IGZO surfaces showed significant changes in the metal-OH states. The metal-OH bond fractions normalized to the total areal intensity in each metal ion increase with increase in UV irradiation; this trend corresponds to an increase in the OH bond fraction in the O1s XPS spectra corresponding to UV irradiation. The chemical reason for higher binding energies of Zn-OH-related bonds is due to the higher group electronegativity of OH compared to O. Although the group electronegativity of OH varies at 2.3 to 3.9 due to the lone pair π electrons with the remainder of the molecule, Zn-OH configuration is subject to the higher group electronegativity of OH than that of O (3.44) at least since the binding energy of Zn-OH is higher than Zn-O in Zn2p spectra.
The origin of significantly increased OH bond of a-IGZO upon UV irradiation is related to the UV/air photochemistry. As described in the reaction scheme (Figure 3d), due to UV photon energies used in this study, abundant excited OH and H radicals are produced by photochemical water dissociation and react with the a-IGZO surface. Among those radical species, H is most effective for surface reaction due to the fast diffusion near the a-IGZO surface. On the other hand, UV light itself is well known to break O-metal bonds to create O-vacancy sites in metal-oxygen bonds like Zn-O by the photocarrier-induced O desorption. This provides the basis for substitutional H incorporation in addition to interstitial incorporation. Therefore, the proposed a-IGZO surface reaction scheme under UV/air irradiation can be regarded as H incorporation to (1) O-vacancy substitutional sites and (2) interstitial sites (due to a small size of H) and finally appears as OH bonds. It was suggested that H incorporation into a-IGZO always results in surface OH bond formation where conversion of H atoms to H+ ions (i.e., donor ions) increases the carrier concentration greatly as expressed in the following equation: H(ads) + Zn2+ + O2- (in a-IGZO) → H+(in lattice) + Zn2+ + O2- + e- → OH- (in a-IGZO) + Zn2+ + e-9. Here, similar reactions for In and Ga in addition to Zn can be considered. In order words, H atom donates excess electrons while being the positively ionized donor ion in a-IGZO and is finally converted to - OH or - O2-H+. This effect is also confirmed in H-doped ZnO in the view of electronic bond state, and interestingly, it was explained that an excess electron initially occupies the high-lying Zn (4s)-H (1s) antibonding molecular orbital (MO) state above conduction band (CB) edge of ZnO and deexcites to CB minimum states to be free carriers. Similar chemical doping mechanism and coupling of excess electrons with In/Ga (5s)-H (1s) is highly expected. Since electrons are confined in s-orbital character MO state positioned at the edge of CB minimum, the carrier mobility should be higher than electrons trapped at the d-band dominant deep donor level of O-vacancy. The OH formation of a-IGZO upon H-induced n-type doping has been experimentally demonstrated in previous studies using thermal anneal and ion implantation. However, the overall doping effect with such doping methods is not so significant, and this was believed due to the doping effect compensation by the complicated interaction between loosely bound O and H subject to the thermal diffusion throughout the bulk. Nevertheless, UV-induced H-doping in this study reveals the remarkable effect of the insulator-to-metal transition. We regard that the key mechanism for this distinguishable from other H-doping technique is related to double simultaneous photochemical reactions; O-vacancy creation and H incorporation, synergistically forming highly OH-rich a-IGZO surface not throughout the bulk. The surface localized H incorporation is inherent property of UV photochemistry done at room temperature free of significant thermal diffusion or high energy ion penetration. Also, we found no change in the bulk optical bandgap by spectroscopic ellipsometry [see Additional file1: Figure S3 for optical absorption data]. These unchanged optical properties even after UV irradiation are due to weak light absorption in the surface OH region and should have been altered if this is the bulk doping effect since bulk zinc hydroxide (ZnOH2) has at least 1 eV higher bandgap than ZnO.
In addition to the mobility enhancement, it was confirmed that TFTs can be turned on at a lower gate voltage when the carrier concentration increases, and the threshold voltage is gradually lowered owing to the increased length of embedded HECL within a channel path. The relationship between the carrier concentration and threshold voltage has been reported in a previous study. The concurrent changes in crucial TFT parameters such as saturation mobility and Vth are closely related to chemical changes of a-IGZO by UV-induced H-doping. As shown in Figure 3d, the high OH fraction is equivalent to a surface H-doping effect or hydroxide formation on a-IGZO. Thus, the surface potential of an HECL led by UV photochemistry leads to a relatively negative Vth shift in TFT devices.
Additionally, it can be found that intensity of the O-deficient Zn1+ (1,020 eV) peak is decrease with in UV irradiation, as shown in Figure 3. It means that O-vacancy defects acting trap site in the local metal-oxygen-bonding environment decreased. Therefore, increase of HECL length leads to the decrease in the density of trap site at the whole active channel layer. In general, SS value is closely related to the density of trap site in active layer of TFTs. Hence, as the HECL length increases, the SS value of the device also improves.
In this study, we fabricated DAL TFTs via a new approach called permanent photochemical doping to enhance the mobility of existing bottom-gate-structure TFTs. Different from existing DAL TFT mobility enhancement methods, the structure resulting from this approach employs the same phase and material; thus, degradation in electrical properties due to physical interface formation or band offset does not occur. The chemical origin of permanent optical doping in HECL was found as UV photochemistry induced intensive and uniform surface H-doping of a-IGZO proved by XPS. Moreover, the effects of changes in the HECL length on the channel path were investigated. The obtained results showed that the mobility increased monotonically as the length of the embedded HECL increased. This result was attributed to the carrier concentration increase in the active layer channel area triggered by changes in the HECL length. Finally, the highest mobility of 60.2 cm2/Vs was obtained when a 60-μm-long HECL was embedded in an 80-μm-long channel path. This observation confirmed that an HECL length 75% of the total active layer length results in high-performance characteristics for materials with 200% improvement in mobility: a threshold voltage of 2.7 V, SS of 0.25 V/decade, and an on/off ratio of 107. Moreover, the leakage current level was maintained at 10-11 A. All these significant improvements in a-IGZO TFTs are explained by the effective n-doping in HECL by UV-induced H-incorporation on the surface, confirmed by OH-rich surface of a-IGZO. Surface H-doping results in a high electron donation in the HECL even for amorphous a-IGZO without any heat treatment to improve crystallinity and dopant activation. Therefore, owing to its great simplicity, the comprehensive performance improvement achievable, and stability, the doping technique proposed herein can be effectively utilized for large-scale a-IGZO TFT arrays employed in flat-panel displays. The applicability of the H-doping technique proposed in this study can be extended if it becomes possible to carry out selective UV irradiation along with in situ a-IGZO deposition through improvements in process equipment in the future.
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (2013R1A1A2064715) and also supported by the Basic Science Program (NRF-2012R1A1A1005014) through the National Research Foundation (NRF) of the Ministry of Science, ICT and Future Planning.
- Bardsley JN: International OLED technology roadmap. IEEE J Sel Top Quant Electron, IEEE Journal of 2004, 10: 3–9. 10.1109/JSTQE.2004.824077View ArticleGoogle Scholar
- Nomura K, Ohta H, Takagi A, Kamiya T, Hirano M, Hosono H: Room-temperature fabrication of transparent flexible thin-film transistors using amorphous oxide semiconductors. Nature 2004, 432: 488–492. 10.1038/nature03090View ArticleGoogle Scholar
- Yabuta H, Sano M, Abe K, Aiba T, Den T, Kumomi H, Nomura K, Kamiya T, Hosono H: High-mobility thin-film transistor with amorphous InGaZnO4 channel fabricated by room temperature rf-magnetron sputtering. Appl Phys Lett 2006., 89: 112123–1-112123–3 112123-1-112123-3Google Scholar
- Jeong JK, Jeong JH, Yang HW, Park J-S, Mo Y-G, Kim HD: High performance thin film transistors with cosputtered amorphous indium gallium zinc oxide channel. Appl Phys Lett 2007., 91: 113505–1-113505–3 113505-1-113505-3Google Scholar
- Park J-S, Kim H, Kim I-D: Overview of electroceramic materials for oxide semiconductor thin film transistors. J Electroceram 2014, 32: 117–140. 10.1007/s10832-013-9858-0View ArticleGoogle Scholar
- Chiang HQ, McFarlane BR, Hong D, Presley RE, Wager JF: Processing effects on the stability of amorphous indium gallium zinc oxide thin-film transistors. J Non-Cryst Solids 2008, 354: 2826–2830. 10.1016/j.jnoncrysol.2007.10.105View ArticleGoogle Scholar
- Suresh A, Gollakota P, Wellenius P, Dhawan A, Muth JF: Transparent, high mobility InGaZnO thin films deposited by PLD. Thin Solid Films 2008, 516: 1326–1329. 10.1016/j.tsf.2007.03.153View ArticleGoogle Scholar
- Se IO, Godeuni C, Hyunsang H, Wu L, Jae-Hyung J: Hydrogenated IGZO thin-film transistors using high-pressure hydrogen annealing. IEEE Trans Electron Dev 2013, 60: 2537–2541.View ArticleGoogle Scholar
- Kamiya T, Nomura K, Hosono H: Origins of high mobility and low operation voltage of amorphous oxide TFTs: electronic structure, electron transport, defects and doping*. J Display Technol 2009, 5: 468–483.View ArticleGoogle Scholar
- Zan H-W, Yeh C-C, Meng H-F, Tsai C-C, Chen L-H: Achieving high field-effect mobility in amorphous indium-gallium-zinc oxide by capping a strong reduction layer. Adv Mater 2012, 24: 3509–3514. 10.1002/adma.201200683View ArticleGoogle Scholar
- Hosono H: Ionic amorphous oxide semiconductors: Material design, carrier transport, and device application. J Non-Cryst Solids 2006, 352: 851–858. 10.1016/j.jnoncrysol.2006.01.073View ArticleGoogle Scholar
- Iwasaki T, Itagaki N, Den T, Kumomi H, Nomura K, Kamiya T, Hosono H: Combinatorial approach to thin-film transistors using multicomponent semiconductor channels: an application to amorphous oxide semiconductors in In–Ga–Zn–O system. Appl Phys Lett 2007., 90: 242114–1242114–3 242114-1242114-3Google Scholar
- Kim ES, Ryu MK, Son KS, Kim TS, Lee K-H, Park KB, Park JS, Maeng WJ, Kim HS, Seon JB, Choi W, Lee S: Metal-channel-aided oxide thin film transistor. Meeting Abstracts 2010, 1819: MA2010–02.Google Scholar
- Kim MJ, Choi D-k: Effect of enhanced-mobility current path on the mobility of AOS TFT. Microelectron Reliab 2012, 52: 1346–1349. 10.1016/j.microrel.2012.02.012View ArticleGoogle Scholar
- Flores F, Tejedor C: Energy barriers and interface states at heterojunctions. J Phys C Solid State Phys 1979, 12: 731. 10.1088/0022-3719/12/4/018View ArticleGoogle Scholar
- Mosbacker HL, Strzhemechny YM, White BD, Smith PE, Look DC, Reynolds DC, Litton CW, Brillson LJ: Role of near-surface states in ohmic-Schottky conversion of Au contacts to ZnO. Appl Phys Lett 2005., 87: 012102–1-012102–3 012102-1-012102-3Google Scholar
- Tay YY, Li S, Sun CQ, Chen P: Size dependence of Zn 2p3/2 binding energy in nanocrystalline ZnO. Appl Phys Lett 2006., 88: 173118–1-173118–3 173118-1-173118-3Google Scholar
- Lim SJ, Kim J-M, Kim D, Lee C, Park J-S, Kim H: The effects of UV exposure on plasma-enhanced atomic layer deposition ZnO thin film transistor. Electrochem Solid-State Lett 2010, 13: H151-H154. 10.1149/1.3322733View ArticleGoogle Scholar
- Janotti A, Van de Walle CG: Hydrogen multicentre bonds. Nat Mater 2007, 6: 44–47. 10.1038/nmat1795View ArticleGoogle Scholar
- Nomura K, Kamiya T, Hosono H: Effects of diffusion of hydrogen and oxygen on electrical properties of amorphous oxide semiconductor, In-Ga-Zn-O. ECS J Solid State Sci Technol 2013, 2: P5-P8. 10.1149/2.025310jssView ArticleGoogle Scholar
- Bang S, Lee S, Ko Y, Park J, Shin S, Seo H, Jeon H: Photocurrent detection of chemically tuned hierarchical ZnO nanostructures grown on seed layers formed by atomic layer deposition. Nanoscale Res Lett 2012, 7: 290. 10.1186/1556-276X-7-290View ArticleGoogle Scholar
- Seo H, Lucovsky G, Fleming LB, Ulrich MD, Lüning J, Koster G, Geballe TH: Length scales for coherent π-bonding interactions in complex high-k oxide dielectrics and their interfaces. Microelectron Eng 2007, 84: 2298–2301. 10.1016/j.mee.2007.04.069View ArticleGoogle Scholar
- Schroder DK: Semiconductor Material and Device Characterization. Hoboken, New Jersey, United States of America: Wiley-Interscience; 2006.Google Scholar
- Tsao SW, Chang TC, Huang SY, Chen MC, Chen SC, Tsai CT, Kuo YJ, Chen YC, Wu WC: Hydrogen-induced improvements in electrical characteristics of a-IGZO thin-film transistors. Solid State Electron 2010, 54: 1497–1499. 10.1016/j.sse.2010.08.001View ArticleGoogle Scholar
- Nomura K, Kamiya T, Ohta H, Ueda K, Hirano M, Hosono H: Carrier transport in transparent oxide semiconductor with intrinsic structural randomness probed using single-crystalline InGaO3(ZnO)5 films. Appl Phys Lett 2004, 85: 1993–1995. 10.1063/1.1788897View ArticleGoogle Scholar
- Takagi A, Nomura K, Ohta H, Yanagi H, Kamiya T, Hirano M, Hosono H: Carrier transport and electronic structure in amorphous oxide semiconductor, a-InGaZnO4. Thin Solid Films 2005, 486: 38–41. 10.1016/j.tsf.2004.11.223View ArticleGoogle Scholar
- Park JS, Jeong JK, Chung HJ, Mo YG, Kim HD: Electronic transport properties of amorphous indium-gallium-zinc oxide semiconductor upon exposure to water. Appl Phys Lett 2008., 92: 072104–1–072104–3 072104-1–072104-3Google Scholar
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