Transparent electronic devices formed on flexible substrates are expected to meet emerging technological demands where silicon-based electronics cannot provide a solution. Examples of active flexible applications include paper displays and wearable computers1. So far, mainly flexible devices based on hydrogenated amorphous silicon (a-Si:H)2,3,4,5 and organic semiconductors2,6,7,8,9,10 have been investigated. However, the performance of these devices has been insufficient for use as transistors in practical computers and current-driven organic light-emitting diode displays. Fabricating high-performance devices is challenging, owing to a trade-off between processing temperature and device performance. Here, we propose to solve this problem by using a novel semiconducting material—namely, a transparent amorphous oxide semiconductor from the In-Ga-Zn-O system (a-IGZO)—for the active channel in transparent thin-film transistors (TTFTs). The a-IGZO is deposited on polyethylene terephthalate at room temperature and exhibits Hall effect mobilities exceeding 10 cm2 V-1 s-1, which is an order of magnitude larger than for hydrogenated amorphous silicon. TTFTs fabricated on polyethylene terephthalate sheets exhibit saturation mobilities of 6–9 cm2 V-1 s-1, and device characteristics are stable during repetitive bending of the TTFT sheet.

Room-temperature fabrication of transparent flexible thin-film transistors using amorphous oxide semiconductors

We report the fabrication of transparent field-effect transistors using a single-crystalline thin-film transparent oxide semiconductor, InGaO 3 (ZnO) 5 , as an electron channel and amorphous hafnium oxide as a gate insulator. The device exhibits an on-to-off current ratio of ∼10 6 and a field-effect mobility of ∼80 square centimeters per volt per second at room temperature, with operation insensitive to visible light irradiation. The result provides a step toward the realization of transparent electronics for next-generation optoelectronics.

http://science.sciencemag.org/content/sci/300/5623/1269.full.pdf

Thin-Film Transistor Fabricated in Single-Crystalline Transparent Oxide Semiconductor

The present status and prospects for further development of polycrystalline or amorphous transparent conducting oxide (TCO) semiconductors used for practical thin-film transparent electrode applications are presented in this paper. The important TCO semiconductors are impurity-doped ZnO, In2O3 and SnO2 as well as multicomponent oxides consisting of combinations of ZnO, In2O3 and SnO2, including some ternary compounds existing in their systems. Development of these and other TCO semiconductors is important because the expanding need for transparent electrodes for optoelectronic device applications is jeopardizing the availability of indium-tin-oxide (ITO), whose main constituent, indium, is a very expensive and scarce material. Al- and Ga-doped ZnO (AZO and GZO) semiconductors are promising as alternatives to ITO for thin-film transparent electrode applications. In particular, AZO thin films, with a low resistivity of the order of 10−5 Ω cm and source materials that are inexpensive and non-toxic, are the best candidates. However, further development of the deposition techniques, such as magnetron sputtering or vacuum arc plasma evaporation, as well as of the targets is required to enable the preparation of AZO and GZO films on large area substrates with a high deposition rate.

https://iopscience.iop.org/article/10.1088/0268-1242/20/4/004/pdf

Transparent conducting oxide semiconductors for transparent electrodes

Recently, we have demonstrated the potential of amorphous oxide semiconductors (AOSs) for developing flexible thin-film transistors (TFTs). A material exploration of AOSs desired as the channel layer in TFTs is most important for developing high-performance devices. Here, we report our concept of material exploration for AOSs in high-performance flexible and transparent TFTs from the viewpoints of chemical bonding and electronic structure in oxide semiconductors. We find that amorphous In–Ga–Zn–O (a-IGZO) exhibits good carrier transport properties such as reasonably high Hall mobilities (>10 cm2V-1s-1) and a good controllability of carrier concentration from <1015 to 1020 cm-3. In addition, a-IGZO films have better chemical stabilities in ambient atmosphere and at temperatures up to 500 °C. The flexible and transparent TFT fabricated using a-IGZO channel layer at room temperature operated with excellent performances, such as normally-off characteristics, on/off current ratios (~106) and field-effect mobilities (~10 cm2V-1s-1), which are higher by an order of magnitude than those of amorphous Si:H and organics TFTs.

https://iopscience.iop.org/article/10.1143/JJAP.45.4303/pdf

Amorphous Oxide Semiconductors for High-Performance Flexible Thin-Film Transistors

https://iopscience.iop.org/article/10.1088/1468-6996/11/4/044305/pdf

Present status of amorphous In–Ga–Zn–O thin-film transistors

Optically transparent oxides tend to be electrical insulators, by virtue of their large electronic bandgap (⩾3.1 eV). The most notable exceptions are doped versions of the oxides In2O3, SnO2 and ZnO—all n-type (electron) conductors—which are widely used as the transparent electrodes in flat-panel displays1,2. On the other hand, no transparent oxide exhibiting high p-type (hole) conductivity is known to exist, whereas such materials could open the way to a range of novel applications. For example, a combination of the two types of transparent conductor in the form of a pn junction could lead to a ‘functional’ window that transmits visible light yet generates electricity in response to the absorption of ultraviolet photons. Here we describe a strategy for identifying oxide materials that should combine p-type conductivity with good optical transparency. We illustrate the potential of this approach by reporting the properties of thin films of CuAlO2, a transparent oxide having room-temperature p-type conductivity up to 1 S cm−1. Although the conductivity of our candidate material is significantly lower than that observed for the best n-type conducting oxides, it is sufficient for some applications, and demonstrates that the development of transparent p-type conductors is not an insurmountable goal.

P-type electrical conduction in transparent thin films of CuAlO2

A working hypothesis to find wide gap oxide semiconductors was proposed on the basis of simple considerations. The hypothesis predicts that amorphous double oxides composed of heavy metal cations (HMCs) with an electronic configuration (n − 1)d10s0 are promising candidates for a novel class of amorphous semiconductors. Electrical and optical properties of three amorphous double oxides composed of the HMCs, a-AgSbO3, Cd2GeO4 and Cd2PbO4, were examined, following this hypothesis. It was found that when carrier electrons are generated via the formation of oxygen vacancies or doping of excess cations by ion implantation, these three wide band gap amorphous oxides show high electrical conductivities of 10−1 to 102 S cm−1 at ∼ 300 K and the conductivity remains almost constant down to 77 or 4 K for high carrier concentrations (> 1018 cm−3). This high conductivity originates primarily from a large Hall mobility of ∼ 10 cm2 V−1 s−1, which is higher by several orders of magnitude than that in amorphous transition metal oxides, Si:H and chalcogenides. A variety of chemical compositions for a novel oxide amorphous semiconductor are suggested.

Novel oxide amorphous semiconductors: transparent conducting amorphous oxides

Chemical design to find a new transparent conductive oxide having p-type conductivity has been proposed. Following the chemical design, we have selected CuGaO2 and CuAlO2 as candidate materials. CuGaO2 thin films were prepared on silica glass substrates by RF sputtering method. The optical band gap of the film was estimated to be ∼3.4 eV. Positive sign of Seebeck coefficient demonstrated the p-type conductivity of the film. The dc conductivity of the film was 5.6 × 10−3S·cm-1 and the activation energy was 0.22 eV at room temperature. Because of rough texture of the film, the observed conductivity was not an intrinsic property of the material. Further, CuAlO2 thin films were prepared by laser ablation. The film deposited in O2 atmosphere of 1.3 Pa at 690°C showed higher optical transmission in visible and near-infrared regions than previously reported. Contribution of Cu 3d components to upper edge of valence band in CuGaO2 and CuAlO2 were confirmed by photoemission spectroscopic measurements.

Chemical Design and Thin Film Preparation of p-Type Conductive Transparent Oxides

High-temperature thermoelectric properties of the oxide material: Ba1−xSrxPbO3 (x = 0 − 0.6)

To elucidate the thermoelectric properties at high temperatures, perovskite-type La-doped BaSnO3 ceramics were fabricated by a polymerized complex (PC) method and subsequent spark plasma sintering (SPS) technique. Fine powders of Ba1−xLaxSnO3 (x = 0.00–0.07) were prepared by the PC method using citrate complexes, and SPS treatment converted the powders into dense ceramics with relative densities of 93–97%. The La content dependence of the lattice parameter suggested that the solubility of La for Ba sites was approximately x = 0.03. The temperature dependence of the electrical conductivity σ and Seebeck coefficient S showed that each La-doped ceramic was an n-type degenerate semiconductor in the measured temperature range of 373–1073 K. The La content dependence of the S values indicated that the electron carrier concentration increased successively up to x = 0.03, which was the solubility limit of the La atoms. The thermoelectric power factors S2σ increased drastically with La doping, and reached a maximum for x = 0.01 with values of 0.8 × 10−4 W m−1 K−2 at 373 K to 2.8 × 10−4 W m−1 K−2 at 1073 K.

Masahiro Yasukawa

Papers

P-type electrical conduction in transparent thin films of CuAlO2

Novel oxide amorphous semiconductors: transparent conducting amorphous oxides

Chemical Design and Thin Film Preparation of p-Type Conductive Transparent Oxides

High-temperature thermoelectric properties of the oxide material: Ba1−xSrxPbO3 (x = 0 − 0.6)

High-temperature thermoelectric properties of La-doped BaSnO3 ceramics