Optical transparency, tunable conducting properties and easy processability make metal oxides key materials for advanced optoelectronic devices. This Review discusses recent advances in the synthesis of these materials and their use in applications. Metal oxides (MOs) are the most abundant materials in the Earth's crust and are ingredients in traditional ceramics. MO semiconductors are strikingly different from conventional inorganic semiconductors such as silicon and III–V compounds with respect to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and optoelectronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, p–n junctions and complementary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semiconductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin-film transistors, solar cells, diodes and memories.

Metal oxides for optoelectronic applications

BACKGROUND The Information Age was founded on the semiconductor revolution, marked by the growth of high-purity semiconductor single crystals. The resultant design and fabrication of electronic devices exploits our ability to control the concentration, motion, and dynamics of charge carriers in the bulk semiconductor solid state. Our desire to introduce electronics everywhere is fueled by opportunities to create intelligent and enabling devices for the information, communication, consumer product, health, and energy sectors. This demand for ubiquitous electronics is spurring the design of materials that exhibit engineered physical properties and that can enable new fabrication methods for low-cost, large-area, and flexible devices. Semiconductors, which are at the heart of electronics and optoelectronics, come with high demands on chemical purity and structural perfection. Alternatives to silicon technology are expected to combine the electronic and optical properties of inorganic semiconductors (high charge carrier mobility, precise n- and p-type doping, and the ability to engineer the band gap energy) with the benefits of additive device manufacturing: low cost, large area, and the use of solution-based fabrication techniques. Along these lines, colloidal semiconductor quantum dots (QDs), which are nanoscale crystals of analogous bulk semiconductor crystals, offer a powerful platform for device engineers. Colloidal QDs may be tailored in size, shape, and composition and their surfaces functionalized with molecular ligands of diverse chemistry. At the nanoscale (typically 2 to 20 nm), quantum and dielectric confinement effects give rise to the prized size-, shape-, and composition-tunable electronic and optical properties of QDs. Surface ligands enable the stabilization of QDs in the form of colloids, allowing their bottom-up assembly into QD solids. The physical properties of QD solids can be designed by selecting the characteristics of the individual QD building blocks and by controlling the electronic communication between the QDs in the solid state. These QD solids can be engineered with application-specific electronic and optoelectronic properties for the large-area, solution-based assembly of devices. ADVANCES The large surface-to-volume ratio of QDs places a substantial importance on the composition and structure of the surface in defining the physical properties that govern the concentration, motion, and dynamics of excitations and charge carriers in QD solids. Recent studies have shown pathways to passivate uncoordinated atoms at the QD surface that act to trap and scatter charge carriers. Surface atoms, ligands, and ions can serve as dopants to control the electron affinity of QD solids. Surface ligands and surrounding matrices control the barriers to electronic, excitonic, and thermal transport between QDs and between QDs and matrices. New ligand chemistries and matrix materials have been reported that provide freedom to control the dynamics of excitons and charge carriers and to design device interfaces. These advances in engineering the chemical and physical properties of the QD surface have been translated into recent achievements of high-mobility transistors and circuits, high-quantum-yield photodetectors and light-emitting devices, and high-efficiency photovoltaic devices. OUTLOOK The dominant role and dynamic nature of the QD surface, and the strong motive to build novel QD devices, will drive the exploration of new surface chemistries and matrix materials, processes for their assembly and integration with other materials in devices, and measurements and simulations with which to map the relationship between surface chemistry and materials and device properties. Challenges remain to achieve full control over the carrier type, concentration, and mobility in the QD channel and the barriers and traps at device interfaces that limit the gain and speed of QD electronics. Surface chemistries that allow for both long carrier lifetime and high carrier mobility and the freedom to engineer the bandgap and band alignment of QDs and other device layers are needed to exploit physics particular to QDs and to advance device architectures that contribute to improving the performance of QD optoelectronics. The importance of thermal transport in QD solids and their devices is an essential emerging topic that promises to become of greater importance as we develop QD devices.

http://science.sciencemag.org/content/sci/353/6302/aac5523.full.pdf

Building devices from colloidal quantum dots.

Amorphous metal oxides are useful in optical, electronic and electrochemical devices. The bonding arrangement within these glasses largely determines their properties, yet it remains a challenge to manipulate their structures in a controlled manner. Recently, we developed synthetic protocols for incorporating nanocrystals that are covalently bonded into amorphous materials. This 'nanocrystal-in-glass' approach not only combines two functional components in one material, but also the covalent link enables us to manipulate the glass structure to change its properties. Here we illustrate the power of this approach by introducing tin-doped indium oxide nanocrystals into niobium oxide glass (NbOx), and realize a new amorphous structure as a consequence of linking it to the nanocrystals. The resulting material demonstrates a previously unrealized optical switching behaviour that will enable the dynamic control of solar radiation transmittance through windows. These transparent films can block near-infrared and visible light selectively and independently by varying the applied electrochemical voltage over a range of 2.5 volts. We also show that the reconstructed NbOx glass has superior properties-its optical contrast is enhanced fivefold and it has excellent electrochemical stability, with 96 per cent of charge capacity retained after 2,000 cycles.

https://www.pkusz.edu.cn/uploadfile/2013/0824/20130824114836947.pdf

Tunable near-infrared and visible-light transmittance in nanocrystal-in-glass composites

Manipulating metal atoms in a controllable way for the synthesis of materials with the desired structure and properties is the holy grail of chemical synthesis. The recent emergence of single atomic site catalysts (SASC) demonstrates that we are moving toward this goal. Owing to the maximum efficiency of atom-utilization and unique structures and properties, SASC have attracted extensive research attention and interest. The prerequisite for the scientific research and practical applications of SASC is to fabricate highly reactive and stable metal single atoms on appropriate supports. In this review, various synthetic strategies for the synthesis of SASC are summarized with concrete examples highlighting the key issues of the synthesis methods to stabilize single metal atoms on supports and to suppress their migration and agglomeration. Next, we discuss how synthesis conditions affect the structure and catalytic properties of SASC before ending this review by highlighting the prospects and challenges for the synthesis as well as further scientific researches and practical applications of SASC.

Chemical Synthesis of Single Atomic Site Catalysts.

Printable electronics present a new era of wearable electronic technologies. Detailed technologies consisting of novel ink semiconductor materials, flexible substrates, and unique processing methods can be integrated to create flexible sensors. To detect various stimuli of the human body, as well as specific environments, unique electronic devices formed by "ink-based semiconductors" onto flexible and/or stretchable substrates have become a major research trend in recent years. Materials such as inorganic, organic, and hybrid semiconductors with various structures (i.e., 1D, 2D and 3D) with printing capabilities have been considered for bio and medical applications. In this review, we report recent progress in materials and devices for future wearable sensor technologies.

Recent Progress in Materials and Devices toward Printable and Flexible Sensors

A method for annealing metal-oxide semiconductor films with deep-ultraviolet light yields thin-film transistors with performance comparable to that of thermally annealed devices, and widens the range of substrates on which such devices can be fabricated. Solution-processable metal-oxide semiconductors are attractive materials for low-cost, flexible electronics, but the need to anneal the deposited materials at relatively high temperatures limits the range of substrates on which such devices can be fabricated. Now Yong-Hoon Kim and colleagues demonstrate that irradiating the solution-cast films with deep ultraviolet light can obviate the need for an annealing step. In this system, photochemical activation serves essentially the same purpose as annealing, and the resulting semiconducting materials have device performance levels comparable to those produced using the high-temperature techniques. Amorphous metal-oxide semiconductors have emerged as potential replacements for organic and silicon materials in thin-film electronics. The high carrier mobility in the amorphous state, and excellent large-area uniformity, have extended their applications to active-matrix electronics, including displays, sensor arrays and X-ray detectors1,2,3,4,5,6,7. Moreover, their solution processability and optical transparency have opened new horizons for low-cost printable and transparent electronics on plastic substrates8,9,10,11,12,13. But metal-oxide formation by the sol–gel route requires an annealing step at relatively high temperature2,14,15,16,17,18,19, which has prevented the incorporation of these materials with the polymer substrates used in high-performance flexible electronics. Here we report a general method for forming high-performance and operationally stable metal-oxide semiconductors at room temperature, by deep-ultraviolet photochemical activation of sol–gel films. Deep-ultraviolet irradiation induces efficient condensation and densification of oxide semiconducting films by photochemical activation at low temperature. This photochemical activation is applicable to numerous metal-oxide semiconductors, and the performance (in terms of transistor mobility and operational stability) of thin-film transistors fabricated by this route compares favourably with that of thin-film transistors based on thermally annealed materials. The field-effect mobilities of the photo-activated metal-oxide semiconductors are as high as 14 and 7 cm2 V−1 s−1 (with an Al2O3 gate insulator) on glass and polymer substrates, respectively; and seven-stage ring oscillators fabricated on polymer substrates operate with an oscillation frequency of more than 340 kHz, corresponding to a propagation delay of less than 210 nanoseconds per stage.

Flexible metal-oxide devices made by room-temperature photochemical activation of sol–gel films

The suffusion of particles classified as coarse-grained soils in the Unified Soil Classification System has been relatively well investigated in previous studies whereas suffusion of clay particles has not been thoroughly explored. For clay particles, the surface interaction energy between clay and sand can be a critical factor in conjunction with hydraulic gradient. Therefore, this paper presented a series of designed soil-column experiments for assessing the reduction of ionic strength on suffusion of clay particles in the sand-clay mixture. The three most typical clay particles (kaolinite, illite, and montmorillonite) were selected and the ionic strength was decreased during the injection. The results indicate that the sequence of decreasing ionic strength induced substantial suffusion of clay particles, mainly attributed to the decreased attraction between sand grains and clay particles. In addition, among three types of clay particles, the high swelling potential of montmorillonite particles led to the most substantial increase in relative hydraulic conductivity caused by suffusion.

Taehyeong Kim

Papers

Flexible metal-oxide devices made by room-temperature photochemical activation of sol–gel films

Suffusion of sand-clay mixture by three-staged change of ionic strength

Measurement of water concentration along the straight channel of proton exchange membrane fuel cell