Major developments, as well as remaining challenges and the associated research opportunities, are evaluated for three technologically distinct approaches to solar energy utilization: solar electricity, solar thermal, and solar fuels technologies. Much progress has been made, but research opportunities are still present for all approaches. Both evolutionary and revolutionary technology development, involving foundational research, applied research, learning by doing, demonstration projects, and deployment at scale will be needed to continue this technology-innovation ecosystem. Most of the approaches still offer the potential to provide much higher efficiencies, much lower costs, improved scalability, and new functionality, relative to the embodiments of solar energy-conversion systems that have been developed to date.

http://science.sciencemag.org/content/sci/351/6271/aad1920.full.pdf

Research opportunities to advance solar energy utilization

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

Copper-oxide compound semiconductors provide a unique possibility to tune the optical and electronic properties from insulating to metallic conduction, from bandgap energies of 2.1 eV to the infrared at 1.40 eV, i.e., right into the middle of the efficiency maximum for solar-cell applications. Three distinctly different phases, Cu2O, Cu4O3, and CuO, of this binary semiconductor can be prepared by thin-film deposition techniques, which differ in the oxidation state of copper. Their material properties as far as they are known by experiment or predicted by theory are reviewed. They are supplemented by new experimental results from thin-film growth and characterization, both will be critically discussed and summarized. With respect to devices the focus is on solar-cell performances based on Cu2O. It is demonstrated by photoelectron spectroscopy (XPS) that the heterojunction system p-Cu2O/n-AlGaN is much more promising for the application as efficient solar cells than that of p-Cu2O/n-ZnO heterojunction devices that have been favored up to now.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/pssb.201248128

Binary copper oxide semiconductors: From materials towards devices

The development of transparent p-type oxide semiconductors with good performance may be a true enabler for a variety of applications where transparency, power efficiency, and greater circuit complexity are needed. Such applications include transparent electronics, displays, sensors, photovoltaics, memristors, and electrochromics. Hence, here, recent developments in materials and devices based on p-type oxide semiconductors are reviewed, including ternary Cu-bearing oxides, binary copper oxides, tin monoxide, spinel oxides, and nickel oxides. The crystal and electronic structures of these materials are discussed, along with approaches to enhance valence-band dispersion to reduce effective mass and increase mobility. Strategies to reduce interfacial defects, off-state current, and material instability are suggested. Furthermore, it is shown that promising progress has been made in the performance of various types of devices based on p-type oxides. Several innovative approaches exist to fabricate transparent complementary metal oxide semiconductor (CMOS) devices, including novel device fabrication schemes and utilization of surface chemistry effects, resulting in good inverter gains. However, despite recent developments, p-type oxides still lag in performance behind their n-type counterparts, which have entered volume production in the display market. Recent successes along with the hurdles that stand in the way of commercial success of p-type oxide semiconductors are presented.

/pdf/recent-developments-in-p-type-oxide-semiconductor-materials-4iad1efbja.pdf

Recent Developments in p-Type Oxide Semiconductor Materials and Devices.

Due to its abundance, scalability, and nontoxicity, Cu2O has attracted extensive attention toward solar energy conversion, and it is the best performing metal oxide material. Until now, the high efficiency devices are all planar in structure, and their photocurrent densities still fall well below the theoretical value of 14.5 mA cm(-2) due to the incompatible light absorption and charge carrier diffusion lengths. Nanowire structures have been considered as a rational and promising approach to solve this issue, but due to various challenges, performance improvements through the use of nanowires have rarely been achieved. In this work, we develop a new synthetic method to grow Cu2O nanowire arrays on conductive fluorine-doped tin oxide substrates with well-controlled phase and excellent electronic and photonic properties. Also, we introduce an innovative blocking layer strategy to enable high performance. Further, through material engineering by combining a conformal nanoscale p-n junction, durable protective overlayer, and uniform catalyst decoration, we have successfully fabricated Cu2O nanowire array photocathodes for hydrogen generation from solar water splitting delivering unprecedentedly high photocurrent densities of 10 mA cm(-2) and stable operation beyond 50 h, establishing a new benchmark for metal oxide based photoelectrodes.

Cu2O Nanowire Photocathodes for Efficient and Durable Solar Water Splitting

High-efficiency heterojunction solar cells consisting of a nondoped Ga2O3 thin film as an n-type semiconductor layer and a p-type Cu2O sheet as the active layer as well as the substrate, prepared by thermally oxidizing a Cu sheet, are demonstrated. The use of an n-type Ga2O3 thin film can greatly improve the performance of n-Ga2O3/p-Cu2O heterojunction solar cells. The highest efficiency of 5.38% was obtained in an Al-doped ZnO/Ga2O3/Cu2O heterojunction solar cell fabricated with an n-Ga2O3 thin-film layer prepared at room temperature with a thickness of 75 nm by a pulsed laser deposition method.

https://iopscience.iop.org/article/10.7567/APEX.6.044101/pdf

High-Efficiency Cu2O-Based Heterojunction Solar Cells Fabricated Using a Ga2O3 Thin Film as N-Type Layer

High conversion efficiencies were achieved in low cost n–p heterojunction oxide solar cells with an Al-doped ZnO (AZO)/non-doped ZnO (ZO)/Cu2O structure. This achievement was made possible by the formation of an n-ZO thin-film layer, prepared with an appropriate thickness by low damage deposition, on high quality Cu2O sheets produced by the thermal oxidization of copper sheets: n-ZO thin film optimal thickness ranges from 30 to 50 nm. Photovoltaic characteristics such as an open circuit voltage of 0.69 V, a fill factor of 0.55 and a conversion efficiency of 3.83% were attained under simulated AM1.5G solar illumination.

https://iopscience.iop.org/article/10.1143/APEX.4.062301/pdf

High-Efficiency Oxide Solar Cells with ZnO/Cu2O Heterojunction Fabricated on Thermally Oxidized Cu2O Sheets

In this paper, we describe efforts to enhance the efficiency of Cu2O-based heterojunction solar cells fabricated with an aluminum–gallium–oxide (Al–Ga–O) thin film as the n-type layer and a p-type sodium (Na)-doped Cu2O (Cu2O:Na) sheet prepared by thermally oxidizing copper sheets. The optimal Al content [X; Al/(Ga + Al) atomic ratio] of an AlX–Ga1−X–O thin-film n-type layer was found to be approximately 2.5 at. %. The optimized resistivity was approximately 15 Ω cm for n-type AlX–Ga1−X–O/p-type Cu2O:Na heterojunction solar cells. A MgF2/AZO/Al0.025–Ga0.975–O/Cu2O:Na heterojunction solar cell with 6.1% efficiency was fabricated using a 60-nm-thick n-type oxide thin-film layer and a 0.2-mm-thick Cu2O:Na sheet with the optimized resistivity.

https://iopscience.iop.org/article/10.7567/APEX.8.022301/pdf

Heterojunction solar cell with 6% efficiency based on an n-type aluminum–gallium–oxide thin film and p-type sodium-doped Cu2O sheet

Efficiency enhancement was achieved in Cu2O-based heterojunction solar cells fabricated with a zinc–germanium-oxide (Zn1− x Ge x -O) thin film as the n-type window layer and a p-type Na-doped Cu2O (Cu2O:Na) sheet prepared by thermally oxidizing Cu sheets. The Ge content (x) dependence of the obtained photovoltaic properties of the heterojunction solar cells is mainly explained by the conduction band discontinuity that results from the electron affinity difference between Zn1− x Ge x -O and Cu2O:Na. The optimal value of x in Zn1− x Ge x -O thin films prepared by pulsed laser deposition was observed to be 0.62. An efficiency of 8.1% was obtained in a MgF2/Al-doped ZnO/Zn0.38Ge0.62-O/Cu2O:Na heterojunction solar cell.

https://iopscience.iop.org/article/10.7567/APEX.9.052301/pdf

Yuki Nishi

Papers

High-Efficiency Cu2O-Based Heterojunction Solar Cells Fabricated Using a Ga2O3 Thin Film as N-Type Layer

High-Efficiency Oxide Solar Cells with ZnO/Cu2O Heterojunction Fabricated on Thermally Oxidized Cu2O Sheets

Heterojunction solar cell with 6% efficiency based on an n-type aluminum–gallium–oxide thin film and p-type sodium-doped Cu2O sheet

Efficiency enhancement using a Zn1− x Ge x -O thin film as an n-type window layer in Cu2O-based heterojunction solar cells

Cu2O-based heterojunction solar cells with an Al-doped ZnO/oxide semiconductor/thermally oxidized Cu2O sheet structure