Transparent electronics is today one of the most advanced topics for a wide range of device applications. The key components are wide bandgap semiconductors, where oxides of different origins play an important role, not only as passive component but also as active component, similar to what is observed in conventional semiconductors like silicon. Transparent electronics has gained special attention during the last few years and is today established as one of the most promising technologies for leading the next generation of flat panel display due to its excellent electronic performance. In this paper the recent progress in n- and p-type oxide based thin-film transistors (TFT) is reviewed, with special emphasis on solution-processed and p-type, and the major milestones already achieved with this emerging and very promising technology are summarizeed. After a short introduction where the main advantages of these semiconductors are presented, as well as the industry expectations, the beautiful history of TFTs is revisited, including the main landmarks in the last 80 years, finishing by referring to some papers that have played an important role in shaping transparent electronics. Then, an overview is presented of state of the art n-type TFTs processed by physical vapour deposition methods, and finally one of the most exciting, promising, and low cost but powerful technologies is discussed: solution-processed oxide TFTs. Moreover, a more detailed focus analysis will be given concerning p-type oxide TFTs, mainly centred on two of the most promising semiconductor candidates: copper oxide and tin oxide. The most recent data related to the production of complementary metal oxide semiconductor (CMOS) devices based on n- and p-type oxide TFT is also be presented. The last topic of this review is devoted to some emerging applications, finalizing with the main conclusions. Related work that originated at CENIMAT|I3N during the last six years is included in more detail, which has led to the fabrication of high performance n- and p-type oxide transistors as well as the fabrication of CMOS devices with and on paper.

Oxide Semiconductor Thin‐Film Transistors: A Review of Recent Advances

We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

Density functional theory for transition metals and transition metal chemistry

Contemporary theories of defects and impurities in semiconductors rely to a large extent on supercell calculations within density-functional theory using the approximate local-density approximation (LDA) or generalized gradient approximation (GGA) functionals. Such calculations are, however, affected by considerable uncertainties associated with: (i) the ``band-gap problem,'' which occurs not only in the Kohn-Sham single-particle energies but also in the quasiparticle gap (LDA or GGA) calculated from total-energy differences, and (ii) supercell finite-size effects. In the case of the oxygen vacancy in ZnO, uncertainties (i) and (ii) have led to a large spread in the theoretical predictions, with some calculations suggesting negligible vacancy concentrations, even under Zn-rich conditions, and others predicting high concentrations. Here, we critically assess (i) the different methodologies to correct the band-gap problem. We discuss approaches based on the extrapolation of perturbations which open the band gap, and the self-consistent band-gap correction employing the $\text{LDA}+U$ method for $d$ and $s$ states simultaneously. From the comparison of the results of different gap-correction, including also recent results from other literature, we conclude that to date there is no universal scheme for band gap correction in general defect systems. Therefore, we turn instead to classification of different types of defect behavior to provide guidelines on how the physically correct situation in an LDA defect calculation can be recovered. (ii) Supercell finite-size effects: We performed test calculations in large supercells of up to 1728 atoms, resolving a long-standing debate pertaining to image charge corrections for charged defects. We show that once finite-size effects not related to electrostatic interactions are eliminated, the analytic form of the image charge correction as proposed by Makov and Payne leads to size-independent defect formation energies, thus allowing the calculation of well-converged energies in fairly small supercells. We find that the delocalized contribution to the defect charge (i.e., the defect-induced change of the charge distribution) is dominated by the dielectric screening response of the host, which leads to an unexpected effective $1/L$ scaling of the image charge energy, despite the nominal $1/{L}^{3}$ scaling of the third-order term. Based on this analysis, we suggest that a simple scaling of the first order term by a constant factor (approximately 2/3) yields a simple but accurate image-charge correction for common supercell geometries. Finally, we discuss the theoretical controversy pertaining to the formation energy of the O vacancy in ZnO in light of the assessment of different methodologies in the present work, and we review the present experimental situation on the topic.

Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs

This review compiles results of experimental and theoretical studies on thin films and quantum structures of semiconductors with randomly distributed Mn ions, which exhibit spintronic functionalities associated with collective ferromagnetic spin ordering. Properties of p-type Mn-containing III-V as well as II-VI, IV-VI, V-2 -VI3, I-II-V, and elemental group IV semiconductors are described, paying particular attention to the most thoroughly investigated system (Ga, Mn)As that supports the hole-mediated ferromagnetic order up to 190 K for the net concentration of Mn spins below 10%. Multilayer structures showing efficient spin injection and spin-related magnetotransport properties as well as enabling magnetization manipulation by strain, light, electric fields, and spin currents are presented together with their impact on metal spintronics. The challenging interplay between magnetic and electronic properties in topologically trivial and nontrivial systems is described, emphasizing the entangled roles of disorder and correlation at the carrier localization boundary. Finally, the case of dilute magnetic insulators is considered, such as (Ga, Mn)N, where low-temperature spin ordering is driven by short-ranged superexchange that is ferromagnetic for certain charge states of magnetic impurities.

Dilute ferromagnetic semiconductors: Physics and spintronic structures

In recent years, nanocrystals of metal sulfide materials have attracted scientific research interest for renewable energy applications due to the abundant choice of materials with easily tunable electronic, optical, physical and chemical properties. Metal sulfides are semiconducting compounds where sulfur is an anion associated with a metal cation; and the metal ions may be in mono-, bi- or multi-form. The diverse range of available metal sulfide materials offers a unique platform to construct a large number of potential materials that demonstrate exotic chemical, physical and electronic phenomena and novel functional properties and applications. To fully exploit the potential of these fascinating materials, scalable methods for the preparation of low-cost metal sulfides, heterostructures, and hybrids of high quality must be developed. This comprehensive review indicates approaches for the controlled fabrication of metal sulfides and subsequently delivers an overview of recent progress in tuning the chemical, physical, optical and nano- and micro-structural properties of metal sulfide nanocrystals using a range of material fabrication methods. For hydrogen energy production, three major approaches are discussed in detail: electrocatalytic hydrogen generation, powder photocatalytic hydrogen generation and photoelectrochemical water splitting. A variety of strategies such as structural tuning, composition control, doping, hybrid structures, heterostructures, defect control, temperature effects and porosity effects on metal sulfide nanocrystals are discussed and how they are exploited to enhance performance and develop future energy materials. From this literature survey, energy conversion currently relies on a limited range of metal sulfides and their composites, and several metal sulfides are immature in terms of their dissolution, photocorrosion and long-term durability in electrolytes during water splitting. Future research directions for innovative metal sulfides should be closely allied to energy and environmental issues, along with their advanced characterization, and developing new classes of metal sulfide materials with well-defined fabrication methods.

Recent advances in metal sulfides: from controlled fabrication to electrocatalytic, photocatalytic and photoelectrochemical water splitting and beyond

While most of crystalline wide gap oxides are both stoichiometric and insulating, a handful of them including ZnO and ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$ are naturally anion-deficient and electron conductors. Even fewer of the oxides are naturally cation-deficient and hole conductors, the arch-type of which is ${\mathrm{Cu}}_{2}\mathrm{O}$. Based on first principles calculation of equilibrium nonstoichiometry and defect stability, we explain why the ${\mathrm{Cu}}^{(I)}({d}^{10})$ oxide-based materials are both $p$-type and naturally cation-deficient, and why cation vacancies lead to delocalized, conductive states, whereas in other oxides (e.g., ZnO and MgO), they lead to localized, nonconductive states.

Origins of the p -type nature and cation deficiency in Cu 2 O and related materials

Transition-metal atoms embedded in an ionic or semiconducting crystal can exist in various oxidation states that have distinct signatures in X-ray photoemission spectroscopy and 'ionic radii' which vary with the oxidation state of the atom. These oxidation states are often tacitly associated with a physical ionization of the transition-metal atoms--that is, a literal transfer of charge to or from the atoms. Physical models have been founded on this charge-transfer paradigm, but first-principles quantum mechanical calculations show only negligible changes in the local transition-metal charge as the oxidation state is altered. Here we explain this peculiar tendency of transition-metal atoms to maintain a constant local charge under external perturbations in terms of an inherent, homeostasis-like negative feedback. We show that signatures of oxidation states and multivalence--such as X-ray photoemission core-level shifts, ionic radii and variations in local magnetization--that have often been interpreted as literal charge transfer are instead a consequence of the negative-feedback charge regulation.

Charge self-regulation upon changing the oxidation state of transition metals in insulators.

Theoretical methods have greatly influenced experiment in search of the elusive marriage between semiconductor electronics and magnetism, and the development of spintronics. The path has not always been a straight one, but realizing the limitations and strengths of theoretical approaches promises a straighter course.

https://physics.aps.org/articles/pdf/10.1103/Physics.3.53

The quest for dilute ferromagnetism in semiconductors: Guides and misguides by theory

The well-known ``band-gap'' problem in approximate density functionals is manifested mainly in an overly low energy of the conduction band (CB). As a consequence, the localized gap states of $3d$ impurities states in wide-gap oxides such as $\mathrm{ZnO}$ occur often incorrectly as resonances inside the CB, leading to a spurious transfer of electrons from the impurity state into the CB of the host, and to a physically misleading description of the magnetic $3d\text{\ensuremath{-}}3d$ interactions. A correct description requires that the magnetic coupling of the impurity pairs be self-consistently determined in the presence of a correctly positioned CB (with respect to the $3d$ states), which we achieve here through the addition of empirical nonlocal external potentials to the standard density functional Hamiltonian. After this correction, both Co and Cr form occupied localized states in the gap and empty resonances low inside the CB. In otherwise undoped $\mathrm{ZnO}$, Co and Cr remain paramagnetic, but electron-doping instigates strong ferromagnetic coupling when the resonant states become partially occupied.

Magnetic Interactions of Cr-Cr and Co-Co Impurity Pairs in ZnO within a Band-Gap Corrected Density-Functional Approach

$3d$ transition impurities in wide-gap oxides may function as donor/acceptor defects to modify carrier concentrations, and as magnetic elements to induce collective magnetism. Previous first-principles calculations have been crippled by the LDA error, where the occupation of the $3d$-induced levels is incorrect due to spurious charge spilling into the misrepresented host conduction band, and have only considered magnetism and carrier doping separately. We employ a band-structure-corrected theory, and present simultaneously the chemical trends for electronic properties, carrier doping, and magnetism along the series of $3{d}^{1}--3{d}^{8}$ transition-metal impurities in the representative wide-gap oxide hosts ${\text{In}}_{2}{\text{O}}_{3}$ and ZnO. We find that most $3d$ impurities in ${\text{In}}_{2}{\text{O}}_{3}$ are amphoteric, whereas in ZnO, the early $3d$'s (Sc, Ti, and V) are shallow donors, and only the late $3d$'s (Co and Ni) have acceptor transitions. Long-range ferromagnetic interactions emerge due to partial filling of $3d$ resonances inside the conduction band and, in general, require electron doping from additional sources.

Hannes Raebiger

Papers

Origins of the p -type nature and cation deficiency in Cu 2 O and related materials

Charge self-regulation upon changing the oxidation state of transition metals in insulators.

The quest for dilute ferromagnetism in semiconductors: Guides and misguides by theory

Magnetic Interactions of Cr-Cr and Co-Co Impurity Pairs in ZnO within a Band-Gap Corrected Density-Functional Approach

Electronic structure, donor and acceptor transitions, and magnetism of 3d impurities in In2O3 and ZnO