Surface chemistry of nanocrystals determines distinct thermal behaviours of upconversion emission.

HfO 2 films deposited via tetrakis diethylamido hafnium ͑TDEAH͒ precursor using MOCVD ͑metal organic chemical vapor deposition͒ are presented. TDEAH is a promising precursor candidate for the deposition of high permittivity gate dielectrics. We report the impact of process and annealing conditions on the physical and electrical properties of the film. Deposition and annealing temperatures influence the microstructure, density, and impurity levels of TDEAH HfO 2 films. Spectroscopic ellipsometry shows that film microstructure manifests itself in the optical properties of the film, particularly in the presence of a band edge related feature at 5.8 eV. An impurity analysis using Auger electron spectroscopy, secondary ion mass spectroscopy, and Raman spectroscopy, indicates that carbon impurities from the precursor exist as clusters within the HfO 2 dielectric. The impact of deposition temperature and annealing temperature on the capacitance vs. voltage and current density vs. voltage characteristics of platinum gated capacitors is studied. Correlation of physical film properties with the capacitance and leakage behavior of the TDEAH HfO 2 films indicates that impurities, in the form of carbon clusters, and low HfO 2 film density are detrimental to the electrical performance of the gate dielectric.As the smallest feature size on a microprocessor approaches 50 nm, the primary dielectric layer in the field effect transistor, referred to as the gate dielectric or gate oxide, will thin to below 15 Å. Around this thickness, electrical leakage current through the dielectric becomes excessive and is expected to cause problems due to either high power dissipation or circuit reliability. 1 One solution to this problem is to replace SiO 2 dielectrics with higher permittivity dielectrics. A higher permittivity dielectric can be thicker and still achieve the same capacitance as a thinner SiO 2 dielectric. The starting point for identifying possible replacements for SiO 2 dielectrics is to evaluate their thermal stability in direct contact with silicon. Reactions between the high permittivity dielectric and the silicon substrate or electrode are undesirable. Extensive thermodynamic calculations have been performed by Hubbard and Schlom, 2 identifying numerous binary and ternary oxides that are candidate materials. Some of the binary oxides that are leading contenders for replacing SiO 2 include: ZrO 2 , HfO 2 , Y 2 O 3 , and Al 2 O 3 . In addition, there are numerous ternary ͑or mixed͒ oxides that have also been predicted, or experimentally determined, to be stable in contact with silicon.In general, the class IIIB and IVB oxides tend to be the most thermodynamically stable oxides for potential use in integrated circuit manufacturing. Doping the IIIB and IVB oxides with Al 2 O 3 or SiO 2 increases the crystallization temperature. Such amorphous dielectrics are desirable because grain boundaries enhance diffusion of dopants from the electrode to the substrate and possibly contribute to electrical leakage. On the other hand, doping...

In this letter, we present a comparative experimental–simulation study of Au-nanodisc-enhanced upconversion of 1500 nm light in an Er3+ doped TiO2 thin film. The geometry of the Au nanodiscs was guided by finite-element simulations based on a single nanodisc in a finite computational domain and controlled experimentally using electron-beam lithography. The surface-plasmon resonances (SPRs) exhibited a well-known spectral red shift with increasing diameter, well explained by the model. However, an experimentally observed double-peak SPR, which resulted from inter-particle interactions, was expectedly not captured by the single-particle model. At resonance, the model predicted a local-field enhancement of the upconversion yield, and experimentally, the luminescence measurements showed such enhancement up to nearly 7 fold from a nanodisc with 315 nm diameter and 50 nm height. The upconversion enhancement agreed qualitatively with the theoretical predictions, however with 3–5 times higher enhancement, which was attributed to scattered light from neighboring particles.

We propose a simplified rate-equation model for the 1500 nm to 980 nm upconversion in Er 3+ . The simplifications, based on typical experimental conditions as well as on conclusions based on previously published more advanced models, enable an analytical solution of the rate equations, which reproduces known properties of upconversion. We have compared the model predictions with intensity-dependent measurements on four samples with different optical properties, such as upconversion-luminescence yield and the characteristic lifetime of the 4 I 13/2 state. The saturation of the upconversion is in all cases well-described by the model over several orders of magnitude in excitation intensities. Finally, the model provides a new measure for the quality of upconverter systems based on Er 3+ -the saturation intensity. This parameter provides valuable information on upconversion parameters such as the rates of energy-transfer upconversion and cross-relaxation. In the present investigation, we used the saturation intensity to conclude that the differences in upconversion performance of the investigated samples are mainly due to differences in the nonradiative relaxation rates. * brianj@phys.au.dk 1 N. Bloembergen, Phys. Rev. Lett. 2, 84 (1959). 2 F. Auzel, J. Lumin. 31-32, 759 (1984).

Upconversion of sub-band-gap photons constitutes a promising way for improving the efficiency of silicon-based solar cells beyond the Shockley-Queisser limit. 1500 nm to 980 nm upconversion by trivalent erbium ions is well-suited for this purpose, but the small absorption cross section hinders real-world applications. We employ tailored gold nanostructures to vastly improve the upconversion efficiency in erbium-doped TiO 2 thin films. The nanostructures are found using topology optimization and parameter optimization and fabricated by electron beam lithography. In qualitative agreement with a theoretical model, the samples show substantial electric-field enhancements inside the upconverting films for excitation at 1500 nm for both s-and p-polarization under a wide range of incidence angles and excitation intensities. An unprecedented upconversion enhancement of 913 ± 51 is observed at an excitation intensity of 1.7 W cm −2 . We derive a semi-empirical expression for the photonically enhanced upconversion efficiency, valid for all excitation intensities. This allows us to determine the upconversion properties needed to achieve significant improvements in real-world solar-cell devices through photonic-enhanced upconversion.