We review work on In2O3:Sn films prepared by reactive e‐beam evaporation of In2O3 with up to 9 mol % SnO2 onto heated glass. These films have excellent spectrally selective properties when the deposition rate is ∼0.2 nm/s, the substrate temperature is ≳150 °C, and the oxygen pressure is ∼5×10−4 Torr. Optimized coatings have crystallite dimensions ≳50 nm and a C‐type rare‐earth oxide structure. We cover electromagnetic properties as recorded by spectrophotometry in the 0.2–50‐μm range, by X‐band microwave reflectance, and by dc electrical measurements. Hall‐effect data are included. An increase of the Sn content is shown to have several important effects: the semiconductor band gap is shifted towards the ultraviolet, the luminous transmittance remains high, the infrared reflectance increases to a high value beyond a certain wavelength which shifts towards the visible, phonon‐induced infrared absorption bands vanish, the microwave reflectance goes up, and the dc resisitivity drops to ∼2×10−4 Ω cm. The corre...

Evaporated Sn‐doped In2O3 films: Basic optical properties and applications to energy‐efficient windows

The task of quantizing general relativity raises serious questions about the meaning of the present formulation and interpretation of quantum mechanics when applied to so fundamental a structure as the space-time geometry itself. This paper seeks to clarify the foundations of quantum mechanics. It presents a reformulation of quantum theory in a form believed suitable for application to general relativity. The aim is not to deny or contradict the conventional formulation of quantum theory, which has demonstrated its usefulness in an overwhelming variety of problems, but rather to supply a new, more general and complete formulation, from which the conventional interpretation can be deduced. The relationship of this new formulation to the older formulation is therefore that of a metatheory to a theory, that is, it is an underlying theory in which the nature and consistency, as well as the realm of applicability, of the older theory can be investigated and clarified.

"relative State" Formulation of Quantum Mechanics

In this paper we present a unified treatment of non-radiative decay processes in large molecules which involve either electronic relaxation between two electronic states or unimolecular rearrangeme...

The energy gap law for radiationless transitions in large molecules

During the past decade, enormous progress has been made in growing ultrathin organic films and multilayer structures with a wide range of exciting optoelectronic properties. This progress has been made possible by several important advances in our understanding of organic films and their modes of growth. Perhaps the single most important advance has been the use of ultrahigh vacuum (UHV) as a means to achieve, for the first time, monolayer control over the growth of organic thin films with extremely high chemical purity and structural precision.1-3 Such monolayer control has been possible for many years using well-known techniques such as Langmuir-Blodgett film deposition,4 and more recently, self-assembled monolayers from solution have also been achieved.5 However, ultrahighvacuum growth, sometimes referred to as organic molecular beam deposition (OMBD) or organic molecular beam epitaxy (OMBE), has the advantage of providing both layer thickness control and an atomically clean environment and substrate. When combined with the ability to perform in situ highresolution structural diagnostics of the films as they are being deposited, techniques such as OMBD have provided an entirely new prospect for understanding many of the fundamental structural and optoelectronic properties of ultrathin organic film systems. Since such systems are both of intrinsic as well as practical interest, substantial effort worldwide has been invested in attempting to grow and investigate the properties of such thin-film systems. This paper is a review of recent progress made in organic thin films grown in ultrahigh vacuum or using other vapor-phase deposition methods. We will describe the most important work which has been published in this field since the emergence of OMBD in the mid-1980s. Both the nature of thin-film growth and structural ordering will be discussed, as well as some of the more interesting consequences to the physical properties of such organic thin-film systems will be considered both from a theoretical as well as an experimental viewpoint. Indeed, it will 1793 Chem. Rev. 1997, 97, 1793−1896

Ultrathin Organic Films Grown by Organic Molecular Beam Deposition and Related Techniques.

Electrical and optical spectroscopic studies of TiO2 anatase thin filmsdeposited by sputtering show that the metastable phase anatase differs in electronic properties from the well‐known, stable phase rutile. Resistivity and Hall‐effect measurements reveal an insulator–metal transition in a donor band in anatase thin films with high donor concentrations. Such a transition is not observed in rutile thin films with similar donor concentrations. This indicates a larger effective Bohr radius of donor electrons in anatase than in rutile, which in turn suggests a smaller electron effective mass in anatase. The smaller effective mass in anatase is consistent with the high mobility, bandlike conduction observed in anatase crystals. It is also responsible for the very shallow donor energies in anatase. Luminescence of self‐trapped excitons is observed in anatase thin films, which implies a strong lattice relaxation and a small exciton bandwidth in anatase. Optical absorption and photoconductivity spectra show that anatase thin films have a wider optical absorption gap than rutile thin films.

Electrical and optical properties of TiO2 anatase thin films

Using the method of generating function, we have discussed the shape of the absorption band and the probability for non-radiative transition of a trapped electron in insulating or semiconducting crystal, especially their temperature dependence. We have thereby chosen a model for the vibrational motion of the lattice as general as possible, the normal modes for any two electronic states being different as regards not only their equilibrium positions but also the principal axes and frequencies. For non-radia­ tive transition, we have derived, in comparatively general cases, the high and low temperature behaviors of the probability which correspond to the process through activated states and the tunneling of the lattice co-ordinates, respectively. The result is applied to calculations of the probability for thermal ionization of trapped electrons (or holes) and the capture cross-section of impurities for free electrons (or holes) in non-polar semiconductors. Further, the high temperature expansion of a density matrix is used to discuss the transitions on a most general model in which lattice vibration is no longer of harmonic type. Two problems related to the degeneracy of electronic states are discussed briefly. ting or semiconducting crystal has been studied by a number of authors. The simplest but most essential explanation of the broadening effect is found in the text-book of Mott and Gurney/l where they take a one-dimensional model for the lattice configuration space to discuss the breadth of the F-absorption band. More general discussion has been given by Muto2l on a quantum mechanical basis. Inui and Uemura, aJ with one dimensional model, explained the shift of the F-absorption peak by the thermal expansion of the lattice, taking advantage of Ivey's empirical law. Quantum mechanical calculation of adiabatic potentials was first carried out by Williams4l for KCl : Tl crystal, with one dimensional model. Huang and Rhys5l discussed the shape of the F-absorption band and the thermal ionization pro­ bability of the F-electron, taking into account all the longitudinal waves of optical modes of vibration which interact strongly with the electron. Their mathematical technique, though very ingenious in itself, is confined to a single frequency model, and can hardly be genera­ lized to a many-frequency model which involves, for instance, the acoustical modes. Under these circumstances it is very desirable to have a mathematical tool which enables one to discuss radiative and non-radiative transitions on a general model of lattice vibration. One of the present authors6l developed the method of generating function several years ago,

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Application of the Method of Generating Function to Radiative and Non-Radiative Transitions of a Trapped Electron in a Crystal

Excitonic Processes in Solids

Possible patterns of vibration-induced splitting in the absorption band of localized electrons in solid are investigated within the Condon approximation. The modes of lattice vibrations around the imperfection which give rise to the level splitting of degenerate excited states are classified into active and potentially active modes according as they cause the absorption band to split or not. The result is applied to the analysis of the absorption bands of Tl + - like ions in alkali halides. One can explain the triplet structure of the C band and the doublet structure of the A band with its temperature sensitive asymmetry, by introducing the coupling constant c between the p -electron and the trigonal lattice vibrations as a single adjustable parameter. The dependences of c upon the host alkali halide and on the charge of the impurity ion are explained by a point-charge plus point-dipole model for the neighboring halide ions.

Dynamical Jahn-Teller Effect in Alkali Halide Phosphors Containing Heavy Metal Ions

The importance of the acoustical mode of lattice vibration for self- trapping of an electron is shown. It is shown that when the coupling constant between the electron and the acoustical mode vibration exceeds a certain critical value, the effective mass of the electron changes discontinuously to such an enormous value that the electron is practically allowed to take a localized self- trapping state as an eigenstate. This model is in contrast with the case of the pelaron, in which the effective mass changes continuously with coupling constant. This difference is attributed to the different force range of electron-lattice interaction in the two cases. (auth)

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Self-Trapping of an Electron by the Acoustical Mode of Lattice Vibration. I

Theory for the Urbach-Martienssen (U-M) rule on the low energy tail of the fundamental absorption edge of insulators is proposed. The exciton propagator solved for an adiabatic lattice is averaged for lattice vibrations at finite temperature, and the self-energy of exciton is obtained. It describes two characters of exciton in the lattice; the one is the mobile nature of exciton in the undeformed lattice, and the other is the localized nature of exciton trapped momentarily by the lattice deformation due to thermal vibrations. The interplay of the two natures results in the U-M tail below the exciton absorption peak. The result can be interpreted in terms of the Franck-Condon principle where the mobile nature is incorporated in the giant oscillator strength of the momentarily trapped exciton. Emission from this trapped state is discussed in connection with the U-M rule.

Yutaka Toyozawa

Papers

Application of the Method of Generating Function to Radiative and Non-Radiative Transitions of a Trapped Electron in a Crystal

Excitonic Processes in Solids

Dynamical Jahn-Teller Effect in Alkali Halide Phosphors Containing Heavy Metal Ions

Self-Trapping of an Electron by the Acoustical Mode of Lattice Vibration. I

Urbach-Martienseen Rule and Exciton Trapped Momentarily by Lattice Vibrations