Stability Due to Peripheral Halogenation in Phthalocyanine Complexes

2007 ◽  
Vol 13 (2) ◽  
pp. 96-107 ◽  
Author(s):  
Masanori Koshino ◽  
Hiroki Kurata ◽  
Seiij Isoda
Keyword(s):  
Energy Loss ◽  
Radiation Damage ◽  
Copper Phthalocyanine ◽  
Thermal Analyses ◽  
Empty Space ◽  
Decomposition Temperature ◽  
Family Structures ◽  
Transmission Electron ◽  
Unit Cells ◽  
Electron Energy Loss

The effect of peripheral halogenation is examined based on analytical transmission electron microscopy and thermal analyses of two chemical family structures, specifically the vanadyl-phthalocyanine family (VOPcX: X = H16, F14.5) and the copper-phthalocyanine family (CuPcX: X = H16, F16, Cl16, Cl8Br8), focusing on the process of molecular changes and crystalline disintegrations. To clarify the molecular transformations, electron energy-loss spectroscopy (EELS) is applied to two fluorinated phthalocyanines (VOPcF14.5 and CuPcF16), by monitoring mass changes as well as energy loss near edge structures (ELNES). The elemental mass of both VOPcF14.5 and CuPcF16 remain constant up to 0.5 C·cm−2, except in the case of mass reduction attributed to oxygen loss occurring in VOPcF14.5. It is expected that the released oxygen will induce higher radiation damage in VOPcF14.5. Although mass variation is not observed in CuPcF16, it is found from ELNES that the π resonant system of nitrogen is more radiation sensitive than that of carbon. These results imply that the electron sensitivity in VOPcX is triggered by eliminated oxygen or, thus, an induced larger empty space, whereas the sensitivity of CuPcX is dominated only by a large intermolecular empty space resulting in the following bond alterations. It is also found that the decomposition temperature (Td) measured by thermal analyses and the characteristic dose (D1/e) are exponentially correlated to the “effective molecular occupancy” (Oe) evaluated as a volume function of molecules in unit cells. By measuring Td and/or Oe, we discuss the durability of peripheral halogenation with respect to the radiation damage.

Investigation of Switching Mechanism in HfO2-Based Oxide Resistive Memories by In-Situ Transmission Electron Microscopy and Electron Energy Loss Spectroscopy

2017 ◽  
Author(s):  
T. Dewolf ◽  
D. Cooper ◽  
N. Bernier ◽  
V. Delaye ◽  
A. Grenier ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Transmission Electron Microscopy ◽  
Energy Loss ◽  
Electron Energy ◽  
Electron Energy Loss Spectroscopy ◽  
Hafnium Dioxide ◽  
Switching Mechanism ◽  
Transmission Electron ◽  
Electron Energy Loss

Abstract Forming and breaking a nanometer-sized conductive area are commonly accepted as the physical phenomenon involved in the switching mechanism of oxide resistive random access memories (OxRRAM). This study investigates a state-of-the-art OxRRAM device by in-situ transmission electron microscopy (TEM). Combining high spatial resolution obtained with a very small probe scanned over the area of interest of the sample and chemical analyses with electron energy loss spectroscopy, the local chemical state of the device can be compared before and after applying an electrical bias. This in-situ approach allows simultaneous TEM observation and memory cell operation. After the in-situ forming, a filamentary migration of titanium within the dielectric hafnium dioxide layer has been evidenced. This migration may be at the origin of the conductive path responsible for the low and high resistive states of the memory.

Analysis of Diffraction Contrast as A Function of Energy Loss in Energy Filtering Transmission Electron Microscope (EFTEM) Imaging and Possible Implications on High-Resolution Compositional Mapping

1999 ◽  
Vol 5 (S2) ◽  
pp. 620-621
Author(s):  
K.T. Moore ◽  
J.M. Howe
Keyword(s):  
Electron Microscope ◽  
Energy Loss ◽  
Electron Energy ◽  
Transmission Electron Microscope ◽  
Diffraction Contrast ◽  
Energy Filtering ◽  
Background Removal ◽  
Transmission Electron ◽  
Important Relationship ◽  
Electron Energy Loss

The dependence of diffraction contrast on electron energy loss is an important relationship that needs to be understood because of its potential effect on energy-filtering transmission electron microscope (EFTEM) images. Often when either a two-window jump-ratio image or a three-window elemental map is produced diffraction contrast is not totally eliminated and contributes to the intensity of the final EFTEM image. Background removal procedures often are unable to completely account for intensity changes due to dynamical effects (i.e., elastic scattering) that occur between images acquired at different energy losses, leaving artifacts in the final EFTEM image.In this study, the relationship between diffraction contrast and electron energy loss was investigated by obtaining EFTEM images of a bend contour in aluminum in 100 eV increments from 0 to 1000 eV (Fig. 1). EFTEM images were acquired a JOEL 2010F FEG TEM with a Gatan imaging filter (GIF) at a microscope magnification of 8 kX using a 1 eV/pixel dispersion, 2X binning (512 x 512) and exposure times ranging from 0.25 s for 0 eV energy loss up to 132 sec for 1000 eV energy loss.

Electron Energy-Loss Spectroscopy (EELS) of Fe-Bearing Olivine and Laihunite (an Oxidized Olivine)

2000 ◽  
Vol 6 (S2) ◽  
pp. 208-209
Author(s):  
Huifang Xu ◽  
Pingqiu Fu
Keyword(s):  
Electron Microscopy ◽  
Transmission Electron Microscopy ◽  
High Resolution ◽  
Energy Loss ◽  
Electron Energy ◽  
Electron Energy Loss Spectroscopy ◽  
Structure Refinement ◽  
Iron Formation ◽  
Transmission Electron ◽  
Electron Energy Loss

Laihunite that has distorted olivine-type structure with ferric and ferrous irons and ordered distribution of vacancies was first discovered in a high-grade metamorphosed banded iron formation (BIF) [1, 2]. The laihunite coexisting with fayalite (Fe-olivine), magnetite, quartz, ferrosilite, garnet and hedenbergite, formed in the process of oxidation of fayalite [2, 3]. The structure refinement of 1-layer laihunite shows P21/b symmetry and ordered distribution of vacancies in half M1 sites of olivine structure [2, 3]. Early high-resolution transmission electron microscopy (HRTEM) study and HRTEM image simulation of the 1-layer laihunite verified the structure refinement [4].Specimens of weakly oxidized fayalite and laihunite containing fayalite islands collected from Xiaolaihe and Menjiagou of Liaoning Province, NE China, have been studied using selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), electron energy-loss spectroscopy (EELS), and X-ray energy-dispersive spectroscopy.

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