Charge Contrast Imaging of Nonconductive Samples in the High‐Vacuum Field Emission Scanning Electron Microscope

The charge contrast images (CCI) on insulating or poorly conducting samples were observed under steady‐state charging conditions with a thermal field emission scanning electron microscope under high vacuum by using an Everhart‐Thornley detector. The charge contrast on plumbous titanate‐nickel composite particles and patterned sapphires could be the indicators of near‐surface features, compositional variations and conductivity distributions. Optimum imaging conditions for observing the CCI include the electron energy, the electron flux density and the electron dose. Contrast characteristics associated with surface and near‐surface secondary electron emission yield enhanced above the trapped charge‐up regions, as charge trapping selectively enhanced the poorly conductive phase and lattice distorted area. SCANNING 29: 230‐237, 2007. © 2007 Wiley Periodicals, Inc.     

Interpretation of secondary electron images obtained using a low vacuum SEM

Charging of insulators in a variable pressure environment was investigated in the context of secondary electron (SE) image formation. Sample charging and ionized gas molecules present in a low vacuum specimen chamber can give rise to SE image contrast. "Charge-induced" SE contrast reflects lateral variations in the charge state of a sample caused by electron irradiation during and prior to image acquisition. This contrast corresponds to SE emission current alterations produced by sub-surface charge deposited by the electron beam. "Ion-induced" contrast results from spatial inhomogeneities in the extent of SE signal inhibition caused by ions in the gaseous environment of a low vacuum scanning electron microscope (SEM). The inhomogeneities are caused by ion focusing onto regions of a sample that correspond to local minima in the magnitude of the surface potential (generated by sub-surface trapped charge), or topographic asperities. The two types of contrast exhibit characteristic dependencies on microscope operating parameters such as scan speed, beam current, gas pressure, detector bias and working distance. These dependencies, explained in terms of the behavior of the gaseous environment and sample charging, can serve as a basis for a correct interpretation of SE images obtained using a low vacuum SEM.     

Charging in scanning electron microscopy "from inside and outside"

This paper is an attempt to analyse most of the complicated mechanisms involved in charging and discharging of insulators investigated by scanning electron microscopy (SEM). Fundamental concepts on the secondary electron emission (SEE) yield from insulators combined with electrostatics arguments permit to reconsider, first, the widespread opinion following which charging is minimised when the incident beam energy E0 is chosen to be equal to the critical energy E(o)2, where the nominal total yield delta(o) + eta(o) = 1. For bare insulators submitted to a defocused irradiation, it is suggested here that the critical energy under permanent irradiation EC2 corresponds to a range of primary electrons, R, and nearly equals the maximum escape depth of the secondary electrons, r. This suggestion is supported by a comparison between published data of the SEE yield delta(o) of insulators (short pulse experiments) and experimental results obtained from a permanent irradiation for EC2. New SEE effects are also predicted at the early beginning of irradiation when finely focused probes are used. Practical considerations are also developed, with specific attention given to the role of a contamination layer where a negative charging may occur at any beam energy. The role of the various time constants involved in charging and discharging is also investigated, with special attention given to the dielectric time constant, which explains the dose rate-dependent effects on the effective landing energy in the steady state. Numerical applications permit to give orders of magnitude of various effects, and several other practical consequences are deduced and illustrated. Some new mechanisms for the contrast reversal during irradiation or with the change of the primary electron (PE) energy are also suggested.     

A study of electron beam-induced conductivity in resists.

The charging of polymeric resist materials during electron beam irradiation leads to significant problems during imaging and lithography processes. Charging occurs because of charge deposition in the polymer and charge generation/trapping due to formation of electron-hole pairs in the dielectric. The presence of such charge also results in the phenomena of electron beam-induced conductivity (EBIC). Electron beam-induced conductivity data have been obtained for three commercial e-beam resists under a variety of dose rate and temperature conditions. From the observed values of induced conductivity under varying conditions significant information about the generation of electron-hole pair and the transport of charge in the resist can be obtained. Three electron beam resists, EBR900, ZEP7000, and PBS are examined by an external bias method. The difference in resist chemistry is considered to play the role in the initial state EBIC behaviors among three resists even though the way that it affects the behaviors is not clear. A comparison of the power consumption comparison is proposed as a measure to give a preliminary estimate of the carrier concentration and carrier drift velocity differences among the resists. A simple single trap model with constant activation energy is proposed and provides good agreement with experiment.     

Dynamic secondary electron contrast effects in liquid systems studied by environmental scanning electron microscopy

We report an investigation into a dynamic contrast phenomenon in water-oil emulsions imaged in the environmental scanning electron microscope. Secondary electron contrast between oil and water phases is shown to change with scan rate, even inverting in extreme cases. This effect is attributed to the fact that charge carriers in liquids have intermediate mobilities compared with those in metallic conductors and solid insulators. Thus, increasing the electron energy flux density (via slower scan rates) results in the temporary accumulation of excess charge, which in turn gives rise to increased secondary electron emission. Excess charge dissipates between frames, however, such that classical charging of the specimen is not observed. The oils used here have conductivities lower than that of water, making them more susceptible to the effect. However, the material within the primary electron interaction volume is a conductive medium. We demonstrate that charging effects are not seen in regions of the oil where the interaction volume is in contact with the more conductive continuous water phase. Secondary electron emission from these regions therefore approximates to the intrinsic yield.     

The assessment of microscopic charging effects induced by focused electron and ion beam irradiation of dielectrics

Energetic beams of electrons and ions are widely used to probe the microscopic properties of materials. Irradiation with charged beams in scanning electron microscopes (SEM) and focused ion beam (FIB) systems may result in the trapping of charge at irradiation induced or pre-existing defects within the implanted microvolume of the dielectric material. The significant perturbing influence on dielectric materials of both electron and (Ga(+)) ion beam irradiation is assessed using scanning probe microscopy (SPM) techniques. Kelvin Probe Microscopy (KPM) is an advanced SPM technique in which long-range Coulomb forces between a conductive atomic force probe and the silicon dioxide specimen enable the potential at the specimen surface to be characterized with high spatial resolution. KPM reveals characteristic significant localized potentials in both electron and ion implanted dielectrics. The potentials are observed despite charge mitigation strategies including prior coating of the dielectric specimen with a layer of thin grounded conductive material. Both electron- and ion-induced charging effects are influenced by a delicate balance of a number of different dynamic processes including charge-trapping and secondary electron emission. In the case of ion beam induced charging, the additional influence of ion implantation and nonstoichiometric sputtering from compounds is also important. The presence of a localized potential will result in the electromigration of mobile charged defect species within the irradiated volume of the dielectric specimen. This electromigration may result in local modification of the chemical composition of the irradiated dielectric. The implications of charging induced effects must be considered during the microanalysis and processing of dielectric materials using electron and ion beam techniques.     

The effects of space charge on contrast in images obtained using the environmental scanning electron microscope

We present experimental evidence for the existence of a space charge in the environmental scanning electron microscope. Space charge formation is attributed to differences in the mobilities of negative and positive charge carriers in the imaging gas. A model is proposed for the behavior of space charge during image acquisition. The effects of space charge on images acquired using the gaseous secondary electron detector, ion current, and backscattered electron signals are interpreted using the proposed model.     

Helium ion microscopy for high-resolution visualization of the articular cartilage collagen network

The articular cartilage collagen network is an important research focus because network disruption results in cartilage degeneration and patient disability. The recently introduced helium ion microscope (HIM), with its smaller probe size, longer depth of field and charge neutralization, has the potential to overcome the inherent limitations of electron microscopy for visualization of collagen network features, particularly at the nanoscale. In this study, we evaluated the capabilities of the helium ion microscope for high-resolution visualization of the articular cartilage collagen network. Images of rabbit knee cartilage were acquired with a helium ion microscope; comparison images were acquired with a field emission scanning electron microscope (FE-SEM) and a transmission electron microscope (TEM). Sharpness of example high-resolution helium ion microscope and field emission scanning electron microscope images was quantified using the 25-75% rise distance metric. The helium ion microscope was able to acquire high-resolution images with unprecedented clarity, with greater sharpness and three-dimensional-like detail of nanoscale fibril morphologies and fibril connections, in samples without conductive coatings. These nanoscale features could not be resolved by field emission scanning electron microscopy, and three-dimensional network structure could not be visualized with transmission electron microscopy. The nanoscale three-dimensional-like visualization capabilities of the helium ion microscope will enable new avenues of investigation in cartilage collagen network research.     

Evaluation of the effective cross‐sections for recombination and trapping in the case of pure spinel

In this paper, we have investigated the evolution of the secondary electron emission in the case of pure spinel during electron irradiation, achieved in a scanning electron microscope at room temperature, which is derived from the measurement of the induced and the secondary electron currents. It was observed from the experimental results, that there are two regimes during the charging process: a plateau followed by a linear variation, which are better identified by plotting the logarithm of the secondary electron emission yield lnσ as function of the total surface density of trapped charges in the material Q_T. For positive charging, E₀ = 1.1 and 5 keV, the slope of the linear part, whose value is of about 10^?10 cm² charge^?1, is independent of the primary electron energy. It is interpreted as a microscopic cross section for electron–hole recombination. For negative charging of pure spinel, E₀ = 15 and 30 keV, the slope is associated with an electron trapping cross section close to 10^?14 cm² charge^?1, which can be assigned to the microscopic cross section for electron trapping. This trapping cross section is four orders of magnitude lower than the recombination one.     

Imaging of semiconducting polymer blend systems using environmental scanning electron microscopy and environmental scanning transmission electron microscopy

This study has investigated the potential of environmental electron microscopy techniques for studying the structure of polymer‐based electronic devices. Polymer blend systems composed of F8BT and PFB were examined. Excellent contrast, both topographical and compositional, can be achieved using both conventional environmental scanning electron microscopy (ESEM) and a transmission detector giving an environmental scanning transmission electron microscope (ESTEM) configuration. Controllable charging effects present in the ESEM were observed, giving rise to a novel voltage contrast. This shows the potential of such contrast to provide excellent images of phase structure and charge distributions.     

Beam damage of polypropylene in the environmental scanning electron microscope: an FTIR study

The environmental scanning electron microscope allows the examination of virtually any specimen in a gaseous environment without the need for coating or drying. Experimental evidence, however, suggests that significant electron beam damage occurs in hydrated specimens. It is thought that water molecules, ionized by the electron beam, produce hydrogen and hydroxyl free radicals which attack the organic material of the sample. In order to elucidate the beam damage mechanisms, areas of polypropylene films were exposed to the electron beam at varying doses and exposure times under both hydrating and dehydrating conditions. The chemical changes occurring as a result of electron-beam irradiation were determined using Fourier transform infra-red microscopy. Direct interaction of the electron beam with the polymer results in extensive cross-linking. In the presence of water, free-radical-initiated reactions lead to hydrolysis and oxidation of the polymer.     

Effect of the sample annealing temperature and sample crystallographic orientation on the charge kinetics of MgO single crystals subjected to keV electron irradiation

This paper focuses on the effect of sample annealing temperature and crystallographic orientation on the secondary electron yield of MgO during charging by a defocused electron beam irradiation. The experimental results show that there are two regimes during the charging process that are better identified by plotting the logarithm of the secondary electron emission yield, lnσ , as function of the total trapped charge in the material Q_T. The impact of the annealing temperature and crystallographic orientation on the evolution of lnσ is presented here. The slope of the asymptotic regime of the curve lnσ as function of Q_T, expressed in cm² per trapped charge, is probably linked to the elementary cross section of electron–hole recombination, σ_hole, which controls the trapping evolution in the reach of the stationary flow regime.     

Possibility of charge contrast imaging of polymeric materials

Preliminary results illustrate the possibility of charge contrast imaging (CCI) of polymeric materials. Possible CCI images of low-density polyethylene and polyvinyl chloride reveal details that may aid in the characterization of the microstructure of polymeric materials. These pictures were obtained with a Hitachi S-3000N variable pressure scanning electron microscope with the environmental secondary electron detector (ESED).     

Signal components in the environmental scanning electron microscope

We demonstrate that the gas-amplified secondary electron signal obtained in the environmental scanning electron microscope has both desired and spurious components. In order to isolate the contributions of backscattered and secondary electrons, two sets of samples were examined. One sample consisted of a pair of materials having similar secondary emission coefficients but different backscatter coefficients, while the other sample had a pair with similar backscatter but different secondary emission coefficients. Our results show how the contribution of the two electron signals varies according to the pressure of the amplifying gas. Backscatter contributions, as well as background due to gas ionization from the primary beam, become significant at higher pressure. Furthermore, we demonstrate that the relative amplification efficiencies of various electron signals are dependent upon the chemistry of the gas.     

Investigation of quantitative secondary electron imaging of semiconducting polymer materials using environmental scanning electron microscopy

The development of environmental scanning electron microscopy has opened the way for the examination of a wide variety of new sample types that were previously inaccessible to conventional scanning electron microscope techniques. With the advent of such a new methodology comes also the potential for new contrast mechanisms. We investigated the use of environmental scanning electron microscopy on semiconducting organic polymer materials. We observed contrast from these materials in secondary electron images, this contrast being attributed to differences in electron yield due to the polymer's electronic structure. Further study of these materials, and specifically the influence of film thickness on signal, has indicated a significant effect as the secondary electrons move through the sample. Systematic studies such as these are needed for a full understanding of the relationship between electronic properties and signal and, hence, the ability to probe structure–property relationships in greater depth.     

The role of induced contrast in images obtained using the environmental scanning electron microscope

Generation of contrast in images obtained using the environmental scanning electron microscope (ESEM) is explained by interpretation of images acquired using the gaseous secondary electron detector (GSED), ion current, and the Everhart-Thornley detector. We present a previously unreported contrast component in GSED and ion current images attributed to signal induction by changes in the concentration of positive ions in the ESEM chamber during image acquisition. Changes in positive ion concentration are caused by changes in electron emission from the sample during image acquisition and by a discrepancy between the drift velocities of negative and positive charge carriers in the imaging gas. The proposed signal generation mechanism is used to explain contrast reversal in images produced using the GSED and ion current signals and accounts for discrepancies in contrast observed, under some conditions, in these types of images. Combined with existing models of signal generation in the ESEM, the proposed model provides a basis for correct interpretation of ESEM images.     

Determination of secondary electron spectra from insulators

A new technique for the determination of secondary electron (SE) spectra of insulators in a scanning electron microscope environment is presented. It is based on a capacitatively coupled charge measurement by subjecting the insulating film to a controlled pulsed electron beam. With the use of a planar grid analyzer configuration, an algorithm is used to estimate the SE spectrum based on normalized values of the S-curve obtained. Secondary electron spectra from several insulating materials employed in integrated circuit manufacturing, including silicon nitride (Si3N4), AZ 1350J photoresist, and pyralin polyimide, have been measured.     

New technique for in-situ measurement of backscattered and secondary electron yields for the calculation of signal-to-noise ratio in a SEM

The quality of an image generated by a scanning electron microscope is dependent on secondary emission, which is a strong function of surface condition. Thus, empirical formulae and available databases are unable to take into account actual metrology conditions. This paper introduces a simple and reliable measurement technique to measure secondary electron yield (δ) and backscattered electron yield (η) that is suitable for in-situ measurements on a specimen immediately prior to imaging. The reliability of this technique is validated on a number of homogenous surfaces. The measured electron yields are shown to be within the range of published data and the calculated signal-to-noise ratio compares favourably with that estimated from the image.     

Monte Carlo simulation of secondary electron and backscattered electron images in scanning electron microscopy for specimen with complex geometric structure

A new Monte Carlo technique for the simulation of secondary electron (SE) and backscattered electron (BSE) of scanning electron microscopy (SEM) images for an inhomogeneous specimen with a complex geometric structure has been developed. The simulation is based on structure construction modeling with simple geometric structures, as well as on the ray-tracing technique for correction of electron flight-step-length sampling when an electron trajectory crosses the interface of the inhomogeneous structures. This correction is important for the simulation of nanoscale structures of a size comparable with or even less than the electron scattering mean free paths. The physical model for electron transport in solids combines the use of the Mott cross section for electron elastic scattering and a dielectric function approach for electron inelastic scattering, and the cascade SE production is also included.     

A method for imaging single clay platelets by scanning electron microscopy

A method for preparing and observing clay platelets for size and shape analysis using scanning electron microscopy (SEM) was developed. Samples of the clay platelets were prepared by polyelectrolyte-assisted adsorption onto a pyrolytic graphite surface. The use of graphite as a substrate was advantageous because of the low number of secondary electrons emitted from it during imaging by SEM. The resulting low background noise allowed the emission from the approximately 1 nm thick clay sheets to be clearly visualized. Images of centrifuged montmorillonite showed large exfoliated platelets with lateral dimensions between 200 and 600 nm. In contrast, uncentrifuged montmorillonite appeared to contain a large amount of unexfoliated clusters. Although it was not possible to obtain high-quality images of the smaller sheets of Laponite RD, the images of this material did contain size features comparable to the approximately 30 nm2 size reported previously using light scattering, as well as transmission electron and atomic force microscopies.