Category Archives: Materials Characterization

X-Ray Fluorescence Spectroscopy (XRF)

X-ray fluorescence spectroscopy (XRF) is one of the most common techniques used for studying the elemental composition of different materials. In this materials characterization method the sample is irradiated with x-ray radiation, which knocks out electrons from atoms, leaving them in an excited state. During the relaxation of these atoms the excess energy is released in the form of x-ray radiation. The energy and intensity of this radiation however depends directly on the composition of the material. Therefore it is possible to study a materials composition by detecting the x-rays that come out of the sample. Watch our video to learn more!

Low-Energy Ion Scattering Spectroscopy (LEIS)

 

Low-energy ion scattering spectroscopy (LEIS) is an exciting technique that allows to study the structure and chemical composition of a materials surface.

In this materials characterization method the sample is bombarded with a stream of ions and the positions, velocities and energies of the scattered ions are observed. The energy of scattered ions depends on the mass of the target, so there are distinct peaks in the energy spectrum of the scattered ions. These peaks give information about the samples elemental composition. The uniqueness of this technique lies in its sensitivity to the very first atomic layer on a sample and with forward scattering setup it is even capable of directly observing hydrogen atoms.

One of the main components of the system is the ion gun, that shoots ions at the studied substrate. The most widely used ions for that purpose are ionized noble gas or alkali atoms. Noble gas such as helium, neon or argon is ionized with electrons, giving them a positive charge. Alkali ion beams can be created by heating alkali wafers. In low-energy ion scattering spectroscopy the ions usually have an energy from 500 eV to 10 000 eV. The precise desired energy of the ions is obtained by applying a suitable accelerating voltage.

Before interacting with the substrate, the ions first need to pass through the ion beam manipulator, that narrows the beam and also filters the ions based on mass and velocity. For some experiments the ion beam is also chopped with an unipolar electrical chopper – a pulsed-wave generator, that lets through ions only when no voltage is applied. As a result the ion beam leaves the ion beam manipulator in pulses. By using short ion pulses, one can separate backscattered primary ions, for example He, from sputtered ions of different masses by time gating. This makes it possible to detect signals that would otherwise be buried in the background that is caused by ions sputtered from the sample surface.

The sample itself is attached to a special holder that allows the operator to adjust the position and angle of the sample for different experiments. When the ions hit the substrate, different interactions take place. Some ions are scattered at a certain angle and also their energy will be different after the impact. Some ions however become neutral as they pick up electrons from the substrate. The ions may also be implanted into the material or deposited on the substrate surface. The primary beam ions may also kick out electrons or atoms from the substrate and the atoms may even be ionized in the process. Radiation may also be emitted from the substrate as the excited atoms undergo a relaxation process.

The electrostatic analyzer is commonly used to detect the velocities and energies of the scattered ions. In this hemispheric device an electrical potential is applied between the inner and outer wall. The outer wall with positive potential repels the positive ions and the inner wall with negative potential attracts the positive ions. Neutral particles are unaffected by the field and hit the wall and thus never reach the detector. Positive ions with too low energy are pulled to the inner wall and also don’t reach the detector. If the cations energy is too high however then it simply hits the outer wall. Only if the ions energy is just right, it can pass through the analyzer and create a signal by interacting with the detector. By changing the potential between the walls, the operator can scan through a wide energy range in order to find out the energy of the emitted particles. In newer systems however a double toroidal analyzer is preferred as it integrates the signal over the scattering azimuth, so the intensity is some orders of magnitude higher compared to a hemispherical analyzer. The drift tube is used in TOF experiments in order to detect the energies and velocities of the scattered ionic and also neutral particles. Neutrals can easily be seperated from ions with the accelerator. There are two types of detectors that are commonly used – channel electron multipliers and microchannel plates. If the ion or a neutral particle with sufficient energy hits the detector then a cascade of secondary electrons is created and the signal significantly amplified. Microchannel plates also give information about the particles position but that comes at the cost of sensitivity.

Measurements with low-energy ion scattering spectroscopy are performed in ultra-high vacuum in order to avoid interactions with the surrounding gas. Having a good vacuum also ensures that the studied substrate and system parts are clean. Ultra-high vacuum is achieved with turbomolecular and ion pumps with the help of rough vacuum pumps.

Samples that have been exposed to open air are always contaminated for this type of surface sensitive characterization method and therefore they need to be cleaned inside the system in vacuum with appropriate equipment. Common ways to remove the contaminated top layer are sputtering, annealing or exposing to atomic oxygen.

There are of course few other surface sensitive materials characterization techniques such as XPS, AFM and SEM but each of them has distinct advantages and disadvantages. Therefore they are often used together when studying novel nanomaterials as they compensate each others weaknesses and allow to get a better overview.

 

Penetration of Nuclear Gamma Radiation

Nuclear radiation is emitted from a material when the nucleus of an unstable atom loses energy by emitting ionizing radiation. The emitted radiation consists of gamma rays, alpha particles (He2+), beta particles (high energy electrons or positrons) and conversion electrons. From these components gamma rays are most dangerous for humans as they can easily penetrate the skin and cause severe damage to internal organs. Although gamma radiation is often an unwanted byproduct when producing nuclear power, it also has found use in medicine and food industry. In medicine gamma radiation is used for cancer treatment as it kills the cancer cells. In food industry the radiation is used to sterilize food as it kills bacteria and leaves the food unharmed. Gamma radiation can easily penetrate different materials and this makes radiation protection difficult. The penetration depends on the atomic number and therefore heavy metals such as Pb (lead) are used for shielding. In this experiment we use a geiger counter to measure the radiation emitted from a cobalt-60 isotobe and see how well we can block the radiation by using different materials such as wood, aluminum, steel, tungsten, pork cutlets and led casing.

X-Ray Photoelectron Spectroscopy (XPS)

Photoelectric effect, photoelectron spectroscopy (XPS) and scanning photoelectron microscopy (SPEM) are explained in this short lecture. The photoelectric effect occurs when the inner shell electrons of the sample atoms are kicked out by high energy electromagnetic radiation. These electrons, that were kicked out, are called photoelectrons and their energy depends on the energy of the exciting radiation, the electrons initial binding energy and on the work function. When having a radiation source with well defined energy and measuring the energy of the emitted electrons, it is possible to get information about the samples composition and chemical state. In the case of photoelectron microscopy the exciting beam is focused into a narrow spot on the sample surface. The sample is then moved in such a way that the spot moves row by row across the sample surface and as a result photoelectrons are emitted from each irradiated spot. By collecting these photoelectrons, it is possible to map the composition or chemical state across the selected sample area (for example 100 x 100 microns area on a 2 x 2 cm sample). Photoelectrons can escape the material only from near the surface and this means that these methods are very surface sensitive, which makes them extremely useful for surface studies. This also means that the surfaces need to be very clean (cleaned with ion bombardment before measurements) and therefore ultra-high vacuum is needed.

Atomic Force Microscopy (AFM)

Atomic force microscope (AFM) is a powerful tool that is used to study materials by scanning over the surface with a very sharp tip. When a sharp tip approaches a surface then first Van der Waals attractive forces apply that pull the tip closer to the surface and therefore also bend the cantilever. When the tip is close enough then electrostatic repulsive forces apply. The bending of the cantilever is monitored with a lazer beam that is focused on the cantilever and reflected into the detector.This method allows to obtain greatly magnified high resolution 3D images of the studied substrates (even atomic resolution is possible). The main working modes are contact, non-contact and tapping mode. In then case of contact mode the tip is in direct contact with the material. This is suitable for studying hard surfaces. In the case of non-contact mode the tip is vibrating close to the surface. This mode is used for studying sticky and soft surfaces. In the tapping mode the tip vibrates with a greater amplitude and briefly touches the sample at its lowest point of the trajectory. This method is useful for obtaining a “real” image of the studied surface as the tip penetrates the thin film of water that is always present on substrates when measuring in open air. There are also other types of scanning probe microscopes where different information can be obtained from the sample. For example a if one uses a thermocouple as a sharp tip for scanning then it is possible to study heat distribution on microscopic electronic devices in order to detect possible spots where oveheating occurs. In the case of scanning tunnel microscopy an electric potential is applied between the tip and the sample, which causes the movement of electrons from one to other. By measuring the tunneling current, it is possible to obtain valuable information about the state of the surface. Even atomic resolution is possible in STM and therefore can be used to study novel materials such as graphene. It is also possible to use magnetic needles or thin optical cables as tip for scanning over the studied surface.

Scanning Electron Microscopy (SEM)

Scanning Electron Microscopy

The scanning electron microscope is a powerful tool used by many scientists for studying and developing materials. This device uses electrons instead of photons and that allows the operator to visualize even nano-scaled surface details. Therefore it is very useful for also studying corrosion processes and creating efficient thin coatings which have a thickness of less than a micrometer.

In the video above you will see the working principle of this microscope and how it is operated.

The electrons are generated in the electron gun on top of the microscope. There are different source types but one of the oldest used is a tungsten filament that is heated over 2400 degrees celsius by passing a current through it. At this temperature electrons emit from the filament and are pulled down the column with the help of an anode. The operator selects the voltage that accelerates the electrons. It can be up to 30 kV in conventional scanning electron microscopes. The accelerated electrons are scattered and need to be focused – this is done with the help of multiple focusing lenses. These lenses also tune the amount of electrons that reach the sample. For example by broadening the electron beam, the electrons are absorbed by the column and dont reach the sample. In order to scan across the sample row by row, the electron beam needs to be moved in such a manner. This is achieved with the help of scanning coils that are placed below the focusing lenses. The final focusing of the beam is done with objective lenses located below the scanning coils. In order to get an image of the substrate the surface is scanned row by row with the electron beam. In each spot signals like secondary electrons, backscattered electrons or characteristic X-Rays are generated. By detecting the signal emitted from each scanned spot, an image of the surface is generated. So for example by detecting secondary electrons a secondary electron image is generated.

Secondary electrons are generated when the primary beam electrons kick out electrons from the substrate atoms. In that process primary beam electrons lose energy as it is transfered to the secondary electrons. These secondary electrons generaly have low energy and escape only from near the surface, giving a good image of the substrates topography. The electrons are collected with a special detector that has a positively charged collector  for pulling the negatively charged electrons towards it.

Backscattered electrons are primary beam electrons that are scattered back in a similar direction as they interact with the substrate atoms nucleous. In that process they dont lose much energy and can be emitted even from deep layers of the substrate. Therefore they carry the bulk information of the sample and generated images are not completely topographic. The electron yield strongly depends on the atomic number of the substrate. For example regions on substrate with higher atomic number appear brighter on the image as more electrons are backscattered in these regions.

Characteristic X-Rays are generated when sample atoms exited by primary beam electrons are undergoing a relaxation process where the inner shell vacant spot is filled with an outer shell electron. The emitted radiations energy depends strictly on the atoms number and on the electrons binding energies that are involved in this process. Therefore this signal can be used to detect different elements and do quantitative element analysis.

For a real SEM study the sample first needs to be prepared – it has to be dry, conductive and with a suitable size. Non-conductive samples can be coated with a thin (couple nanometers) layer of metal (Au, Pt..), which allows SEM studies as they conduct away the heat and negative charge caused by electrons. The sample is moved into the microscope through an airlock or the main chamber door and placed on a stage with a special holder. The stage can move in any desired direction (x,y,z, rotate, tilt). The sample is then moved under the electron column to a suitable working distance. After focusing and other adjustments the first electron image can be taken.

Element microanalysis can be done in several ways but first an electron image of the sample is obtained. The most common way to do element analysis is selecting a characteristic spot on the sample and then bombard it with the narrow (couple nm wide) electron beam. As a result X-Rays are emitted from the couple micrometer wide interaction volume. This gives information from a very localized area but in some cases an average composition of the material is needed. For that a larger area (lets say 50 x 50 microns) is bombarded by electrons and the X-Rays emitted from that area are detected. It is also possible to map the distribution of elements on a larger area by scanning across the surface with the electrons row by row and collect X-Rays from each scanned point. Based on the detected X-Rays an image is created that shows the distribution of certain elements.

In order to see what is inside a material a focused ion beam (FIB) is used to make  a cross-section or a thin lamella. The cross-sections or lamella are then studied with electrons at a suitable angle by tilting it with the help of the stage.

Scanning electron microscopes generally work in a high vacuum in order to prevent surface contamination and electron or x-ray interactions with the gas in the chamber which would affect the quality of the image. However there are also specially designed environmental scanning electron microscopes (ESEM-s), that work in low vacuum. The ESEM can therefore even be used to study living cells or bacteria.