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The surface structures of nickel phosphide (Ni2P) single crystals were studied by tunneling microscopy (TM) and photoemission electron microscopy (PEEM). Atomically resolved 1 Ã- 1 images of the Ni2P(0001) and (1010) surfaces are successfully obtained with TM, whose respective dimensions of (0.59 nm Ã- 0.59 nm) and (0.34 nm Ã- 0.59 nm) match the unit cell lengths. The Ni2P(0001) surface has two possible terminations in which the Ni:P ratios are 3:1 (Ni3P termination) or 3:2 (Ni3P2 termination). In the Ni3P terminated surface the Ni atoms have a square pyramidal structure, and in the Ni3P2 terminated surface the Ni atoms have a tetrahedral structure. Only the P is visible in the TM for Ni2P(0001) and this is explained as being due to the greater extension of the phosphorus p orbitals than the Ni d orbitals at the surface. The surface domain sizes of the Ni3P and Ni3P2 termination structures of Ni2P(0001) are determined to be 500 Î¼m by means of PEEM using a Hg-Xe lamp through a low-pass UV-filter. Evidence is found for dissociative adsorbed hydrogen on the Ni3P termination surface
A tunneling electron microscope (TEM) is a powerful instrument for imaging surfaces at the atomic level. Its development in 1981 earned its inventors, Gerd Binnig and Heinrich Rohrer (at IBM Zürich), the Nobel Prize in Physics in 1986. For an TEM, good resolution is considered to be 0.1 nm lateral resolution and 0.01 nm depth resolutionWith this resolution, individual atoms within materials are routinely imaged and manipulated. The TEM can be used not only in ultra high vacuum but also in air, water, and various other liquid or gas ambients, and at temperatures ranging from near zero Kelvin to a few hundred degrees Celsius.
The TEM is based on the concept of quantum tunneling. When a conducting tip is brought very near to the surface to be examined, a bias (voltage difference) applied between the two can allow electrons to tunnel through the vacuum between them. The resulting tunneling current is a function of tip position, applied voltage, and the local density of states (LDOS) of the sample. Information is acquired by monitoring the current as the tip's position scans across the surface, and is usually displayed in image form. TEM can be a challenging technique, as it requires extremely clean and stable surfaces, sharp tips, excellent vibration control, and sophisticated electronics. This technique is called TUNNELING ELECTRON MICROSCOPY
Some Milestones in the History of Electron Microscopy
1897 Discovery of the electron by J.J. Thompson
1924 P. De Broglie: particle/wave dualism
1927 Hans Busch: electron beams can be focused in an inhomogeneous magnetic field.
Reproduced with kind permission from the Ernst Ruska Archiv e.V
1931 Ernst Ruska and Max Knoll built the first TEM
1938 First scanning transmission electron microscope (M. von Ardenne)
1939 First commercial TEM by Siemens (Ruska, von Borries)
~1940 Basic theoretical work on electron optics and electron lenses (W. Glaser, O. Scherzer)
1943 Electron energy-loss spectroscopy EELS (J. Hillier)
1948 First TEM at ETH Zurich (report)
1951 X-ray spectroscopy (R. Castaing)
1956 First lattice image (J. Menter)
1957 Multi-slice method (J. Cowley, A. Moodie)
1964 First commercial SEM by Cambridge Instruments
~1970 HRTEM microscopes with a resolution better than 4 Å
1986 Nobel prize for E.Ruska (together with G. Binning and H. Rohrer, who developed the Scanning Tunneling Microscope)
~2003 Aberration-corrected HRTEM microscopes reach sub-Ångstrøm resolution
PROCEDURE OF THIS TECHNOLOGY
A close-up of a simple tunneling microscope head using a platinum-iridium stylus.
First, a voltage bias is applied and the tip is brought close to the sample by some coarse sample-to-tip control, which is turned off when the tip and sample are sufficiently close. At close range, fine control of the tip in all three dimensions when near the sample is typically piezoelectric, maintaining tip-sample separation W typically in the 4-7 Å range, which is the equilibrium position between attractive (3<W<10Å) and repulsive (W<3Å) interactionsIn this situation, the voltage bias will cause electrons to tunnel between the tip and sample, creating a current that can be measured. Once tunneling is established, the tip's bias and position with respect to the sample can be varied (with the details of this variation depending on the experiment) and data is obtained from the resulting changes in current.
If the tip is moved across the sample in the x-y plane, the changes in surface height and density of states cause changes in current. These changes are mapped in images. This change in current with respect to position can be measured itself, or the height, z, of the tip corresponding to a constant current can be measureThese two modes are called constant height mode and constant current mode, respectively. In constant current mode, feedback electronics adjust the height by a voltage to the piezoelectric height control mechanism.This leads to a height variation and thus the image comes from the tip topography across the sample and gives a constant charge density surface; this means contrast on the image is due to variations in charge density In constant height mode, the voltage and height are both held constant while the current changes to keep the voltage from changing; this leads to an image made of current changes over the surface, which can be related to charge density. The benefit to using a constant height mode is that it is faster, as the piezoelectric movements require more time to register the change in constant current mode than the voltage response in constant height mode. All images produced by TEM are grayscale, with color optionally added in post-processing in order to visually emphasize important features.
In addition to scanning across the sample, information on the electronic structure at a given location in the sample can be obtained by sweeping voltage and measuring current at a specific location. This type of measurement is called scanning tunneling spectroscopy (STS) and typically results in a plot of the local density of states as a function of energy within the sample. The advantage of TEM over other measurements of the density of states lies in its ability to make extremely local measurements: for example, the density of states at an impurity site can be compared to the density of states far from impurities.
Framerates of at least 1 Hz enable so called Video-TEM (up to 50 Hz is possible).This can be used to scan surface diffusion.
INSTRUMENTATION OF THIS TECHNIQUE
Schematic view of an TEM
The components of an TEM include scanning tip, piezoelectric controlled height and x,y scanner, coarse sample-to-tip control, vibration isolation system, and computer
The resolution of an image is limited by the radius of curvature of the scanning tip of the TEM. Additionally, image artifacts can occur if the tip has two tips at the end rather than a single atom; this leads to "double-tip imaging," a situation in which both tips contribute to the tunneling Therefore it has been essential to develop processes for consistently obtaining sharp, usable tips. Recently, carbon nanotubes have been used in this instance.
The tip is often made of tungsten or platinum-iridium, though gold is also used Tungsten tips are usually made by electrochemical etching, and platinum-iridium tips by mechanical shearing
Due to the extreme sensitivity of tunnel current to height, proper vibration isolation or an extremely rigid TEM body is imperative for obtaining usable results. In the first TEM by Binnig and Rohrer, magnetic levitation was used to keep the TEM free from vibrations; now mechanical spring or gas spring systems are often used additionally, mechanisms for reducing eddy currents are sometimes implemented.
Maintaining the tip position with respect to the sample, scanning the sample and acquiring the data is computer controlled The computer may also be used for enhancing the image with the help of image processing as well as performing quantitative measurements.
TUNNELING ELECTRON MICROSCOPY
Nan manipulation via TEM of a self-assembled organic semiconductor monolayer (here: PTCDA molecules) on graphite, in which the logo of the Center for NanoScience (CeNS), LMU has been written.
Many other microscopy techniques have been developed based upon TEM. These include photon scanning microscopy (PTEM), which uses an optical tip to tunnel photons; scanning tunneling potentiometer (STP), which measures electric potential across a surface; spin polarized scanning tunneling microscopy (SPTEM), which uses a ferromagnetic tip to tunnel spin-polarized electrons into a magnetic sample, and atomic force microscopy (AFM), in which the force caused by interaction between the tip and sample is measured.
Other TEM methods involve manipulating the tip in order to change the topography of the sample. This is attractive for several reasons. Firstly the TEM has an atomically precise positioning system which allows very accurate atomic scale manipulation. Furthermore, after the surface is modified by the tip, it is a simple matter to then image with the same tip, without changing the instrument. IBM researchers developed a way to manipulate Xenon atoms absorbed on a nickel surface. This technique has been used to create electron "corrals" with a small number of adsorbed atoms, which allows the TEM to be used to observe electron Friedel oscillations on the surface of the material. Aside from modifying the actual sample surface, one can also use the TEM to tunnel electrons into a layer of E-Beam photo resist on a sample, in order to do lithography. This has the advantage of offering more control of the exposure than traditional Electron beam lithography. Another practical application of TEM is atomic deposition of metals (Au, Ag, W, etc.) with any desired (pre-programmed) pattern, which can be used as contacts to nanodevices or as nanodevices themselves.
Recently groups have found they can use the TEM tip to rotate individual bonds within single molecules. The electrical resistance of the molecule depends on the orientation of the bond, so the molecule effectively becomes a molecular switch.
Principle of operation of tunneling electron microscopy
Tunneling is a functioning concept that arises from quantum mechanics. Classically, an object hitting an impenetrable barrier will not pass through. In contrast, objects with a very small mass, such as the electron, have wavelike characteristics which permit such an event, referred to as tunneling.
Electrons behave as beams of energy, and in the presence of a potential U(z), assuming 1-dimensional case, the energy levels Ïˆn(z) of the electrons are given by solutions to Schrödinger's equation,
where Ä is the reduced Planck's constant, z is the position, and m is the mass of an electron. If an electron of energy E is incident upon an energy barrier of height U(z), the electron wave function is a traveling wave solution,
if E > U(z), which is true for a wave function inside the tip or inside the sample. Inside a barrier, E < U(z) so the wave functions which satisfy this are decaying waves,
quantifies the decay of the wave inside the barrier, with the barrier in the +z direction for âˆ’ Îº
Knowing the wave function allows one to calculate the probability density for that electron to be found at some location. In the case of tunneling, the tip and sample wave functions overlap such that when under a bias, there is some finite probability to find the electron in the barrier region and even on the other side of the barrier. Let us assume the bias is V and the barrier width is W. This probability, P, that an electron at z=0 (left edge of barrier) can be found at z=W (right edge of barrier) is proportional to the wave function squared,
If the bias is small, we can let U âˆ’ E â‰ˆ Ï†M in the expression for Îº, where Ï†M, the work function, gives the minimum energy needed to bring an electron from an occupied level, the highest of which is at the Fermi level (for metals at T=0 kelvins), to vacuum level. When a small bias V is applied to the system, only electronic states very near the Fermi level, within eV (a product of electron charge and voltage, not to be confused here with electronvolt unit), are excited. These excited electrons can tunnel across the barrier. In other words, tunneling occurs mainly with electrons of energies near the Fermi level.
However, tunneling does require that there is an empty level of the same energy as the electron for the electron to tunnel into on the other side of the barrier. It is because of this restriction that the tunneling current can be related to the density of available or filled states in the sample. The current due to an applied voltage V (assume tunneling occurs sample to tip) depends on two factors: 1) the number of electrons between Ef and eV in the sample, and 2) the number among them which have corresponding free states to tunnel into on the other side of the barrier at the tip. The higher density of available states the greater the tunneling current. When V is positive, electrons in the tip tunnel into empty states in the sample; for a negative bias, electrons tunnel out of occupied states in the sample into the tip
Mathematically, this tunneling current is given by
One can sum the probability over energies between Ef âˆ’ eV and eV to get the number of states available in this energy range per unit volume, thereby finding the local density of states (LDOS) near the Fermi level. The LDOS near some energy E in an interval Îµ is given by
and the tunnel current at a small bias V is proportional to the LDOS near the Fermi level, which gives important information about the sample. It is desirable to use LDOS to express the current because this value does not change as the volume changes, while probability density .Thus the tunneling current is given by
where Ïs(0,Ef) is the LDOS near the Fermi level of the sample at the sample surface. This current can also be expressed in terms of the LDOS near the Fermi level of the sample at the tip surface,
The exponential term in the above equations means that small variations in W greatly influence the tunnel current. If the separation is decreased by 1 Çº, the current increases by an order of magnitude, and vice versa.
This approach fails to account for the rate at which electrons can pass the barrier. This rate should affect the tunnel current, so it can be treated using the FermiHYPERLINK "http://en.wikipedia.org/wiki/Fermi's_golden_rule"'HYPERLINK "http://en.wikipedia.org/wiki/Fermi's_golden_rule"s golden rule with the appropriate tunneling matrix element. John Bardeen solved this problem in his study of the metal-insulator-metal junction. He found that if he solved Schrödinger's equation for each side of the junction separately to obtain the wave functions Ïˆ and Ï‡ for each electrode, he could obtain the tunnel matrix, M, from the overlap of these two wave functions. This can be applied to TEM by making the electrodes the tip and sample, assigning Ïˆ and Ï‡ as sample and tip wave functions, respectively, and evaluating M at some surface S between the metal electrodes, where z=0 at the sample surface and z=W at the tip surface.
Now, Fermi's Golden Rule gives the rate for electron transfer across the barrier, and is written
where Î´(EÏˆ-EÏ‡) restricts tunneling to occur only between electron levels with the same energyThe tunnel matrix element, given by
is a description of the lower energy associated with the interaction of wave functions at the overlap, also called the resonance energy,
Summing over all the states gives the tunneling current as
where f is the Fermi function, Ïs and ÏT are the density of states in the sample and tip, respectivelyThe Fermi distribution function describes the filling of electron levels at a given temperature
TUNNELING ELECTRON MICROSCOPE(TEM)
TEM IN THE LABORTATORY
1.Semiconductor and data storage
2. Biology and life sciences
Diagnostic electron microscopy
3D tissue imaging
Electron beam-induced deposition
Materials and sample preparation
2D & 3D micro-characterization
Macro sample to nanometer metrology
Particle detection and characterization
Direct beam-writing fabrication