3In the early 1980's two IBM scientists, Binnig & Rohrer, developed a new technique for studying surface structure - Scanning Tunnelling Microscopy ( STM ). This invention was quickly followed by the development of a whole family of related techniques which, together with STM, may be classified in the general category of Scanning Probe Microscopy ( SPM ) techniques. Of these later techniques, the most important is Atomic Force Microscopy ( AFM ).The development of these techniques has without doubt been the most important event in the surface science field in recent times, and opened up many new areas of science and engineering at the atomic and molecular level.
4Basic Principles of SPM Techniques All of the techniques are based upon scanning a probe (typically called the tip in STM , since it literally is a sharp metallic tip) just above a surface whilst monitoring some interaction between the probe and the surface.
5The interaction that is monitored in : STM - is the tunnelling current between a metallic tip and a conducting substrate which are in very close proximity but not actually in physical contact.AFM - is the van der Waals force between the tip and the surface; this may be either the short range repulsive force (in contact-mode) or the longer range attractive force (in non-contact mode).For the techniques to provide information on the surface structure at the atomic level (which is what they are capable of doing ! ) :the position of the tip with respect to the surface must be very accurately controlled (to within about 0.1 Å) by moving either the surface or the tip.the tip must be very sharp - ideally terminating in just a single atom at its closest point of approach to the surface.
6The attention paid to the first problem and the engineering solution to it is the difference between a good microscope and a not so good microscope - it need not worry us here, sufficient to say that it is possible to accurately control the relative positions of tip and surface by ensuring good vibrational isolation of the microscope and using sensitive piezoelectric positioning devices.Tip preparation is a science in itself - having said that, it is largely serendipity which ensures that one atom on the tip is closer to the surface than all others.
7Let us look at the region where the tip approaches the surface in greater detail .... ... the end of the tip will almost invariably show a certain amount of structure, with a variety of crystal facets exposed ...
8… and if we now go down to the atomic scale .... ... there is a reasonable probability of ending up with a truly atomic tip.
9If the tip is biased with respect to the surface by the application of a voltage between them then electrons can tunnel between the two, provided the separation of the tip and surface is sufficiently small - this gives rise to a tunnelling current.The direction of current flow is determined by the polarity of the bias.If the sample is biased -ve with respect to the tip, then electrons will flow from the surface to the tip as shown above, whilst if the sample is biased +ve with respect to the tip, then electrons will flow from the tip to the surface as shown below.
10The name of the technique arises from the quantum mechanical tunnelling-type mechanism by which the electrons can move between the tip and substrate. Quantum mechanical tunnelling permits particles to tunnel through a potential barrier which they could not surmount according to the classical laws of physics - in this case electrons are able to traverse the classically-forbidden region between the two solids as illustrated schematically on the energy diagram below.This is an over-simplistic model of the tunnelling that occurs in STM but it is a useful starting point for understanding how the technique works.In this model, the probability of tunnelling is exponentially-dependent upon the distance of separation between the tip and surface : the tunnelling current is therefore a very sensitive probe of this separation.
11Imaging of the surface topology may then be carried out in one of two ways: in constant height mode (in which the tunnelling current is monitored as the tip is scanned parallel to the surface)in constant current mode (in which the tunnelling current is maintained constant as the tip is scanned across the surface)If the tip is scanned at what is nominally a constant height above the surface, then there is actually a periodic variation in the separation distance between the tip and surface atoms. At one point the tip will be directly above a surface atom and the tunnelling current will be large whilst at other points the tip will be above hollow sites on the surface and the tunnelling current will be much smaller.A plot of the tunnelling current v's tip position therefore shows a periodic variation which matches that of the surface structure - hence it provides a direct "image" of the surface (and by the time the data has been processed it may even look like a real picture of the surface ! ).
12In practice, however, the normal way of imaging the surface is to maintain the tunnelling current constant whilst the tip is scanned across the surface. This is achieved by adjusting the tip's height above the surface so that the tunnelling current does not vary with the lateral tip position. In this mode the tip will move slightly upwards as it passes over a surface atom, and conversely, slightly in towards the surface as it passes over a hollow.The image is then formed by plotting the tip height (strictly, the voltage applied to the z-piezo) v's the lateral tip position.
14AFMThe AFM consists of a microscale cantilever with a sharp tip (probe) at its end that is used to scan the specimen surface. The cantilever is typically silicon or silicon nitride with a tip radius of curvature on the order of nanometers. When the tip is brought into proximity of a sample surface, forces between the tip and the sample lead to a deflection of the cantilever according to Hooke's law.Typically, the deflection is measured using a laser spot reflected from the top of the cantilever into an array of photodiodes.
15If the tip were scanned at a constant height, there would be a risk that the tip would collide with the surface, causing damage. Hence, in most cases a feedback mechanism is employed to adjust the tip-to-sample distance to maintain a constant force between the tip and the sample. Traditionally, the sample is mounted on a piezoelectric tube, that can move the sample in the z direction for maintaining a constant force, and the x and y directions for scanning the sample.The AFM can be operated in a number of modes, depending on the application. In general, possible imaging modes are divided into static (also called Contact) modes and a variety of dynamic (or non-contact) modes.
16AFM cantilever (after use) in the SEM, magnification 1,000 x
18The atoms of a Sodium Chloride crystal viewed with an Atomic Force Microscope
19Lithography and micromanipulation The interactions between the STM tip and substrate can be used to modify the surface in a controlled way.This can be done in a number of ways.Eg Eigler and Schweizer manipulated xenon atoms on a Nickel(110) surface under UHV conditions, with everything at 4K.They reported that under these conditions everything was stable for days.This allowed them to move single atoms at a time until they achieved the following result.
20Obtained by manipulating CO on a Pt(111) surface.
21The first Atomic Force Microscope - Science Museum London
22Typically resolution achieved by AFM is less than that achieved using STM.
23AFM vs SEMThe AFM has several advantages over the scanning electron microscope (SEM). Unlike the electron microscope which provides a two-dimensional projection or a two-dimensional image of a sample, the AFM provides a true three-dimensional surface profile. Additionally, samples viewed by AFM do not require any special treatments (such as metal/carbon coatings) that would irreversibly change or damage the sample. While an electron microscope needs an expensive vacuum environment for proper operation, most AFM modes can work perfectly well in ambient air or even a liquid environment. This makes it possible to study biological macromolecules and even living organisms. In principle, AFM can provide higher resolution than SEM. It has been shown to give true atomic resolution in ultra-high vacuum (UHV). UHV AFM is comparable in resolution to Scanning Tunneling Microscopy and Transmission Electron Microscopy.A disadvantage of AFM compared with the scanning electron microscope (SEM) is the image size. The SEM can image an area on the order of millimetres by millimetres with a depth of field on the order of millimetres. The AFM can only image a maximum height on the order of micrometres and a maximum scanning area of around 150 by 150 micrometres.
24Another inconvenience is that an incorrect choice of tip for the required resolution can lead to image artifacts. Traditionally the AFM could not scan images as fast as an SEM, requiring several minutes for a typical scan, while a SEM is capable of scanning at near real-time (although at relatively low quality) after the chamber is evacuated. The relatively slow rate of scanning during AFM imaging often leads to thermal drift in the image (Lapshin, 2004, 2007), making the AFM microscope less suited for measuring accurate distances between artifacts on the image. However, several fast-acting designs were suggested to increase microscope scanning productivity (Lapshin and Obyedkov, 1993) including what is being termed videoAFM (reasonable quality images are being obtained with videoAFM at video rate - faster than the average SEM). To eliminate image distortions induced by thermodrift, several methods were also proposed (Lapshin, 2004, 2007).
25Due to the nature of AFM probes, they cannot normally measure steep walls or overhangs. Specially made cantilevers can be modulated sideways as well as up and down (as with dynamic contact and non-contact modes) to measure sidewalls, at the cost of more expensive cantilevers and additional artifacts.