Scanning Quantum Dot Microscopy
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Scanning quantum dot microscopy (SQDM) is a
scanning probe microscopy Scanning probe microscopy (SPM) is a branch of microscopy that forms images of surfaces using a physical probe that scans the specimen. SPM was founded in 1981, with the invention of the scanning tunneling microscope, an instrument for imaging ...
(SPM) that is used to image nanoscale
electric potential Electric potential (also called the ''electric field potential'', potential drop, the electrostatic potential) is defined as electric potential energy per unit of electric charge. More precisely, electric potential is the amount of work (physic ...
distributions on surfaces. The method quantifies surface potential variations via their influence on the potential of a
quantum dot Quantum dots (QDs) or semiconductor nanocrystals are semiconductor particles a few nanometres in size with optical and electronic properties that differ from those of larger particles via quantum mechanical effects. They are a central topic i ...
(QD) attached to the apex of the scanned probe. SQDM allows, for example, the quantification of surface dipoles originating from individual
adatom An adatom is an atom that lies on a crystal surface, and can be thought of as the opposite of a surface vacancy. This term is used in surface chemistry and epitaxy, when describing single atoms lying on surfaces and surface roughness. The word ...
s,
molecule A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
s, or
nanostructure A nanostructure is a structure of intermediate size between microscopic and molecular structures. Nanostructural detail is microstructure at nanoscale. In describing nanostructures, it is necessary to differentiate between the number of dimen ...
s. This gives insights into surface and interface mechanisms such as
reconstruction Reconstruction may refer to: Politics, history, and sociology *Reconstruction (law), the transfer of a company's (or several companies') business to a new company *''Perestroika'' (Russian for "reconstruction"), a late 20th century Soviet Union ...
or relaxation, mechanical distortion, charge transfer and
chemical interaction A chemical substance is a unique form of matter with constant chemical composition and characteristic properties. Chemical substances may take the form of a single element or chemical compounds. If two or more chemical substances can be combine ...
. Measuring electric potential distributions is also relevant for characterizing organic and inorganic
semiconductor device A semiconductor device is an electronic component that relies on the electronic properties of a semiconductor material (primarily silicon, germanium, and gallium arsenide, as well as organic semiconductors) for its function. Its conductivit ...
s which feature electric dipole layers at the relevant
interfaces Interface or interfacing may refer to: Academic journals * ''Interface'' (journal), by the Electrochemical Society * '' Interface, Journal of Applied Linguistics'', now merged with ''ITL International Journal of Applied Linguistics'' * '' Inter ...
. The probe to surface distance in SQDM ranges from 2 nm to 10 nm and therefore allows imaging on non-planar surfaces or, e.g., of
biomolecule A biomolecule or biological molecule is loosely defined as a molecule produced by a living organism and essential to one or more typically biological processes. Biomolecules include large macromolecules such as proteins, carbohydrates, lipids ...
s with a distinct 3D structure. Related imaging techniques are Kelvin Probe Force Microscopy (KPFM) and Electrostatic Force Microscopy (EFM).


Working principle

In SQDM, the relation between the potential at the QD and the surface potential (the quantity of interest) is described by a
boundary value problem In the study of differential equations, a boundary-value problem is a differential equation subjected to constraints called boundary conditions. A solution to a boundary value problem is a solution to the differential equation which also satis ...
of electrostatics. The boundary \mathcal is given by the surfaces of sample and probe assumed to be connected at infinity. Then, the potential \Phi_\text = \Phi(\mathbf) of a point-like QD at \mathbf can be expressed using the
Green's function In mathematics, a Green's function (or Green function) is the impulse response of an inhomogeneous linear differential operator defined on a domain with specified initial conditions or boundary conditions. This means that if L is a linear dif ...
formalism as a sum over volume and surface integrals, where \mathcal denotes the volume enclosed by \mathcal and \mathbf' is the surface normal. \Phi_\text = \Phi(\mathbf)=\iiint\limits_\mathcal G(\mathbf, \mathbf') \fracd^3\mathbf'+ \frac\oint\limits_\mathcal \bigg (\mathbf, \mathbf')\frac-\Phi(\mathbf')\frac\bigg^2\mathbf'. In this expression, \Phi_\text depends on the charge density \rho inside \mathcal and on the potential \Phi on \mathcal weighted by the Green's function G(\mathbf,\mathbf')=\frac + F(\mathbf,\mathbf'), where F satisfies the
Laplace equation In mathematics and physics, Laplace's equation is a second-order partial differential equation named after Pierre-Simon Laplace, who first studied its properties in 1786. This is often written as \nabla^2\! f = 0 or \Delta f = 0, where \Delt ...
. By specifying F and thus defining the
boundary conditions In the study of differential equations, a boundary-value problem is a differential equation subjected to constraints called boundary conditions. A solution to a boundary value problem is a solution to the differential equation which also satis ...
, these equations can be used to obtain the relation between \Phi_\text and the surface potential \Phi_\text(\mathbf'), \quad \mathbf' \in \mathcal for more specific measurement situations. The combination of a conductive probe and a conductive surface, a situation characterized by
Dirichlet boundary condition In mathematics, the Dirichlet boundary condition is imposed on an ordinary or partial differential equation, such that the values that the solution takes along the boundary of the domain are fixed. The question of finding solutions to such equat ...
s, has been described in detail. Conceptually, the relation between \Phi_\text(\mathbf) and \Phi_\text(\mathbf') links data in the imaging plane, obtained by reading out the QD potential, to data in the object surface - the surface potential. If the sample surface is approximated as locally flat and the relation between \Phi_\text(\mathbf) and \Phi_\text(\mathbf') therefore translationally invariant, the recovery of the object surface information from the imaging plane information is a
deconvolution In mathematics, deconvolution is the inverse of convolution. Both operations are used in signal processing and image processing. For example, it may be possible to recover the original signal after a filter (convolution) by using a deconvolution ...
with a
point spread function The point spread function (PSF) describes the response of a focused optical imaging system to a point source or point object. A more general term for the PSF is the system's impulse response; the PSF is the impulse response or impulse response ...
defined by the boundary value problem. In the specific case of a conductive boundary, the mutual screening of surface potentials by tip and surface lead to an exponential drop-off of the point spread function. This causes the exceptionally high lateral resolution of SQDM at large tip-surface separations compared to, for example, KPFM.


Practical implementation

Two methods have been reported to obtain the imaging plane information, i.e., the variations in the QD potential \Phi_\text(\mathbf) as the probe is scanned over the surface. In the compensation technique, \Phi_\text is held at a constant value \Phi_\text^0. The influence of the laterally varying surface potentials on \Phi_\text is actively compensated by continuously adjusting the global sample potential via an external bias voltage V_\text. \Phi_\text^0 is chosen such that it matches a discrete transition of the QD charge state and the corresponding change in probe-sample force is used in
non-contact atomic force microscopy Non-contact atomic force microscopy (nc-AFM), also known as dynamic force microscopy (DFM), is a mode of atomic force microscopy, which itself is a type of scanning probe microscopy. In nc-AFM a sharp probe is moved close (order of angstroms) to th ...
to verify a correct compensation. In an alternative method, the vertical component of the
electric field An electric field (sometimes called E-field) is a field (physics), physical field that surrounds electrically charged particles such as electrons. In classical electromagnetism, the electric field of a single charge (or group of charges) descri ...
at the QD position is mapped by measuring the energy shift of a specific optical transition of the QD which occurs due to the
Stark effect The Stark effect is the shifting and splitting of spectral lines of atoms and molecules due to the presence of an external electric field. It is the electric-field analogue of the Zeeman effect, where a spectral line is split into several compon ...
. This method requires an additional optical setup in addition to the SPM setup. The object plane image \Phi_\text(\mathbf') can be interpreted as a variation of the
work function In solid-state physics, the work function (sometimes spelled workfunction) is the minimum thermodynamic work (i.e., energy) needed to remove an electron from a solid to a point in the vacuum immediately outside the solid surface. Here "immediately" ...
, the surface potential, or the surface dipole density. The equivalence of these quantities is given by the
Helmholtz equation In mathematics, the Helmholtz equation is the eigenvalue problem for the Laplace operator. It corresponds to the elliptic partial differential equation: \nabla^2 f = -k^2 f, where is the Laplace operator, is the eigenvalue, and is the (eigen)fun ...
. Within the surface dipole density interpretation, surface dipoles of individual nanostructures can be obtained by integration over a sufficiently large surface area.


Topographic information from SQDM

In the compensation technique, the influence of the global sample potential V_\text on \Phi_\text depends on the shape of the sample surface in a way that is defined by the corresponding boundary value problem. On a non-planar surface, changes in \Phi_\text can therefore not uniquely be assigned to either a change in surface potential or in surface topography t_\text if only a single charge state transition is tracked. For example, a protrusion in the surface affects the QD potential since the gating by V_\text works more efficiently if the QD is placed above the protrusion. If two transitions are used in the compensation technique the contributions of surface topography t_\text and potential \Phi_\text can be disentangled and both quantities can be obtained unambiguously. The topographic information obtained via the compensation technique is an effective ''dielectric topography'' of metallic nature which is defined by the geometric topography and the dielectric properties of the sample surface or of a nanostructure.


References

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External links

*https://www.fz-juelich.de/pgi/pgi-3/EN/Groups/LTSTM/Research/SQDM.html *https://poggiolab.unibas.ch/research/Scanning%20Quantum%20Dot%20Microscopy/ *http://momalab.org/index.php/?action=devices Scanning probe microscopy