MOLECULAR BEAM EPITAXY

Molecular Beam Epitaxy (MBE) is a material fabrication process used to produce

high-purity nano-scale materials. A material is grown through interactions between
a substrate and one or more beams of atoms or molecules incident upon the
substrate's surface. he beams are generated by sublimation of a solid source
material. he entire process is performed under ultra high !acuum. "ome
ad!antages of using MBE o!er other processes are# significantly impro!ed purity$
arbitrarily sharp deposition resolution$ and operation at low temperatures.

SYSTEM DESCRIPTION
%eneral MBE Apparatus &ayout$ in growth position.
he main MBE apparatus is composed of two ma'or sections( the substrate
chamber and the effusion cells. All sections must be e!acuated to low pressures to
ensure that the molecular beam condition is achie!ed. his condition re)uires that
the free path of a particle be greater than the dimensions of the substrate chamber.
*or a typical MBE set up$ a pressure of +,
--
orr is sufficient$ but pressures on the
order of +,
-+,
orr are commonly used.
EFFUSION CELLS
he effusion cells are the source of the molecular beams. A source material is
placed in a crucible within the cells and heated by radiation from a resisti!e
heating source. he solid source material sublimates due to the increased
temperature and high !acuum. he pressure of the !apour can be controlled by
!arying the temperature of the solid phase$ which in turn is controlled by !ariations
in crucible heating. Because the beam intensity within the substrate chamber
depends on the effusion cell pressures$ the amount of material reaching the surface
can be controlled by !arying the source temperature.
SUBSTRATE STAGE
he effusion cells are attached to the chamber and oriented so as to direct the beam
upon the substrate holder. he substrate holder is heated with a resisti!e element$
as in the effusion cells.
he substrate is the material that the film will grow on. .ommon substrate
materials are silicon$ %a$ As$ and sapphire$ but other substrates can be used. he
choice of substrate is !ery important$ and has been shown to effect the thin film
microstructure.
SHUTTERS
he shutters at the end of the collimation tunnel enable an operator to terminate the
material flux from each cell separately. he shutter closing time is significantly
smaller than a single layer deposition time. his means that the composition of the
final material can be controlled at the monolayer le!el.
he orientation of the shutters relati!e to the beam direction is important for
predictable operation of the system. /t is suggested that the shutters be placed some
distance away from the effusion cells and at an angle$ so that the beam is simply
directed away from the substrate stage$ as opposed to returned into the effusion
cell. Any beam that hits the chamber wall is captured$ so this process decreases
materials efficiency as more is wasted$ but increases reproducibility and control
o!er the system. he balance between these two is application specific and must be
ta0en into account.
RHEED
A 12EE3 (1eflection 2igh Energy Electron 3iffraction) monitoring system is
implemented in modern MBE e)uipment. he 12EE3 system is used to monitor
the growth surface during deposition. 2igh energy electrons are incident upon the
surface$ producing a diffraction pattern upon the 12EE3 screen. he diffraction
pattern can be analy4ed to determine surface characteristics$ li0e the material
structure$ as well as composition. he intensity of the diffraction pattern has been
found to !ary predictably with the surface layer formation$ and can be used to
determine when a monolayer has been fully formed. his information can be used
to control the effusion cell shutters to produce an atomically flat surface.
5ne further benefit of the 12EE3 apparatus is that it allows the operator to
in!estigate the surface without re)uiring a direct !iew of the surface. his a!oids
the problems associated with !iewing screens on 627 e)uipment.

PRINCIPLES OF OPERATION
Molecular beam epitaxy is a complicated process. An understanding of how and
why it wor0s$ howe!er$ can be had merely by understanding the basic materials
engineering principles that underlie the process. here are two ma'or topics within
materials science that dri!e the MBE process( phase e)uilibrium within the
effusion cells$ and surface diffusion at the growth surface.
PHASE EQUILIBRIUM
8ithin the effusion cells$ the ma'or process dri!ing flux generation is the solid-
!apour phase e)uilibrium. he pressure at which the MBE process is underta0en is
below the triple point (where the three lines meet)$ and thus the only phases present
at e)uilibrium are solid and !apour. E)uilibrium is met at normal operating
conditions if the effusion cell is properly designed. %ibb's phase law states
F = N +2 P
8here * is the number of degrees of freedom of a system$ 9 is the number of
chemical components present$ and : is the number of phases present. /n the
effusion cell$ there is one chemical component and two phases. hus$ there is only
one degree of freedom$ meaning that pressure and temperature cannot be changed
independently. .on!ersely$ this means that the pressure of the cell can be
controlled by altering the temperature. he temperature and pressure are
exponentially related.
SURFACE DIFFUSION
he material grows upon the substrate$ the rate and type of crystal growth are
controlled by the energy a!ailable to the atoms. he rate of surface diffusion is
generally greater than that of bul0 lattice diffusion. 2owe!er$ the surface area of a
typical material is se!eral orders of magnitude smaller than the bul0$ and so is
often ignored in diffusion considerations. 3uring MBE growth$ howe!er$ a !ery
significant portion of the crystal is affected by its proximity to the surface. A
greater amount of surface diffusion increases the rate of growth$ as well as the
surface )uality. /f atoms arri!ing can tra!el farther along the surface$ they are more
li0ely to arri!e at the lowest energy$ defect-free$ state. Although limiting defects is
energetically fa!oured$ due to its lowering of surface energies$ defect formation is
fa!oured by entropic considerations. o o!ercome this$ the surface area must be
heated sufficiently so that the thermal energy of the diffusing atoms is great enough
to diffuse out defects.
Minimi4ation of surface energy is a ma'or dri!ing force for growth in MBE.
EFFICIENCY CONSIDERATIONS
+. SELECTION OF MATERIALS FOR APPARATUS
he choice of materials for use within an MBE apparatus is moti!ated by the 627
en!ironment and the demands for low contaminant le!els. Any material chosen for
use in high !acuum must ha!e a !ery low !apour pressure. he low rate of
e!aporation limits system damage$ but$ more importantly$ also decreases the
concentration of contaminant atoms in the atmosphere. Any atom that lea!es the
containment !essel and reaches the substrate stage has a high probability of 'oining
the sample surface and contaminating the sample. his re)uirement can be met by
using refractory metals for the apparatus.
9ote howe!er$ that not all refractory metals are satisfactory. *or example$
molybdenum has acceptable material properties for use in high !acuum$ but cannot
be used for MBE. 3ue to the processing method used to produce molybdenum
parts$ a significant amount of sulfur is embedded within molybdenum parts. hese
impurities will diffuse out of the surface and into the !acuum atmosphere. "ulfur is
notable as a dopant for semiconductors. Any stray dopant particles can lead to
compromised film properties$ and are to be a!oided all costs. *or this reason$
tantalum is used for many !essel components (e.g. resisti!e heating elements$
effusion cell shutters).
he effusion cell crucible material must also be chosen carefully. As the crucible is
in direct contact with the source material$ and at high temperatures$ a !ery low
reacti!ity and e!aporation rate are desired. he industry standard for effusion cell
crucibles for the production of semiconductors is boron nitride.
;. SYSTEM SEGREGATION
&i0e any system under !acuum$ an MBE apparatus must be pressuri4ed
occasionally for cleaning and maintenance. /n order to load a substrate$ or refill an
empty effusion cell$ the entire apparatus must also be pressuri4ed. 8hene!er the
apparatus is returned to atmospheric pressure$ the system is refilled with
contaminants. /n terms of process efficiency$ the less often any part of the system is
pressuri4ed and then returned to !acuum$ the better. 5ne solution to this issue in
MBE is through system segregation.
Modern MBE systems are di!ided into at least two distinct chambers( one in which
substrates are exchanged$ and another in which the material is grown. his enables
the loading and unloading of substrates without the associated pressuri4ing
problems. 8hen a new substrate is loaded$ only the much smaller substrate
exchange chamber needs to be returned to !acuum$ while the growth chamber
remains at 627. Another popular additional sectioning is to isolate the effusion
cells. his will allow the operator to refill an empty effusion cell without
pressuri4ing the growth chamber$ and e!en without stopping the growth process$ if
other cells are also operating. 1educing the number of pressuri4ing steps will
decrease processing time and increase sample purity significantly.

<. SURFACTANTS
As mentioned pre!iously$ film growth during MBE is dri!en by surface diffusion.
he rate of film growth can be increased by increased the rate of surface diffusion.
5ne method to achie!e this is by increasing temperature. he only other way to
increase diffusion is by reducing the pre-exponential diffusion coefficient.
5ne group has shown success in increasing system mobility at low temperatures in
the epitaxial growth of %aAs by the use of a hydrogen flux acting as a surfactant.
By directing a beam of atomic hydrogen toward the surface of a %aAs film being
grown by MBE$ the process temperature could be dropped from =,, degrees
.elsius to <<, degrees without any drop in film )uality. he mechanism is belie!ed
to be related to hydrogen atoms bonding with surface arsenic atoms$ which greatly
decreases the surface energy and increases the mobility of gallium atoms along the
surface. he hydrogen atoms were then displaced by the gallium atoms to form an
almost perfect layer.
Another benefit of the hydrogen flux was its surface cleaning effect. he hydrogen
atoms$ which ha!e no detrimental effect on the film end product$ displaced
possible surface contaminants. he increased pressure near the substrate surface
caused by the hydrogen flux would push other atoms out of the way$ increasing
surface )uality. he additional flux can also be used to cool and clean the film at
the end of the processing