HOPG
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| Highly Ordered Pyrolytic Graphite |
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HOPG - Highly Oriented Pyrolitic Graphite is the material produced by the application of uniaxial pressure on deposited pyrocarbon at very high temperatures (sometimes more than 3000ºC). Depending on deformation, temperature and annealing time one can get material with different mosaic spreads, amounts of defects and granular structures (average size of the grains and crystallites).
The most suitable HOPG for STM/SPM applications should have large grains and crystallites, a uniform surface with minimal steps (parts of broken carbon planes) and should allow easily cleaving of very thin layers, such that the surface of the sample can be refreshed many times for investigations.
Atomic lattice of graphite (HOPG).
Image size 1.7 ? 1.7 ? 0.2 nm (ATC, Scan-8)
Courtesy Advanced Technologies Center (www.nanoscopy.net)
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| HOPG STRUCTURE |
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Graphite belongs to lamellar materials and consists of identical staked
planes. Carbon atoms within a single plane interact much stronger than
with those from adjacent planes. That explains lamellar behavior of graphite.
Each atom within a single plane has three nearest neighbours. Network
of carbon atoms connected by shortest bonds looks like honeycomb. This
two-dimensional and single-atom thick plane is called "graphene".
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| Positional relationship between two
identical graphene planes A and B. Graphite structure can be described as
an alternite succession of these planes ...ABABAB...
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"Typical" graphite, especially natural one, exhibits quite imperfect
structure due to plenty of defects and inclusions. A number of technologies
are developed for preparation of perfect graphite samples to take advantage
of its unique structure. Of these, pyrolysis of organic compounds is the
most common and effective.
To characterize perfection of HOPG samples, one uses term "mosaic
spread" which originates from X-ray crystallography. Similar to mica,
HOPG specimens are layered polycrystals resembling a mosaic of microscopic
monocrystal grains that are slightly disoriented with respect to each
other. The disorientation of the graphene sheets is responsible for the
broadening of the (002) diffraction peak.
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| HOW THEY MAKE HOPG? |
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According to the nature of graphite, higher annealing temperatures and longer annealing times reduce the
number of defects in the material and allow it to approach “ideal” graphite. In principle, mosaicity, defects
and granular structure may vary independently when annealing parameters change. But in the frame of the
standard technology of HOPG production, a correlation between mosaic spread, defects and granular structure exists.
Therefore samples annealed at higher temperatures have lower mosaicity and a more ”ideal“ structure.
Annealing at 3000ºC under high pressure is a very complicated technological process, which imposes some
restrictions on the annealed volume and causes a significant temperature gradient especially in the vicinity
of the pressing pistons. As a result, the quality of the material is best at the center of the annealed volume
where the highest temperature is achieved, while the amount of defects as well as mosaicity increase towards
the outer part of the annealed plate, so that the external part that directly contacts the piston (the last 0.5-0.7 mm)
could hardly be called HOPG at all.
Due to historical and price reasons, samples cut near these external regions (near the pistons) were used until
recently for STM/SPM application, while the inner part of the annealed volume (plate) was used mainly for neutron
and X-ray monochromators.
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| CHARACTERIZATION OF MIKROMASCH HOPG |
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The mosaic spread is characterized by measuring (in degrees) a full width
at half maximum (FWHM) of the rocking curve (Cu-Ka radiation peak).
Mosaic spread is measured by the standard method. Measurements are carried out with CuKα radiation and the
beam illuminating a significant part of the crystal simultaneously (approximately 8 X 8 mm taking into account
the incident angle). This is important because the measured value of the mosaic spread depends not only on crystal quality,
but also on the energy and the cross section of the reflected beam. This effect is caused mainly by large-scale surface
inplanarity or large-scale inplanarity of the carbon layers. Small regions tested by a narrow beam could have additional
mutual mismatch that increases the measured value of mosaic spread when the crystal is illuminated by a wide beam covering both
regions simultaneously. In a similar way the large-scale mismatch between outer layers and deeper layers that start to involve
reflection could increase the value of mosaicity measured with harder X-rays or with neutrons which have a larger penetration
depth than CuKα radiation.
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| Grade |
Mosaic Spread |
Side
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thickness
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Chip size, mm |
Application |
| Value |
Accuracy |
| ZYA |
0.4° |
±0.1° |
Double |
1; 2 mm |
10x10 |
SPM, X-Ray |
| ZYB |
0.8° |
±0.2° |
Double Single |
1; 2 mm 1.5 mm |
SPM, X-Ray SPM |
| ZYD |
1.5° |
±0.3° |
Double Single |
1; 2 mm 1; 1.5; 2 mm |
SPM, X-Ray SPM |
| ZYH |
3.5° |
±0.5° |
Double |
1; 1.5; 1.75; 2 mm |
SPM, X-Ray |
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Typical STM image of HOPG surface.
Corresponding fragment of graphene structure is superimposed.
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| X-Ray |
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Due to good quality confirmed by precise X-ray control, our HOPG can
be used not only as an STM substrate, but also as crystal-monochromators
for X-rays and neutrons (nevetheless, it is important to inform us in advance
that certain samples are going to be used as monochromators – we will choose
crystals with better planarity from a batch).
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| *If you need other sizes or thicknesses, feel free to ask us. |
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