 |
We now have hyperpure poly-Si, already doped
to the desired level, and the next step must be to convert it to a single
crystal. There are essentially two methods for crystal growth used in this case:
|
|  | Czochralski or crucible grown crystals
(CZ crystals). |
|
| | Float zone or FZ
crystals. |
| The
latter method produces crystals with the highest purity, but is not easily used at large diameters.
150 mm crystals are already quite difficult to make and nobody so far has made a 300
mm crystal this way. Float zone crystal growth, while the main method at the beginning
of the Si age, is now only used for some specialities and therefore will not be discussed
here; some details can be found in the
link. |
| |
The Czochralski method, invented by the Polish scientist J. Czochralski in 1916, is the method of choice
for high volume production of Si single crystals of exceptional quality and shall be
discussed briefly. Below is a schematic drawing of a crystal growth apparatus employing the
Czochralski method. More details can be
found in the link. |
| | |
|
|
Essentially, a crystal is "pulled" out of a vessel
containing liquid Si by dipping a seed
crystal into the liquid which is subsequently slowly withdrawn at a surface temperature
of the melt just above the melting point. |
|
|
The pulling rate (usually
a few mm/min) and the temperature profile determines the
crystal diameter (the problem is to get rid of the heat of crystallization). |
| | Everything
else determines the quality and homogeneity - crystal growing is still as much an art as a science! Some interesting points are contained
in the link. |
| Here we only look at one major point, the
segregation coefficient kseg of impurity atoms. |
| | The
segregation coefficient in thermodynamic equilibrium gives the relation between the concentration
of impurity atoms in the growing crystal and that of the melt. It is usually much lower than
1 because impurity atoms "prefer" to stay in the melt. This can be seen from
the liquidus and solidus lines in the respective phase diagrams. |
| | In other words,
the solubility of impurity atoms in the melt is larger
than in the solid. |
| | "Equilibrium" refers to a growth speed of 0 mm/min
or, more practically, very low growth rates. For finite growth rates, kseg
becomes a function of the growth rate (called kseff) and approximates 1
for high growth rates (whatever comes to the rapidly moving interface gets incorporated). |
| This
has a positive and a negative side to it: |
|
|
On the positive side, the crystal will be cleaner than the liquid, crystal growing is simultaneously a purification
method. Always provided that we discard the last part of the crystal where all the impurities
are now concentrated. After all, what was in the melt must be in the solid after solidification
- only the distribution may now be different. |
| | This defines the negative
side: The distribution of impurities - and that includes
the doping elements and oxygen - will change along the length of a
crystal - a homogeneous doping etc. is difficult to achieve. |
| | That
segregation can be a large effect with a sensitive dependence on the growth rate is shown
below for the possible doping elements; the segregation coefficients of the unwanted impurities
is given in a table. |
| | | | | Atom |
Cu | Ag | Au | C | Ge |
Sn |
| |
kseg | 4 · 10–4
| 1 · 10–6 |
2,5 · 10–5 | 6 · 10–2 | 3,3 · 10–1 | 1,6 · 10–2 |
| | Atom |
O | S | Mn | Fe | Co |
Ni | Ta | |
kseg | 1,25 | 1 · 10–5 | 1 · 10–5 | 8 · 10–6 |
8 · 10–6 | 4 ·
10–4 | 1 · 10–7
| |
| |
We recognize one
reason why practically only As, P, and B is used for doping! Their segregation
coefficient is close to 1 which assures half-way homogeneous distribution during crystal
growth. Achieving homogeneous doping with Bi, on the other hand, would be exceedingly
difficult or just impossible. |
| Present day single crystals of silicon are the most perfect objects on this side
of Pluto - remember that perfection can be measured by using the second law of thermodynamics;
this is not an empty statement! A very interesting and readable article dealing with the history and the development
of Si crystal growth from W. Zulehner
(Wacker Siltronic), who was working on this subject from the very beginning of commercial
Si crystal growth until today, can be found in the link. |
| | What
the finished crystal looks like can be seen
in the link. What we cannot see is that there is no other crystal of a different material
that even comes close in size and perfection. |
| | Our crystal does not contain dislocations
- a unique feature that only could be matched by Germanium crystals at appreciable sizes (which
nobody grows or needs)1). It also does not contain
many other lattice defects. With the exception of the doping atoms (and possible interstitial
oxygen, which often is wanted in a concentration of about 30 ppm), substitutional and
interstitial impurities are well below a ppb if not ppt level (except for relatively
harmless carbon at about 1 ppm) - unmatched by most other "high purity" materials. |
| | Our crystal is homogeneous. The concentration of the doping atoms (and possibly
interstitial oxygen) is radially and laterally rather constant, a feat not easily achieved. |
| The crystal
is now ready for cutting into wafers. |
|
|
| Wafer Technology |
| |
|
| |
It may appear rather trivial now to cut the crystal
into slices which, after some polishing, result in the wafers used
as the starting material for chip production. |
| | However, it is not
trivial. While a wafer does not look like much, its not easy to manufacture. Again, making
wafers is a closely guarded secret and it is possibly even more difficult to see a wafer production
than a single Si crystal production. |
|
| | First, wafers must all be made to exceedingly tight geometric
specifications. Not only must the diameter and the thickness be precisely what they ought
to be, but the flatness is constrained to about 1 µm. |
| | This means that
the polished surface deviates at most about 1 µm from an ideally flat reference
plane - for surface areas of more than 1000 cm2 for a 300 mm wafer! |
| | And
this is not just true for one wafer, but for all 10.000 or so produced daily in one factory. The number of Si wafers sold in 2001 is about
100.000.000 or roughly 300.000 a day! Only tightly
controlled processes with plenty of know-how and expensive equipment will assure these specifications.
The following picture gives an impression of the first step of a many-step polishing procedure. |
| |
 |
© "Smithsonian", Jan 2000, Vol 30, No. 10
Reprinted with
general permission | |
| In contrast to e.g. polished metals, polished
Si wafers have a perfect surface - the crystal just
ends followed by less than two nm of "native oxide"
which forms rather quickly in air and protects the wafer from chemical attacks. |
| |
Polishing Si is not easy (but fairly well understood) and so is keeping the surface
clean of particles. The final polishing and cleaning steps are done in a cleanroom
where the wafers are packed for shipping. |
| | Since chip structures are always aligned along
crystallographic directions, it is important to indicate the crystallography of a wafer. This
is done by grinding flats (or, for very large wafer
- 200 mm and beyond notches) at precisely defined
positions. |
| | The flats also encode the doping types - mix ups are
very expensive! The convention for flats is as follows: |
| |
|
|
| | |
The main flat is always along a <110>
direction. However, many companies have special agreements with wafer producers and have "customized"
flats (most commonly no secondary flat on {100} p-type material). |
| | |
| More about flats in the link |
| | |
| Typical wafer specifications may contain more
than 30 topics, the most important ones are: |
| |
Doping type: n or p-type (p-type is by far the most common
type) and dopant used (P, As or B).
Resistivity (commonly between 100 W
cm to 0,001 Wcm with (5 - 1) Wcm
defining the bulk of the business. All numbers with error margins and homogeneity requirements |
| | Impurity concentrations for metals and other
"life time killers" (typically below 1012 cm–3),
together with the life time or diffusion length (which
should be several 100 µm). |
|
|
Oxygen and carbon concentration (typically around 6 · 1017
cm–3 or 1 · 1016 cm–3, respectively.
While the carbon concentration just has to be low, the oxygen concentration often is specified
within narrow limits because the customer may use "internal
gettering", a process where oxygen precipitates are formed intensionally in the
bulk of the wafer with beneficial effects on the chips in the surface near regions. |
| |
Microdefect densities (after all, the point defects generated
in thermal equilibrium during crystal growth must still be there in the form of small agglomerates).
The specification here may simple be: BMD ("bulk micro defect")
density = 0 cm–3. Which simply translates into: Below the detection
limit of the best analytical tools. |
|
|
Geometry, especially
several parameters relating to flatness. Typical tolerances are always in the 1 µm
regime. |
|
| Surface cleanliness: No particles
and no atomic or molecular impurities on the surface! |
|
This link provides a grapical overview of the complete production process - from sand to Si wafers -
and includes a few steps not covered here. |
|
| | Appreciate that the production of wafers -
at last several thousands per day - with specifications that are always at the cutting edge
of what is possible - is an extremely involved and difficult process. |
| | At
present (Jan. 2004), there are only a handfull of companies world wide that can do it.
In fact, 4 companies control about 80% of the market. |
| This link leads
to a recent (1999) article covering new developments in Si CZ crystal growth and wafer technology (from A.P. Mozer; Wacker Siltronic) and gives an impression of
the richness of complex issues behind the production of the humble Si wafer. |
| This link shows commercial wafer specifications. |
|
|
To give an idea of the size iof the industry: In
2004 a grand totoal of about 4.000.000 m2 of polished Si
wafers was produced, equivalent to about 1.25 · 108 200 mm wafers. |
| |
|
© H. Föll (Electronic Materials -
Script)
