13/9/2010 types of pores, pores in Silicon

Short history and types of pores in Silicon

Macropores, mesopores and nanopores are the three types of pores observed in Si.
What are pores in silicon, how they look like and how they can be made!

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1.1. Short history and types of pores in Silicon: macropores,
Chapter 1
mesopores and nanopores
1.1 Short history
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1.2.1 N-type
m acropore s in Si
From many points of view microelectronics is one of the most important
field of the modern industry. Computers, internet, mobile phones etc.
1.2.2 P-type technologies w ouldn't be possible without the invention of transistor by
m acropore s in Si Bardeen and Brattain [1, 2] and the idea of making integrated circuits (IC)
proposed by Kilby [3].
Chapter 2
Although the first transistors were demonstrated on Germanium (Ge), the
Chapter 3 modern microelctronics technology is dominated by Silicon (Si). There are
many reasons which "force" the industry to prefer Silicon in 95 from 100
Chapter 4 cases. Here are some of them:
Chapter 5

Chapter 6 First of all, Si is the second frequently met element on the earth.
Mainly in the form of silicon dioxide, it makes more than 27 % of the
Appendixes
accessible earth chemical elements;
Si crystal grow th technology is the most evolved one regarding
Papers
purity, crystal defects and w afer size for processing. 300 mm Si
Sitemap wafers are standard wafers in Si microelectronics at the moment of
writing (2005);
SiO 2 , the native oxide of Si, is very stable and makes a very good
interface with Si substrates. Therefore, it can be easily used as
passivation layer for photolithography or as gate oxide in field effect
transistors (FET);
Last but not least, it is a lucky material. The microelectronic industry,
in spite of its modern aura, it is one of the most conservative
industries. It w orks under the motto "never change a w inning team",
Last Updated on
i.e. Si and its technology.
2009-10-08

How ever, advantages are always accompanied by disadvantages. Here

are some Si disadvantages with respect to other semiconductors:

Si is an indirect semiconductor and therefore has a very inefficient

electron-hole radiative recombination. As a consequence, bulk Si can
not be used in optoelectronics for the fabrication of Light Emitting
Diodes (LEDs) or lasers;
The mobility of electrons and holes in Si is relatively small. This makes
Si devices to be slow er as compared to GaAs devices for example;
Si has a relatively small electronic band gap (1.1 eV) and can not be
used at temperatures higher than 500 K. This is not true for other
semiconductors like GaN for example (3.3 eV).

Concerning the fist "disadvantage" mentioned above, an interesting

discovery w as made simultaneously but independent by Lehmann and
Canham at the beginning of the nineties of the last century [4, 5]. They
observed that the emission of light from Si can be considerably improved if
Si is made porous. "Porous" in this context means that billions of
nanometer-size holes, similar to those in cheese, are made in a normal
single crystalline Si substrate. Thus, a device based on porous Si will emit
efficiently light, w hereas one based on a normal single crystalline Si
substrate w ill not.
A real investigation boom began immediately after this discovery was
published. This w as triggered by the hope that porous Si w ill make
possible the integration of passive optical devices like gratings,

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13/9/2010 types of pores, pores in Silicon

w aveguides etc., on the same substrate with porous Si light emitting

devices, i.e. LEDs. Such an integration would make true an old dream - to
produce integrated optoelectronic circuits on cost-effective and well
investigated Si substrates.
Unfortunately, this dream did not become reality even after 14 years of
research and trials. The main problem up to now is the stability of the
emitted light from porous structures. This means that the emission
degrades w ith time and therefore it is not good enough for commercial
applications.
Nevertheless, two important conclusions should be made at this point:

By structuring a bulk material, in our case by making a semiconductor

porous, novel material with totally new properties have been
obtained;
A new approach for nanostructuring at the nanometer scale w as
found, about w hich we said nothing up to now .

Did Lehmann and Canham use mechanical nanometer drilling machines or

something similar for obtaining their porous structures? The answ er is
definitely "No". Both of them used the well known electrochemical etching
or dissolution.
Electrochemical dissolution is a result of anodic current flow at solid-liquid
interfaces. The exact definition of anodic currents w ill be given in the next
chapters. In more simple terms, in order to obtain the porous structures,
Lehmann and Canhamm simply applied a positive potential on a Si
electrode and forced a current to flow through the Si/HF interfaces.
The positive potential will force the positive charge carriers (i.e. holes, see
next chapters for definition of carrier types in semiconductors) from the
semiconductor to move tow ards the Si/HF interface. As w e will see later, a
hole is nothing else than a missing electron in a bond betw een tw o atoms
of the semiconductor. Thus, a surface atom surrounded by many holes will
be less strongly bonded to the substrate and consequently much easier
removed, i.e. dissolved, from the surface of the substrate as compared to
an atom w ithout holes in its surrounding. As a rule of thumb, it can be
said that a semiconductor region w ith a higher density of holes w ill have a
higher dissolution rate during the anodization as compared to a region
w ith lower hole density.
How ever, it is reasonable to assume that if an anodic current is forcing
the holes to go towards the Si/HF interface, then the density of the holes
should be constant over the whole surface of the electrode. In such a
case the dissolution rate should the same over the w hole sample and the
dissolution should be isotropic.
How ever, as w as demonstrated by Lehmann and Canham for certain
anodization conditions, the dissolution can be anisotropic, resulting in
porous structures like those presented schematically in Figure 1.1.

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13/9/2010 types of pores, pores in Silicon

Figure 1.1. What are pores and how they can be obtained? A Si sample is
immersed in a vessel containing a HF solution. A closed circuit is made
betw een the Si sample and a Pt electrode. A voltage source is applying a
positive potential on the sample, thus forcing a current to flow . One
possible result of the current flow is the formation of small holes in the
substrate. Such holes are called pores.

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At this point, it is important to note that the first observations of porous

silicon layers go 40 years back and w ere done by Uhlir and Turner [6].
They observed that as a result of anodic current flow through Si/HF
interfaces the colour of the samples changed. How ever, they interpreted
the colour change (brow n to black) as precipitation of silicon related
species from the solution used. Therefore, it can be considered that
Lehmann and Canham did nothing else than to prove that the result of
anodization is not a deposition but a selective dissolution process of Si.
The selective dissolution generates small pores in the initial substrate,
leaving the pore w alls in their initial single crystalline form.
After the first experiments on porous Si, it was clear that the morphology
of porous structures strongly depends upon the experimental conditions,
i.e. doping level of the substrate, electrolyte concentration, current
density, applied voltage, temperature of the electrolyte, electrochemical
cell design etc. These findings urged the scientific community to adopt a
standard classification for the different types of electrochemically obtained
pores. According to the International Union of Pure and Applied Chemistry,
for short IUPAC, three categories of pores (not only electrochemically
obtained) have to be distinguished if taking into account only the average
pore diameter and average distance betw een pores:

Micropores or nanopores , w ith pore diameters and pore distances

smaller than 2 nm. These are actually the pores which stimulate an
efficient luminescence in Si. Such kind of pores form more or less a
sponge like structure (Figure 1.2a).
Mesopores , w ith geometries in the 2 to 50 nm range. Formation of
such pores does not result in the emergence of efficient luminescence
in Si. The mesopores have a more defined direction of growth,
how ever the pore w alls are still very rough w ith a lot of side

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13/9/2010 types of pores, pores in Silicon

branches (Figure 1.2b).

Macropores have geometries larger than 50 nm. Similar to
mesopores, the formation of macropores does not lead to efficient
luminescence in Si. Nevertheless, these pores have the most exciting
structure. They expose smooth pore w alls and have well defined
directions of grow th (Figure 1.2d). Macropores w ill be the main
subject of this book.

Figure 1.2: Three types of pores observed in Si; a) Nanopores - sponge-

like structure; b) Mesopores - tree-like structure; c) Macropores - smooth
pore walls.

Figure 1.3: Current voltage characteristics of the Si/aqueous HF interface

w ith back side illumination.

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13/9/2010 types of pores, pores in Silicon

In Si, the bridging betw een the IUPAC pore types and the etching
conditions can be done easily by means of the so called current-voltage
(I-V) characteristics of the Si/HF interface. Schematic examples of typical
Si/HF IV curves for p- and n-type samples are presented in Figure 1.3. The
I-V curves for n- as w ell as for p-type Si can be divided in tw o main
regions:

Pore formation region.

Electropolishing region.

The amazing thing about the pore formation region in Si is that for each of
the three type of pores, a separate sub-region can be found on the I-V
curve. As a rule of thumb, by increasing the current through the Si/HF
interface from 0 to jP SL, first macropores, then meso and near the jP SL
peak nanopores are found.

On the other hand, electropolishing region means that isotropic

dissolution of the substrate w ithout pore formation is taking place. Pore
formation and electropolishing regions are separated by the so called
jPSL /UPSL peak (PSL = Porous Silicon Layer). The second peak on the I-V
curve is called - oxidation peak jO x /UO x .

At its turn, the electropolishing region has tw o sub-regions: non-

oscillating and oscillating. The non-oscillating sub-region is mainly
betw een jPSL /UPSL and jO x /UO x , w hereas oscillations are found after the
oxidation peak jO x /UO x . "Oscillating" in this context means that the
measured voltage across the Si/HF interface oscillates in time if the
current applied to the sample is kept constant (galvanostatic regime), or
vice versa, the measured current oscillate if the applied voltage is kept
constant (potentiostatic regime).
Going back to the pore formation region, it should be noted that there are
many theories explaining the improvement of light emission from
nanoporous Si. The most accepted explanation is based on quantum size
effects. If the thickness of the pore w alls reaches values below several
nanometers, quantum effects can change the band structure of the
nanoparticles (pore w alls), e.g. by transforming it from an indirect into a
direct band. Therefore, nanoporous samples eventually are able to emit
strong visible photo- and electroluminscence.
On the other hand, mesoporous and macroporous materials do not exhibit
efficient luminescence. How ever, due to the fact that a porous skeleton
has a three dimensional configuration (3D) the total surface of the
structure increases considerably as compared w ith the surface initially
exposed to the electrolyte (see Figure 1.4). These huge surface could be
used in different applications were a large surface in a small volume is
required. Surface increase is valid for nanopores as w ell, how ever the
mesoporous and macroporous materials are mechanically more stable as
compared with nanoporous ones. The smoothness of macropores is of
great advantage for applications w ere a high uniformity of the structure is
required, for example in photonic crystal applications.

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13/9/2010 types of pores, pores in Silicon

Figure 1.4: a) Initial surface of a Si sample; b) Increased surface of a

porous sample.

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