A METHOD OF FABRICATING STRUCTURED PARTICLES COMPOSED
OF SILICON OR A SILICON-BASED MATERIAL AND THEIR USE IN
LITHIUM RECHARGEABLE BATTERIES.
Technical Field
The invention relates to a process of fabricating a silicon- containing material
such as a silicon wafer or a silicon particle through a surface etching technique
to form pillars thereon; a method of forming silicon fibres by detaching the
pillars so formed from the underlying material; an electrode containing such
particles and/or fibres as its active material and devices comprising such fibres
and particles, such as an electrochemical cell, solar capacitor or cell, fuel cells,
sensors or filters .
Background Art
The recent increase in the use of portable electronic devices such as mobile
telephones and notebook computers and the emerging trend of using
rechargeable batteries in hybrid electric vehicles has created a need for smaller,
lighter, longer lasting rechargeable batteries to provide the power to devices
such as these. During the 1990s, lithium rechargeable batteries, specifically
lithium-ion batteries, became popular and, in terms of units sold, now dominate
the portable electronics marketplace and are set to be applied to new, cost
sensitive applications. However, as more and more power hungry functions are
added to the above mentioned devices (e.g. cameras on mobile phones),
improved and lower cost batteries that store more energy per unit mass and per
unit volume are required.
The basic composition of a conventional lithium-ion rechargeable battery cell
including a graphite-based anode electrode is shown in Fig. 1. The battery cell
includes a single cell but may also include more than one cell.
The battery cell generally comprises a copper current collector for the negative
electrode (or anode) 10 and an aluminium current collector for the positive
electrode (or cathode) 1 which are both externally connectable to a load or to
a recharging source as appropriate. A graphite-based composite anode layer 14
overlays the current collector 10 and a lithium containing metal oxide-based
composite cathode layer 16 overlays the current collector 12. A porous plastic
spacer or separator 20 is provided between the graphite-based composite anode
layer 14 and the lithium containing metal oxide-based composite cathode layer
16. A liquid electrolyte material is dispersed within the porous plastic spacer or
separator 20, the composite anode layer 14 and the composite cathode layer 16.
In some cases, the porous plastic spacer or separator 20 may be replaced by a
polymer electrolyte material and in such cases the polymer electrolyte material
is present within both the composite anode layer 14 and the composite cathode
layer 16. The polymer electrolyte material can be a solid polymer electrolyte or
a gel-type polymer electrolyte and can incorporate a separator. The electrodes
are referred to as an anode or cathode based upon their function during
discharge of the cell, when current is supplied through a load. This means that
the negative electrode is referred to as the anode and the positive electrode is
referred to as the cathode. However, as known in the art, in a rechargeable cell
each electrode can function as both an anode and a cathode, depending on
whether the cell is being charged or discharged.
When the battery cell is fully charged, lithium has been transported from the
lithium containing metal oxide cathode layer 16 via the electrolyte into the
graphite-based anode layer 14 where it reacts with the graphite to create the
compound, LiC . The graphite, being the electrochemically active material in
the composite anode layer, has a maximum capacity of 372 mAh/g. It will be
noted that the terms "anode" and "cathode" are used in the sense that the
battery is placed across a load.
It is well known that silicon can be used as the active anode material of a
rechargeable lithium-ion electrochemical battery cell (see, for example,
Insertion Electrode Materials for Rechargeable Lithium Batteries, M. Winter, J.
O. Besenhard, M. E. Spahr, and P.Novak in Adv. Mater. 1998, 10, No. 10). It
is generally believed that silicon, when used as an active anode material in a
lithium-ion rechargeable cell, can provide a significantly higher capacity than
the currently used graphite. Crystalline silicon, when converted to the
compound Li22Si 5 by reaction with lithium in an electrochemical cell, has a
maximum theoretical capacity of between 4000 and 4,200 mAh/g, considerably
higher than the maximum capacity for graphite. Thus, if graphite can be
replaced by silicon in a lithium rechargeable battery the desired increase in
stored energy per unit mass and per unit volume can be achieved.
Many existing approaches of using a silicon or silicon-based active anode
material in a lithium-ion electrochemical cell, however, have failed to show
sustained capacity over the required number of charge/discharge cycles and are
thus not commercially viable.
One approach disclosed in the art uses silicon in the form of a powder having
particles with a diameter of IOm in some instances made into a composite
with or without an electronic additive and containing an appropriate binder
such as polyvinylidene difiuoride; this anode material is coated onto a copper
current collector. However, this electrode system fails to show sustained
capacity when subjected to repeated charge/discharge cycles. It is believed that
this capacity loss is due to partial mechanical isolation of the silicon powder
mass arising from the volumetric expansion/contraction associated with lithium
insertion/extraction to and from the host silicon. In turn this gives rise to
electrical isolation of the silicon particles from both the copper current
collector and each other. In addition, the volumetric expansion/contraction
causes the individual particles to be broken up causing a loss of electrical
contact within the spherical element itself.
Another approach known in the art designed to deal with the problem of the
large volume changes during successive cycles is to make the size of the silicon
particles that make up the silicon powder very small, i.e. in the 1-10 nm range.
This strategy does not prevent the electrical isolation of the spherical elements
from both the copper current collector and themselves as the silicon powder
undergoes the volumetric expansion/contraction associated with lithium
insertion/extraction. Importantly, the large surface area of the nano-sized
elements can give rise to the creation of a lithium-containing surface film that
introduces a large irreversible capacity into the lithium-ion battery cell. In
addition, the large number of small silicon particles creates a large number of
particle-to-particle contacts for a given mass of silicon and these each have a
contact resistance and may thus cause the electrical resistance of the silicon
mass to be too high. Furthermore, nano-sized particles tend to agglomerate into
larger particles, making preparation of uniform electrode composites difficult.
The above problems have thus prevented silicon particles from becoming a
commercially viable replacement for graphite in lithium rechargeable batteries
and specifically lithium-ion batteries.
In another approach described by Ohara et al. in Journal of Power Sources 136
(2004) 303-306 silicon is evaporated onto a nickel foil current collector as a
thin film and this structure is then used to form the anode of a lithium-ion cell.
However, although this approach gives good capacity retention, this is only the
case for very thin films (say ~50 nm) and thus these electrode structures do not
give usable amounts of capacity per unit area.
A review of nano- and bulk-silicon-based insertion anodes for lithium-ion
secondary cells has been provided by Kasavajjula et al (J. Power Sources
(2006), doi:10.1016/jpowsour.2006.09.84), herewith incorporated by reference
herein.
Another approach described in UK Patent Application GB2395059A uses a
silicon electrode comprising a regular or irregular array of silicon pillars
fabricated on a silicon substrate. These structured silicon electrodes show good
capacity retention when subjected to repeated charge/discharge cycles and this
good capacity retention is considered by the present inventors to be due to the
ability of the silicon pillars to absorb the volumetric expansion/contraction
associated with lithium insertion/extraction from the host silicon without the
pillars being broken up or destroyed. However, the structured silicon electrodes
described in the above publication are fabricated using a high purity, single
crystal silicon wafer and hence the electrode is expensive.
Selective etching of silicon-based materials to create silicon pillars is also
known from US-7033936. The pillars of this document are fabricated by
depositing hemispherical islands of caesium chloride or silicon dioxide on a
crystalline silicon substrate to form a mask surface, covering the substrate
surface, including the islands, with a film, and removing the hemispherical
structures (including the film covering them) from the surface to form a further
mask having exposed areas where the hemispheres had been. The substrate is
then etched in the exposed areas using reactive ion etching and the resist is
removed, e.g. by physical sputtering, to leave an array of silicon pillars in the
unetched regions, i.e. in the regions between the locations of the hemispheres
attached to the silicon base.
An alternative chemical method for fabricating silicon pillars or nano-wires is
described by Peng K-Q, Yan, Y-J, Gao S-P, and Zhu J., Adv. Materials, 14
(2002), 1164-1 167, Adv. Functional Materials, (2003), 13, No 2 February, 127-
132 and Adv. Materials, 16 (2004), 73-76 . According to the method of Peng,
et al a single silicon wafer (which may be n- or p-type and has the {111} face
exposed to solution) is etched at 50°C using the following solution: 5M HF and
20mM (0.02M) AgNO . The mechanism postulated in these papers is that
isolated nanoclusters of silver are electrolessly deposited on the silicon surface
in an initial stage (nucleation). In a second (etching) stage, the silver
nanoclusters and the areas of silicon surrounding them act as local electrodes
that cause the electrolytic oxidation of the silicon in the areas surrounding the
silver nanoclusters to form SiF6 cations, which diffuse away from the etching
site to leave the silicon underlying the silver nanocluster in the form pillars.
K. Peng et al, Angew. Chem. Int. Ed., 44 (2005), 2737-2742; and K. Peng et
al, Adv. Funct. Mater., 16 (2006), 387-394,describe a method of etching a
single silicon wafer that is similar to that described in the earlier papers by
Peng et al but the nucleation/ silver nanoparticle deposition step and the
etching step are performed in different solutions. In a first (nucleation) step, a
silicon chip is placed in a solution of 4.6M HF and 0.0 1M AgNO3 for 1 minute.
A second (etching) step is then performed in a different solution, namely 4.6M
HF and 0.135M Fe(N0 3)3 for 30 or 50 minutes. Both steps are carried out at
50°C. In these papers, a different mechanism is proposed for the etching step
as compared to the earlier papers, namely that silicon underlying the silver
(Ag) nanoparticles are removed and the nanoparticles gradually sink into the
bulk silicon, leaving columns of silicon in the areas that are not directly
underlying the silver nanoparticles.
In order to increase the uniformity and density of the pillars grown on silicon
wafers and the speed of growth, it has been proposed in WO2007/083 152 to
conduct the process in the presence of an alcohol.
Indeed, Garrido et al, J. Electrochem. Soc. 143(12) 1996 describes the superior
behaviour of HF/ethanol mixtures in the etching of silicon substrates.
It will be appreciated that each of these documents referred to above discloses
methods of fabricating silicon pillars or fibres on silicon wafers or chips.
Wafers or chips are generally expensive to make, which means that any fibres
or wires fabricated there from have a high intrinsic cost.
WO2009/0 10758 discloses the etching of silicon powder instead of wafers, in
order to make silicon material for use in lithium ion batteries. The resulting
etched particles, an example of which is shown in Figure 2, contain pillars on
their surface and the whole of the resulting particles can be used as an anode
material. Alternatively, the pillars can be severed from the particles to form
silicon fibres and only the silicon fibres are used to make the anode. The
etching method used is the same as that disclosed in WO2007/083 152.
PCT/GB2009/002348 discloses a further method that can be used to fabricate
silicon pillars from both highly pure and lower grade (for example,
metallurgical grade) silicon materials such as particulate or granular silicon.
The method involves treating the silicon material with a solution comprising 5
to 10 hydrofluoric acid (HF), 0.01 to 0.1M silver ions (Ag+), 0.02 to 0.2M
nitrate ions (N0 3 ) and adding further nitrate ions to maintain the concentration
of nitrate ions within the range specified during the treatment. The silicon
particles are used in an amount in excess of 6g of silicon per litre of etching
solution.
Pillar arrays or detached silicon fibres have also been used in the fabrication of
fuel cells, filters, sensors, field emitting diodes, chromatographic materials,
solar capacitors, solar cells and electrical capacitors amongst other
applications.
A problem with the methods disclosed in PCT/GB2009/002348 and
WO2007/083152 and the other documents referred to herein above, is that the
etching solution employs a high concentration of hydrofluoric acid (HF).
Although a high fluoride concentration is believed to be essential for the
etching step, a disadvantage of using such high concentrations of HF include
the complications associated with recycling the excess HF left in the etchant
solution after removal of the etched silicon material. Hydrogen fluoride is a
highly corrosive material. The safety requirements associated with the handling
of this material are complex and considerable. If the process involves the
formation of insoluble salts of SiF - the deposition of these salts may also
contaminate the final product. The process of recycling the waste etchant is
therefore both complex and costly. These cost implications have generally been
ignored to date because of the belief in the field that a relatively high HF
concentration is necessary if good quality pillars or fibres are to be produced.
Indeed previous attempts to use lower concentrations of HF have resulted in
very slow etch rates, wastage of the etching solution and poor quality silicon
pillars or fibres.
The system parameters used to etch silicon-containing material such as silicon
granules or powder have been found to be very different to those used for the
etching of silicon wafers. Granules and powders have a much greater surface
area than a silicon wafer of the same volume and tend to react more vigorously
with an etching solution as a result. The rate of etching will, of course, depend
upon the size and surface area of the silicon-containing particles being etched.
It has been found, for example, that etching systems containing a high
concentration of HF and a large quantity of silicon in the form of a granular or
particulate material are liable to generate a considerable amount of heat and
gas, which means that the system may be difficult to control and may result in
an etched product containing silicon pillars that are fused together. Further, if
the relative proportion of etching ingredients is incorrectly determined,
excessive hydrogen gas may be generated and trapped at the surface of the
silver nucleated silicon material thereby reducing access of the etching solution
to the silicon surface and the extent to which the silicon surface can be etched.
Finally it has been observed that if the HF concentration is too high, etching
may proceed in both a vertical and a transverse direction, which may cause the
pillars to become prematurely detached from the silicon surface. There is a
need, therefore, for an etching system that can be used to efficiently etch the
surface of a silicon powder or granule to give an etched silicon-containing
product including on its surface an array of evenly distributed, well defined
silicon-containing pillars having a uniform distribution of lengths and
diameters.
There is a further need for an etching method, which reduces the safety,
handling and cost issues associated with the use of etchant solutions
comprising high concentrations of hydrogen fluoride but which is also able to
produce silicon pillars or fibres of acceptable quality. The present invention
addresses that problem.
Disclosure of the Invention
It has been surprisingly found by the present inventors that it is possible to
fabricate silicon pillars or fibres of acceptable quality on silicon material such
as silicon wafers and silicon containing particles and granules by using
solutions comprising concentrations of HF that are lower than those that have
been previously used. A first aspect of the invention accordingly provides a
process for treating silicon comprising the steps:
exposing silicon-containing material to a solution comprising:
0.01 to 5M HF
0.002 to 0.2M of metal ions capable of nucleating on and forming a porous
layer comprising regions of elemental metal on the silicon surface;
0.001 to 0.7M of an oxidant selected from the group comprising 0 2, 0 , H20 ,
the acid, ammonium or alkali metal salt of N0 S20 NO2 , B 0 7
2 or C10 ~
or a mixture thereof. The treated silicon is suitably separated from the solution
after the treatment. Preferably the silicon material is powdered silicon.
The process of the first aspect of the invention can be used in a process for
etching silicon-containing material such as a silicon wafer or silicon-containing
powder particles and granules to give silicon-containing pillared particles.. The
term pillar should be understood to mean an elongate structure selected from
but not limited to the group comprising rods, columns, nanowires, tubes, fibres,
ribbons and flakes and these terms may be used interchangeably herein. A
pillar can have a uniform or non-uniform cross section along its length and a
circular or non-circular cross-section and can comprise a clump of elongate
structures fused or combined together. The diameter or width of a pillar can
vary along its length. The pillar can be formed upright or at an angle to a
substrate and can have a kink or one or more changes of direction along its
length, for example it can form a zig-zag or spiral shape. Pillars can have
smooth or rough surfaces and can be micro or macro porous. The term pillared
particle should be understood to mean a particle, wafer, chip, granule or other
substrate material with a plurality of pillars attached to or formed on one or
more of its surfaces and extending therefrom. The pillars can be arranged as a
regular or irregular array, an ordered pattern or in a scattered, random
distribution. Silicon-containing fibres can be isolated from the pillared particles
and the term "fibre" should be understood to include but is not limited to
structures selected from the group of rods, ribbons, threads, tubes and wires
and these terms may be used interchangeably herein.
By the term silicon-containing material it should be understood to include
wafers, chips, fragments, granules and particles that are formed from or contain
silicon metal having a purity in the range 90.00% or over by mass, preferably
98.00% or over and especially 99.0% to 99.99%. The term also extends to
silicon alloys, which include within their structure regions of silicon having
these purity levels.
By the term silicon powder, it should be understood to mean a granular or
particulate silicon-containing material having a principle diameter of greater
than m . The terms powder particles and granules should be understood to
include but not be limited to chips and fragments derived from the grinding or
fragmentation of silicon-containing wafers. Suitably the silicon-containing
material of the powder has a principle diameter of less than 1.5mm. The
silicon-containing granules or particles used as starting materials in the process
of the present invention typically have a principle diameter in the range 1 m
to 1.5mm and preferably 3 m h to 800 m . Where the process according to the
present invention is used to manufacture pillared particles the silicon
containing particles or granules preferably have a principal diameter in the
range 1 to 100 mpi, preferably 3 to 50 m i, more preferably 10 to 50 m h, most
preferably 20 to 40mpi and especially 15 mhi to 25 mp . Where the process of
the first aspect of the invention is used to manufacture detached siliconcontaining
fibres, the particles or granules have a principal diameter of up to
1.5mm. Silicon containing fibres are most easily (but not exclusively) prepared
from particles or granules having a principal diameter in the range lOOum to
1.5mm, preferably lOOum to 1mm, more preferably lOOum to 800um and
especially 200um to 500um. Particles or granules having a principal diameter
of less than lOOum can be used to manufacture pillars or fibres, where
appropriate. The particles or granules may be spherical or non-spherical in
shape. Examples of non-spherical particles or granules include, but are not
limited to, cuboidal, prismatic, tetrahedral, octahedral, decahedral and
dodecahedral structures.
The treating solution suitably comprises HF at a concentration of 0.01 to 5 ,
preferably 0.1 to 4M, more preferably 0.25 to 5M, most preferably 0.25 to 4M,
especially 2 to 4M and more especially 2 to 3M.
The process of the first aspect of the invention comprises a nucleation step in
which a porous metal layer or mat is deposited on the surface of the silicon (the
substrate) and an etching step in which the silicon material underlying the
nucleated metal layer or mat is removed to give a silicon based substrate
having silicon containing pillars or fibres extending there from.
The nucleation step requires the use of a solution comprising hydrogen ions
and the use of a solution comprising a metal ion capable of being reduced to
form a porous metal layer or mat on the silicon surface. An oxidant may be
present. The concentration of hydrogen ions in the nucleation solution is not
particularly important but must be sufficient to remove all native oxides from
the silicon surface to facilitate deposition of the metal species thereon. The
solution comprising a metal ion capable of being reduced on the silicon surface
may be provided separately to the solution comprising hydrogen ions providing
oxide formation on the surface of the silicon can be prevented. Preferably the
hydrogen ions and the metal ions are provided in a single solution. Nucleation
suitably requires the use of a solution comprising at least 0.01M H+ and
especially at least 0.5M H+. The hydrogen ion is most suitably provided in the
form of HF. The metal ion capable of being reduced to form a porous metal
layer is suitably present in the solution at a concentration in the range 0.002 to
0.2M, preferably 0.01 to 0.1 5M. Although not essential, it is preferred that the
nucleation solution includes an oxidant; this is suitably present at a
concentration in the range 0.002 to 0.004M. Oxidant concentrations in the
range 0.02 to 0.7M may also be used, but are less preferred for the nucleation
step.
The etching step suitably requires a solution comprising HF and an oxidant
selected from the group comprising 0 2, 0 3, H20 2, the acid, ammonium or alkali
metal salt of NO3 , S2O8
2 , NO2 B40 7
2 or ClO4 or a mixture thereof. The rate
of etching will depend, in part, on the concentration of HF and the nature and
concentration of the oxidant. If the oxidant concentration is too high or if the
oxidant is too strong, the rate of etching may be too fast. Controlled etching is
suitably achieved through the use of an etching solution comprising 0.001 to
0.7M, preferably 0.01 to 0.7M, more preferably 0.02 to 0.7M of an oxidant or
mixture of oxidants referred to above and 0.1 to 5M HF, more preferably 0.25
to 5M HF, most preferably 0.25 to 4 M HF. Alternatively the etching solution
comprises, in addition to HF, 0.003 to 0.7M of an oxidant or mixture of
oxidants referred to above, more preferably 0.01 to 0.7M, most preferably 0.04
to 0.5M and especially 0.04 to 0.07M.
For a fixed silicon loading and particle size, optimal etching of the silicon
surface may be achieved through controlled addition of one or more
components of the etching solution to the reaction chamber during the etching
step. It may be necessary to control one or both of the HF concentration and/or
the oxidant concentration during the etching step and this is best achieved by
monitoring the concentration of the HF and or the oxidant and adding further
HF and/or oxidant to the reaction mixture during the etching step to maintain
the concentration of the HF and/or oxidant within a specified concentration
range. Optimal etching of the silicon material is suitably achieved by
maintaining the concentration of the oxidant within the concentration range
specified herein above during the etching step. The oxidant concentration is
preferably maintained through the addition of oxidant species to the etching
solution; this can be achieved by adding the oxidant species to the solution in
one or more steps or by continual addition.
Preferred oxidants include the acid, ammonium or alkali metal salt of NO ,
H20 2, 0 2, and 0 3. The acid, ammonium or alkali metals salts of NO3 ions are
especially preferred. The nitrate ion is suitably derived from one or more of an
alkali metal nitrate salt, an ammonium nitrate salt or nitric acid. Alkali metal
nitrate salts and ammonium nitrates are especially preferred sources of nitrate
ions.
The rate of etching is also influenced by the concentration or amount of silicon
material per unit volume of etching solution (herein after referred to as the
silicon loading). The etching rate and pillar quality will be affected by both the
silicon loading and by the size and consequently surface area of silicon
particles. It has been observed that the rate of etching tends to be proportional
to the surface area of silicon material up to a loading maximum that depends on
the particle size for a fixed volume of the silicon material being etched. Once
the silicon loading exceeds a certain value, mass transport effects interfere with
the rate at which etchant species arrive at and leave a silicon surface, which
reduces the etching efficiency and results in the formation of poor quality
pillars. The optimal silicon loading for any one system will depend on the
concentration of the etching species (oxidant and HF) as well as the size of the
silicon particles being etched and an optimum silicon loading can be readily
determined through the use of methods known to a skilled person.
It has been observed that the silicon loading in the treatment solution can
strongly affect the nature of the product formed. If the silicon loading is too
high, the silicon-containing pillars formed are of a poor quality. Additionally, if
the silicon surface area is high, a high HF concentration must be avoided to
prevent the rate of etching from proceeding too rapidly. The optimal silicon
loading for a particular concentration of HF will depend, in part, upon the
particle size. Silicon loadings of between 2 and 60g/l have been found to give
products having acceptable pillar and/or fibre quality. Depending on the size
and surface area of particles being treated and the HF/Oxidant concentrations
used, higher loadings may be possible. For particles or granules having an
average principle diameter of the order of 25m , pillars and pillared particles
of acceptable quality can be obtained by loading silicon at a level of 15 to 40g/l
in a treating solution having an HF concentration of 7.5M. We have found that
the best results have been obtained by using 1 to lOg, suitably 2 to 8g and
preferably 4 to 8g of silicon granules of dimensions 15 to 25m for every litre
of etching solution having an HF concentration in the range 2 to 3.5M. Using
HF etching solutions having a concentration in the range 2 to 3.5M, silicon
loadings of 4 to 8g/l for particle sizes in the range 15 to 25mpi have been found
to give acceptable results. For silicon particles or granules having an average
principle diameter of 12 m , acceptable results can be obtained using a silicon
loading in the range 15 to 20g/l. A silicon loading of 7 to lOg/1 can be used for
silicon particles having an average principle diameter of 6 mh . A silicon
loading of between 2 and 8g/l has been used for silicon particles or granules
having an average principle diameter of between 200 and 800mpi. Preferably
the silicon loading is at least lg/1, more preferably at least 2g l, most preferably
at least 4g/l, especially at least 8g/l. Suitable maximum limits on silicon
loading are no more than 500g/l, more suitably no more than 100 g/1, especially
no more than 80 g/1.
It will be appreciated from the foregoing that for a fixed silicon loading and
particle size, the nature of the product of the treatment process of the first
aspect of the invention will depend upon the concentration in which the
individual components (HF, metal ions and oxidant) are present in the solution.
If the treating solution contains a relatively high concentration of metal ions
and a lower concentration of oxidant, the product of the process will generally
be in the form of nucleated silicon/silver particles or granules having a
minimally etched surface. If the treating solution contains a relatively high
concentration of HF and oxidant, the product of the process will generally be in
the form of an etched silicon particle or granule.
As indicated above, the metal ions provided by the treating solution must be
able to form a porous film or mat on the surface of the silicon during
nucleation. Without wishing to be constrained by theory, it is believed that the
formation of etched silicon pillars can only be achieved through the formation
of a porous film during nucleation; the porous metal film or mat is believed to
catalyse the etching step causing the silicon material underneath the nucleated
metal to be etched away more rapidly than the exposed silicon material
adjacent thereto, resulting in the formation of silicon pillars on the substrate
surface.
The nucleating metal ions provided in the treating solution are able to form a
porous mat over the surface of the silicon to be etched. The formation of a
dendritic mat is especially preferred. Examples of metals ions that are able to
form porous films on the silicon surface upon nucleation include silver, gold,
platinum, copper, nickel, lead, cobalt, cadmium, chromium, zinc and tin and
mixtures thereof. Where a mixture of metal ions are used it is preferable
(although not essential) to use metal ions having similar redox potentials. Metal
ions such as silver, gold, platinum and tin are preferred. Solutions containing
silver ions are especially preferred as silver ions are able to form a dendritic
mat or layer over the surface of the silicon to be etched on nucleation.
A first preferred embodiment according to the first aspect of the invention
provides a process for treating silicon comprising the steps of exposing silicon
powder to a solution comprising:
0.01 to 5M HF
0.002 to 0.2M Ag+ ions
0.001 to 0.7M N0 3 ions derived from nitric acid, ammonium nitrate and an
alkali metal nitrate. The treated silicon is suitably separated from the solution.
Preferably the silicon material is powdered silicon. The HF is suitably provided
at a concentration of 0.01 to 5M, preferably 0.1 to 4M, most preferably 0.25 to
5M, especially 0.25 to 4M, more especially 2 to 4M and particularly 2 to 3M.
The Ag+ ions are suitably provided at a concentration of 0.002 to 0.2M,
preferably 0.01 to 0.15M.
The process of the present invention will be described herein after with
reference to solutions containing silver ions as the nucleating species. It should
be appreciated, therefore, that where reference is made to solutions containing
silver ions, this should be understood to extend to treating solutions containing
ions such as gold, platinum, copper, lead, zinc, cobalt, cadmium, chromium,
nickel and tin and mixtures thereof.
As indicated above, the process of the first aspect of the invention comprises a
nucleation step in which a dendritic silver mat is deposited on the surface of the
silicon substrate and an etching step in which the silicon material underlying
the nucleated material of the silver mat is removed to give a silicon based
substrate having silicon containing pillars or fibres extending there from.
The silver film or mat formed as a result of the nucleation step comprises an
interconnected network of nucleated regions of silver atoms bound to the
silicon surface, which nucleated regions are interconnected by dendritic
branches formed there between as a result of the dendritic growth of silver
atoms extending from and between the originally nucleated regions of silver
atoms on the surface of the silicon. The resulting silicon surface comprises
regions of exposed silicon separated by regions defining a dendritic silver mat.
At the start of the process, nucleation and etching will generally occur
simultaneously in the solution. An oxidant may be present at this stage.
However, the nucleation step will dominate until substantially all the silver ions
are consumed. Once the silver ions have been substantially consumed, the
etching step dominates.
For the avoidance of doubt, it should be understood that, in the context of the
present invention, the period or phase during the process of the first aspect of
the invention over which the nucleation step dominates is known as the
nucleation step. During this phase the concentration of silver ions remains
above a minimum value. The period or phase over which the etching step
dominates is known as the etching step.
By the term silicon nanowires it should be understood to mean elongate
structures selected from but not limited to the group comprising fibres, tubes,
ribbons and flakes. The term "fibre" should be understood to include pillars,
threads and wires and these terms may be used interchangeably herein.
It will be appreciated from the foregoing that the nucleated silver mat will
typically catalyse the oxidation and etching of the silicon substrate material
underneath the regions of nucleated silver thereby supporting the continued
propagation of silicon nanowires until the HF concentration is insufficient to
support further etching.
It should be appreciated that where the treating solution comprises metal ions
or a mixture of metal ions, the resulting film may be a non-dendritic porous
film in which regions of nucleated metal are separated by areas of the exposed
silicon surface on which they are deposited. Where a treating solution
comprising a mixture of metal ions is used, it is preferred that the treating
solution contain a smaller concentration of the metal ion having a more positive
redox (or electrochemical potential) and a larger concentration of a metal ion
having a less positive redox potential. The metal ion having a more positive
redox potential will tend to nucleate on the silicon substrate surface in
preference to the metal ion having a less positive redox potential. The
concentration of the metal ion having a more positive redox potential is
preferably sufficient to provide areas of nucleation over the surface of the
silicon but is insufficient to support the formation of a continuous coat or layer.
The metal having the less positive redox potential will suitably nucleate
preferentially at the nucleation sites provided by the reduction at the silicon
surface of ions having a more positive redox potential; this ion will preferably
be present in a concentration sufficient to support the formation of a porous
layer or mat, which extends from these nucleated areas over the surface of the
silicon substrate.
Where a mixture of ions are used in the nucleation step, these can be provided
as a mixture in a single solution so that the nucleation can be carried out in a
single step or as separate solutions to allow the nucleation step to be carried out
in a sequential manner.
As indicated above, a solution comprising 0.01 to 5M HF and 0.001 to 0.7M of
an oxidant selected from the group comprising 0 2, 0 3, H20 2, the acid,
ammonium or alkali metal salt of N0 3 , S2O 2 , N0 2
~, B40 7
2 and C104 or a
mixture thereof. Preferred oxidants include the acid, ammonium or alkali metal
salts of O3 ions, 0 2, 0 3 and H20 2 or mixtures thereof can be used for the
etching step. The use of the acid, ammonium or alkali metal salts of NO3 ions
as an oxidant is particularly preferred. The concentration at which the oxidant
is used in solution will depend upon the nature of the oxidant itself; a stronger
oxidant (characterised by a more positive reduction potential) will be used at a
lower concentration range than a weaker oxidant. Suitably the etching solution
comprises 0.001 to 0.7M of an oxidant or mixture of oxidants referred to
above, preferably 0.003 to 0.7M, more preferably 0.02 to 0.7 , most
preferably 0.04 to 0.5M and especially 0.04 to 0.07M. Preferably, the etching
solution comprises HF at a concentration of 0.1 to 5M, preferably 0.1 to 4M,
more preferably 0.25 to 5M, most preferably 0.25 to 4 , especially 2 to 4M
and more especially 3 to 4M.
As indicated above, the rate at which the silicon material is etched will be
affected by one or more parameters selected from the concentration of HF, the
concentration of oxidant, the silicon loading and the surface area of the silicon
material. It will therefore be appreciated that for a fixed silicon loading and
surface area the etching rate can be controlled by maintaining the concentration
of one or both of HF or oxidant in the etching solution over the etching period.
Preferably the HF and/or oxidant concentration is maintained through the
addition of HF and/or an oxidant species over the course of the etching step.
Since the handling of HF is potentially hazardous, the etching rate is preferably
controlled by maintaining the concentration of the oxidant over the etching
period. The etching rate is most preferably maintained through the addition of
an oxidant species to the etching solution over the course of the etching step;
this can be accomplished through continuous or sequential addition of oxidant.
In a preferred embodiment of the first aspect of the invention, the rate of
etching can be controlled through the addition of an oxidant selected from the
group comprising NO3 ions, O2, 0 3 and H20 2 or mixtures thereof. The use of
N0 3 ions as an oxidant is especially preferred.
A second preferred embodiment of the first aspect of the invention provides a
process for treating silicon, the process comprising the steps of exposing
silicon-containing material to a solution comprising:
0.01 to 5M HF
0.002 to 0.2M of a metal ion capable of nucleating on and forming a porous
layer comprising regions of elemental metal on the silicon surface;
0.001 to 0.7M of an oxidant selected from the group 0 2, 0 , H20 2, the acid,
ammonium or alkali metal salts of N0 3 , S2O 2 , N0 2 , B 0 7 and C104 or a
mixture thereof;
and adding further oxidant species to the solution to maintain the concentration
of oxidant within the above range. The treated silicon may be separated from
the solution. The silicon material is preferably powdered silicon.
The process of the first aspect of the invention can be applied to siliconcontaining
wafers and silicon-containing chips, wafer fragments, granules and
particles. The terms "silicon-containing chips, wafer fragments, granules and
particles" will hereafter collectively be referred to as silicon-containing
powder. In a preferred embodiment of the first aspect of the invention the
silicon-containing material is a silicon-containing powder.
Where the process of the present invention refers to an etching solution, this
will be described herein after with reference to etching solutions containing
N0 3 ions as the oxidant. It should be appreciated, therefore, that where
reference is made to solutions containing N0 ions, this should be understood
to extend to solutions containing 0 , 0 , the acid, ammonium or alkali metal
salts of N0 3 , S20 8
~, N0 2 , B40 7
2 , C104 and H20 2 or mixtures thereof.
A third preferred embodiment of the first aspect of the invention provides a
process for treating silicon, the process comprising the steps of exposing
silicon-containing material to a solution comprising:
0.01 to 5M HF
0.002 to 0.2M of Ag+;
0.001 to 0.7M of N0 3 ions;
and adding further NO3 ions to the solution to maintain the concentration of
N0 3 within the above range, wherein the NO3- are provided in the form of the
an acid, ammonium or alkali metal nitrate; and separating the treated silicon
from the solution. Preferably the silicon-containing material is a siliconcontaining
powder.
It will be appreciated from the foregoing that the nucleation step can either
occur substantially simultaneously with the etching step or can be partially
separated there from by controlling the concentration of HF, metal ions and
oxidant in the treating solution.
The process according to the first aspect of the invention is simple to operate
on a commercial scale. In a fourth preferred embodiment of the first aspect of
the invention, the nucleation step can be substantially separated from the
etching step. This can be achieved by carrying out the etching and nucleation
step in separate baths or by adding HF and/or an oxidant to the reaction
chamber at the end of the nucleation step to bring the concentration of species
in the treatment solution within the range specified for the nucleation and
etching steps respectively. The concentration of species in the treating solution
that are used for the nucleation step may be different to the concentration of
species used for the etching step. Preferably the concentration of HF and/or
oxidant used for the nucleation step is lower (eg 0.5M) than the concentration
of HF and/or oxidant used in the etching step (eg 3 to 4M).
Alternatively, in a fifth preferred embodiment of the first aspect of the
invention, nucleation and etching can be carried out substantially
simultaneously. This can be achieved by contacting the silicon particles or
granules with a solution comprising 0.01 to 5M HF, 0.002 to 0.2M of metal
ions capable of nucleating on and forming a porous layer on the silicon surface,
preferably 0.01 to 0.1 5M and 0.001 to 0.7M, preferably 0.01 to 0.1 5M of an
oxidant in the same bath. Preferably the solution comprises 0.1 to 4M,
preferably 0.25 to 4M, more preferably 2 to 4M HF and especially 3 to 4M HF.
Preferably the etching solution comprises 0.003 to 0.7M (for example 0.02 to
0.7M or 0.04 to 0.5M) of an oxidant or mixture of oxidants referred to above,
more preferably 0.01 to 0.1M and especially 0.04 to 0.05M. It is further
preferred that the HF and the oxidant are present in a concentration ratio in the
range 100:1 to 300:1, preferably 175:1 to 275:1 and especially 250:1. The
metal ion is preferably a silver ion. The oxidant is preferably a nitrate ion. The
treating solution suitably comprises an aqueous solution of HF and a source of
nitrate ions derived from one or more of an alkali metal nitrate, ammonium
nitrate and nitric acid in the concentration ranges specified above.
As indicated above, it has been found that advantageous results have been
obtained by performing the nucleation step at a lower HF concentration and by
performing the etching step at a higher HF concentration. Without wishing to
be constrained by theory, it is believed that by carrying out the nucleation step
in a solution in which the concentration of HF is within the ranges specified
herein and is less than the concentration of HF in the solution used for etching,
the nucleation step is more controlled, which results in improved pillar
formation. The nucleation step is suitably carried out using a treating solution
having an HF concentration of less than 5M. Suitably the treating solution used
for nucleation has an HF concentration in the range 0.01 to 5M, preferably 0.25
to 5M, more preferably 0.24 to 5M, most preferably 1 to 5M, especially 2 to
4M and more especially 2 to 3M. Alternatively the treatment solution used for
nucleation has an HF concentration in the range 0.01 to 4M, preferably 0.1 to
2M, more preferably 0.1 to 1M and especially 0.5M.
Etching is suitably carried out using a treating solution having an HF
concentration of greater than 0.1M, with the proviso that the HF concentration
of the etching solution is greater than that of the nucleation solution, for
example at least 0.5-2M higher. The treating solution used for etching typically
has an HF concentration in the range 0.1 to 5M, preferably 0.1 to 4 , more
preferably 0.25M to 5M, most preferably 0.25 to 4M, especially 2 to 4M and
more especially 3 to 4M. Alternativelya treatment solution used for etching
may suitably have an HF concentration in the range 0.25 to 10M, preferably 1
to 8M, more preferably 2 to 7.5M, most preferably 4 to 7.5M and especially 6
to 7.5M.
It will be appreciated that the process described in accordance with the fourth
embodiment of the first aspect of the invention can be achieved though a
number of different approaches. A first preferred approach provides a process
for treating silicon, the process comprising a nucleating step and an etching
step, wherein the nucleating step requires exposing silicon to a solution
comprising 0.01 to 5M HF and 0.002 to 0.2M of a solution of a metal ion as
defined herein above and the etching step requires exposing the nucleated
silicon to a solution comprising 0.25 to 10M HF and 0.003 to 0.7M of an
oxidant or mixture of oxidants referred to above with the proviso that the
concentration of HF used in the etching step is greater than the concentration of
HF used in the nucleation step, for example at least 0.5-2 M higher. Suitably
the treating solution used for nucleation has an HF concentration in the range
0.01 to 5M, preferably 0.1 to 4M, more preferably 0.25 to 5M, most preferably
1 to 5M, especially 1 to 4M and more especially 2 to 4M, for example 2 to 3M.
Alternatively the treatment solution used for nucleation has an HF
concentration in the range 0.01 to 5M, preferably 0.1 to 4M, more preferably
0.1 to 2M, most preferably 0.1 to 1 and especially 0.5M. The treating
solution used for etching typically has an HF concentration in the range 0.1 to
5M, preferably 0.1 to 4M, more preferably 0.25M to 4M, most preferably 2 to
4M and especially 3 to 4M. Alternatively a treatment solution used for etching
may suitably have an HF concentration in the range 0.25 to 10M, preferably 1
to 8M, more preferably 2 to 7.5M, most preferably 4 to 7.5M and especially 6
to 7.5M.
Although in accordance with the fourth embodiment of the first aspect of the
invention, it is preferred to carry out the nucleation step using a solution having
an HF concentration of less than 4M or 5M, nucleation solutions having HF
concentrations of greater than 4M or 5M can be used for the nucleation step,
with the proviso that the concentration of HF in the etching solution is greater
than the concentration of HF used in the nucleation solution. It will thus be
appreciated that it will be possible to carry out nucleation at an HF
concentration of up to 7M, preferably up to 6M and especially up to 5M.
Preferably, nucleation will be carried out using a treatment solution having an
HF concentration in the range 0.01 to 7M, preferably 0.01 to 6 and especially
0.01 to 5M.
It is preferred that, in accordance with the fourth embodiment of the first aspect
of the invention, where the nucleation step is carried out substantially
separately from the etching step, the silicon is treated in a first step with a
solution comprising 0.002 to 0.2M, preferably 0.01 to 0.1 M of metal ions and
HF having a concentration of at least 0.0 1M, preferably at least 0.25M and
especially 0.5M to form a silver coated silicon product and, in a second step,
the silver coated silicon product is treated with an etching solution comprising
0.1 to 10M HF and 0.001 to 0.7M, preferably 0.02 to 0.7M of an oxidant with
the proviso that the concentration of HF in the nucleating solution is smaller
than the concentration of HF in the etching solution, for example at least 0.5 to
2 smaller. The HF concentration used for etching is typically greater than the
HF concentration used for nucleation by between 2 and 6 pH points. The
concentration of HF and/or the oxidant can be maintained during the etching
process by adding HF and/or oxidant to the etching solution. Suitably, the
concentration of HF and/or oxidant can be continuously monitored and further
HF and/or oxidant may be added to the etching solution, either in one or more
discrete steps or continuously over the duration of the etching period to
maintain the concentration of HF and/or oxidant within the concentration
ranges specified herein. In a preferred embodiment of the first aspect of the
invention, the concentration of oxidant is maintained over the duration of the
etching step and the concentration of HF is allowed to drop.
Where, according to the fourth aspect of the invention, nucleation is carried out
separately, the concentration of the silver ions is suitably monitored during the
nucleation phase until their concentration falls below a minimum value; a silver
mat collects on the surface of the silicon and the silver-coated silicon product
forms a deposit in the solution during this phase. The silver/silicon deposit can
be separated from the solution either by filtration or decantation, where liquid
is drained away from the solid. As indicated above, the nucleating solution
contains, in addition to silver ions (as nitrate salt), HF at a concentration range
of 0.01 to 5M. Preferably the HF is provided in a concentration range of 0.01 to
4M, more preferably 0.1 to 2M, most preferably 0.1 to 1M and especially
0.5M.
The resulting silver/silicon solid can then be transferred to an etching solution,
which has an HF and nitrate ion concentration falling within the ranges
specified herein with the proviso that the HF concentration of a solution used
for the nucleation step is less than the HF concentration of a solution used for
the etching step, and gently stirred. Alternatively, the etching solution can be
added to the solid silver/silicon deposit formed in the nucleation step. During
the etching step, the HF and N0 3
~ concentrations are carefully monitored and
the N0 3 concentration is maintained within the concentration ranges specified
herein. The end of the etching step is considered to be reached at a point in
time when the HF concentration drops below a minimum value, typically 2-3M
or lower. Alternatively, the etching step can be carried out over a fixed period
of time by maintaining both the HF and N0 3 concentrations within the ranges
specified. In the former case it will be necessary to add extra N0 3 ions to
maintain the concentration of these ions within the range given. In the latter
case it may be necessary to add extra HF as well as extra N0 3 ions to maintain
the levels of both HF and N0 3 within the ranges given.
An etching solution typically comprises HF at a concentration in the range 0.1
to 5M, preferably 0.1 to 4M, more preferably 0.25 to 4M, most preferably 2 to
4M and especially 3 to 4M.
Alternatively and as will be appreciated from the foregoing, because it is
possible to carry out the nucleation step at an HF concentration of greater than
4M, preferably at a concentration in the range 4 to 6M and especially 4.5 to
5.5M, it will be necessary to use solutions having a concentration of HF of
greater than 4M, preferably greater than 5M and especially greater than 6M for
etching. Preferably a solution used for etching will have an HF concentration of
4 to 10M, preferably 5 to 9M, most preferably 6 to 8M and especially 7.5M.
Typically, in accordance with a fourth embodiment of the first aspect of the
invention, the nucleation step is carried out using a treatment solution having
an HF concentration of less than 5M and the etching step is carried out using a
treatment solution having an HF concentration of greater than 5M. It is
especially preferred to carry out the nucleation step using a treatment solution
having an HF concentration of 2M and to carry out the etching step using a
treatment solution having an HF concentration in the range 3 to 10M,
preferably 7.5M. A preferred process according to the fourth embodiment of
the first aspect of the invention provides a nucleating solution having an HF
concentration of 0.5M and an etching solution having an HF concentration of
between 3 and 4M.
In a further preferred approach according to the fourth embodiment of the first
aspect of the invention, the nucleating solution has an HF concentration of 2M
and the etching solution has an HF concentration of 7.5M.
Where the nucleation step employs a mixture of nucleating metal species, the
nucleating species may be provided in the form of separate nucleating
solutions. Separate reaction chambers (baths) will typically be provided for
each nucleating solution.
It will be appreciated that where nucleation and etching are carried out
separately, it may be possible to better control and therefore optimise the
reaction parameters for each of the nucleation and etching steps by controlling
the concentration and composition of each of the nucleating and etching
solutions within concentration ranges falling within those concentration ranges
defined herein above. This can be achieved through the use of separate reaction
chambers or baths or through the use of a reaction chamber having reagent inlet
means via which nucleation and/or etching solutions can be introduced and
outlet means via which the spent nucleation and/or etching solutions can be
removed as required. The use of separate reaction chambers is preferred since
this means that it is possible for the process according to the first aspect of the
invention to be carried out in batches. A batch method can be used to good
effect when processing larger quantities of silicon, since the silicon can be
divided up into a number of portions so that etching of a nucleated portion of
silicon can be carried out at the same time as the etching of a silicon portion
that has not undergone nucleation. It has been found that by using the process
according to the first aspect of the invention in which the HF concentration in
the solution used for nucleation is smaller than the HF concentration in the
solution used for etching, the products formed are characterised by an even
distribution of pillars over the substrate surface and by pillars having a narrow
range of diameters and lengths.
The separation of the nucleation and the etching steps (either through the use of
separate baths or through the provision of a reaction vessel which allows easy
introduction and removal of reaction solutions) means that it is possible to
conduct the nucleation step on a different quantity of silicon material to that
used for etching, for example. For example, it may be possible to divide a
silicon sample up into a number of smaller portions for nucleation and to
recombine all or a number of the nucleated portions for etching. The separation
of the nucleation and the etching step means that it is possible to process the
silicon in batches and to optimise the conditions for both the nucleation and the
etching steps.
A particularly preferred embodiment of the fourth embodiment of the first
aspect of the invention provides a process for processing silicon, which process
comprises separately treating, either simultaneously or sequentially, one or
more portions of silicon with a nucleating solution as defined herein above;
combining the nucleated silicon portions and treating the combined silicon
portions with an etching solution as defined herein above.
As indicted above, in a fifth embodiment of the first aspect of the invention, the
nucleation and etching steps can also be carried out together in a single reaction
chamber. This can be achieved by preparing a treatment solution according to
the first aspect of the invention or according to any of its preferred
embodiments and placing this treatment solution in a container or reaction bath
together with the silicon to be etched, monitoring the concentration of HF and
NO3
' over the course of the treatment process, maintaining the concentration of
NO3
" within the ranges specified herein and terminating the treatment either
when the concentration of HF falls below a predetermined value or by
removing etched silicon from an etching solution in which both the
concentration of HF and NO3 ions has been maintained within the ranges
specified herein after a fixed period of time. Reaction times have been found to
be dependent on parameters such as the quantity and size of the silicon
particles or granules, process conditions such as temperature, pressure and
reagent concentration. Reaction times of between 30 and 600 minutes,
preferably between 30 and 400 minutes and especially between 60 and 300
minutes are typical, although reaction times falling outside these ranges may be
employed. Where the nucleation and etching steps are carried out
simultaneously, the concentration of N0 3 is maintained within the ranges
specified herein above by adding NOj to the treating solution. The
concentration of HF is suitably in the range 0.01 to 5M, preferably 0.1 to 4M,
more preferably 0.25 to 4M, most preferably 2 to 4M and especially 3 to 4M.
The concentration of silver ions is typically in the range 0.002 to 0.2M, for
example 0.01 to 0.15M.
Secondly, a single container or reaction bath may be provided with a fluid inlet
and a fluid outlet via which nucleation and etching solutions may be introduced
into and removed there from. The silicon to be etched may be introduced into
the container or reaction bath before or after the introduction of reagents.
Preferably the nucleating solution is introduced into the reaction chamber
before the silicon to be etched. The treatment of the silicon can be carried out
by mixing the silicon with the nucleating solution in the chamber, monitoring
the concentration of Ag+ in solution and then adding the etching solution to this
mixture when the concentration of silver ions has dropped below a minimum
concentration. Alternatively the spent nucleation solution can be removed from
the container or reaction bath when the concentration of silver ions had
dropped below a minimum value; the etching solution can then be introduced
into the bath. During etching the HF and N0 ~concentrations are carefully
monitored and the N0 3 concentration is maintained within the concentration
ranges specified herein; this is best achieved through addition of N0 3 ions.
The end of the etching step is considered to be reached when the concentration
of HF falls below a minimum value. As indicated above, where the etching step
is separated from the nucleation step the etching solution preferably contains
HF at a concentration in the range 0.1 to 5M, preferably 0.1 to 4M, more
preferably 0.25 to 5M, most preferably 2 to 4M and especially 3 to 4M. An
etching solution containing HF at a concentration of 0.25 to 10M, preferably 2
to 8M, more preferably 3 to 7.5M, most preferably 4 to 7.5M and especially 6
to 7.5M can also be used. An intermediate washing step may be carried out
between the nucleation and etching stages. In a preferred embodiment, the
nucleation solution is removed from the chamber at the end of the nucleation
phase and prior to the introduction of the etching solution.
As indicated above, etching can be carried out in one or more steps. It is
preferable to control one or both of the concentration of HF and/or NO3 during
this step. NO3 ions will be added to an etching solution comprising HF and
NO3 ions to maintain the N0 3 concentration over the etching period. If
desired, additional HF can be added to the etching solution, either in a single
step, in two or more steps or continuously over the etching period to maintain
the concentration of HF within the ranges specified herein.
An advantage of the process of the present invention lies in the fact that it only
requires the use of a small number of ingredients whose concentration can be
easily controlled. In particular it does not require the use of oxidising metal
ions in addition to the silver ions to secure efficient etching of the silicon
surface. This greatly improves the logistics of processing the spent etching
solution and means that the process of the present invention is much simpler,
cheaper and safer to operate than previous processes.
The process of the present invention can be used to fabricate silicon pillars or
fibres from lower purity silicon materials such as silicon powders derived, for
example, from metallurgical grade silicon as well as powders derived from
higher purity silicon wafers or chips. The silicon materials may include coated
and uncoated structures. Coated structures include particles or granules having
a silicon coating applied to a non-silicon substrate as well as particles or
granules having a silicon coating having a first composition applied to a silicon
substrate having a second composition that is different to that of the first
composition. Where the silicon materials include a silicon coating applied to a
non-silicon substrate, the substrate may be an electroactive material, a
conductive but non-electroactive material or an insulator. Examples of
electroactive materials include graphite, hard carbon, tin, aluminium, gallium,
germanium, an electroactive ceramic material, a transition metal oxide, a
chalconide or a structure formed from one or more of these electroactive
materials. Examples of non-electroactive conducting materials include
conductive carbons such as carbon black or conductive polymer materials. For
both coated and uncoated starting materials the silicon can include within its
structure a dopant such as a p-type dopant or an n-type dopant. The inclusion of
dopants typically improves the conductivity of the materials. Examples of ptype
dopants for silicon include B, Al, In, Mg, Zn, Cd and Hg. Examples of ntype
dopants for silicon include P, As, Sb and C.
Using the process according to the first aspect of the invention typically gives a
product in the form of silicon-comprising "pillared particles", i.e. particles
having pillars formed on their surface. Alternatively, where the etched pillars
are totally or partially removed from the granular silicon during the etching
step, the product of the process can include fibres instead of or in addition to
pillared particles, for example. The products of the process of the present
invention can be used in the manufacture of anode material for lithium ion
cells; these materials have been found to be excellent for this application.
Description of the Drawings
Fig. 1 is a schematic diagram showing the components of a battery cell;
Fig. 2 is an electron micrograph of a pillared particle produced according to the
method described in WO 2009/010758.
Fig. 3 is an electron micrograph of a pillared particle produced according to the
method of Example 1 of the present invention.
Fig. 4 is an electron micrograph of fibres produced according to the method of
the invention using a 2.5M HF solution.
Figure 5 is an electron micrograph of a pillared particle produced according to
the method of Example 2 of the present invention.
Figure 6 is an electron micrograph of pillared particles produced according to
the method of the invention using a treatment solution having an HF
concentration of less than 5M for both the nucleation and the etching steps.
Figure 7 is an electron micrograph of pillared particles produced according to
the method of the invention using a treatment solution having an HF
concentration of less than 5M for both the nucleation step and a treating
solution having an HF concentration of greater than 5M for the etching step.
Figure 8 is an electron micrograph of fibres produced according to the method
of the invention using a treatment solution having an HF concentration of less
than 5M for both the nucleation step and a treating solution having an HF
concentration of greater than 5M for the etching step.
Specific Description of preferred embodiments
In the following description, the invention will be described by reference to
etching of granular silicon to form etched silicon particles using silver ions for
the nucleation step. It will be understood from the foregoing that the invention
is not limited to the use of silver ions as the nucleating species and extends to
other metal ions that are able to form a porous layer on the silicon surface upon
nucleation.
It should be understood from the foregoing that the invention is not limited to
the use of NO3 as an oxidant and extends to other oxidants selected from the
group comprising H20 2, 0 2, O , acid, ammonium and alkali metal salts of
C10 , KMnO , Cr2O7
2 , S2O 2 , N0 2 and B30 7
2 , for example.
It is generally believed that the treatment process according to the first aspect
of the invention involves two processes: nucleation and etching. At the start of
the process, the nucleation step dominates until substantially all the nucleating
ions in the solution have been consumed. At this point, the etching step
becomes more dominant and proceeds until substantially all the fluoride ions in
solution have been consumed.
During the nucleation stage, islands of silver are deposited electrolessly on the
silicon granules according to the reaction:
4Ag+ + 4e 4Ag (metal)
Nucleation will generally take up to about 1 minute. Longer nucleation times
(up to 40 minutes) have been used. The nucleating reaction is generally carried
out at a temperature of greater than 0°C. Preferably the nucleating temperature
does not exceed 80°C. Nucleation is suitably carried out at a temperature of
between 15°C and 70°C, preferably 25°C to 50°C and especially 25°C to 40°C.
Nucleation may be carried out in the light or in the dark.
At the beginning of the treatment process according to the first aspect of the
invention, etching occurs preferentially along certain crystal planes and the
silicon is etched into columns. The silicon is etched according to the following
equation:
Si + 6F SiF6
2 + 4e Half-reaction (l)
The electrons generated by half reaction (1) are conducted through the silicon
to the deposited (nucleated) silver where the counter reaction occurs in which
silver ions in the solution are reduced to elemental silver:
4Ag+ + 4e 4Ag (metal) Half-reaction (2)
The elemental silver deposited according to half-reaction (2) forms dendrites,
which extend from and between the initially deposited islands of silver. The
dendrites will interlock with dendrites on the same deposited particle (island)
and on other deposited particles (islands) and so form a mat. The
interconnection of the dendrites speeds up the electrolytic process because
there are more sites where the reduction half reaction (2) can take place and the
charge can be delocalised. Without wishing to be constrained by theory, it is
believed that the nucleated silver mat catalyses half-reaction (1) causing the
silicon material under the nucleated silver islands to be etched away in
preference to silicon material not so covered. This results in the formation of
silicon pillars on the silicon substrate. Some gas will be evolved in the process
and this can cause the mat to float.
Although not essential, the reaction mixture is preferably subjected to gentle
stirring. The mixture can be stirred using a magnetic stirrer or by gently
bubbling gas through the mixture. The rate of stirring must be sufficient to
facilitate the formation of and maintain the integrity of the dendritic silver mat
during the nucleation step and etching step. The rate of stirring will be apparent
to a skilled person and will depend in part on factors such as the silicon loading
and the silver concentration.
The granular or particulate silicon starting material may comprise undoped
silicon, doped silicon of either the p- or n-type or a mixture, such as a siliconaluminium
doped silicon. It is preferred that the silicon includes within its
structure a dopant such as a p-type dopant or an n-type dopant. The inclusion of
dopants typically improves the conductivity of the materials. Examples of ptype
dopants for silicon include B, Al, In, Mg, Zn, Cd and Hg. Examples of ntype
dopants for silicon include P, As, Sb and C. Dopants such as Germanium
and Silver can also be used. We have found that p-doped silicon having 10 19 to
10 carriers/cc works well. Such material may be obtained by grinding doped
silicon, e.g. silicon from the IC industry, and then sieving the ground material
to obtain granules with the desired size.
Alternatively, the granules or particles may be of relatively low purity
metallurgical grade silicon, typically with a silicon purity of 99.4-99.9%, which
is available commercially; metallurgical grade silicon is particularly suitable
because of the relatively high density of defects (compared to silicon wafers
used in the semiconductor industry) and the presence of dopant impurities such
as Al. This leads to a low resistance and hence high conductivity, which is
advantageous when the pillar particles or fibres are used as anode material in
rechargeable cells. Such silicon may be ground and graded as discussed above.
An example of such silicon is "Silgrain™" from Elkem of Norway, which can
be ground and sieved (if necessary) to produce particles. Granules having a
mean particle diameter in the range l to 1.5mm, preferably Impi to 1mm,
more preferably IOmhi to 800mpi may be used. Granules having a diameter in
the range 1 to IOOmih, preferably 3 to IOOmpi, more preferably 10 to 50 mh ,
most preferably 20 to 40m and especially 15 to 25mpi are generally (but not
exclusively) used for making pillared particles. Granules having a mean
diameter in the range 100 to 800m h are generally (but not exclusively) used for
making fibres. The granules may be regular or irregular in cross section.
When making silicon fibres, the granules remaining after the fibres have been
removed can be recycled.
The particles or granules used as starting materials may have a silicon-purity of
90.00% or over by mass, preferably 98.00% or over. Silicon granules or
particles having a silicon-purity in the range 99.0% to 99.99% are especially
preferred. The silicon can be doped with any material for example,
germanium, phosphorous, aluminium, silver, boron and/or zinc
The granules used for etching may be crystalline for example mono- or polycrystalline
with a crystallite size equal to or greater than the required pillar
height. The polycrystalline particle may comprise any number of crystals for
example two or more.
The etching step may be carried out at a temperature of 0°C to 70°C, suitably
between 10 and 50°C, preferably between 15 and 40°C and especially at room
temperature since only very expensive containers will be able to withstand the
highly corrosive HF at temperatures towards the top end of the above range.
For that reason the temperature will generally not exceed 50°C. If necessary,
the reaction mixture may have to be cooled in the course of the process since it
is exothermic.
The reaction mixture may also be light irradiated during the nucleation and
etching step. The intensity and wavelength of the light used will depend on the
nature of the silicon being etched. The reaction material will suitably be
irradiated with a light source having a wavelength in the region of the bandgap
of the silicon material being etched. The use of visible light is preferred.
Reaction containers may be fabricated from or may include light transmitting
materials such as polyethylene. Other suitable materials that can be used in the
fabrication of reaction chambers include fluorocarbon plastics, polypropylene,
lead and platinum. The reaction chambers may be lined with HF-resistant
materials, such as HF-resistant rubbers.
The process should be terminated at a time when the silicon has been etched
sufficiently to provide well-defined pillars of at least lOOnm, preferably at least
500nm. The pillar height is preferably no more than 1mm, more preferably no
more than 500mp . Suitable ranges for the pillar height are 1 to 500m ,
preferably 1 to 300m i, eg 1 to 100 m i and more preferably 1to 40m . The
pillar height for pillared particles will generally be 1 to 5mh , preferably 2 to 4
m h and especially 3 to 4 mhi and when making isolated fibres will be larger,
e.g. 10 to IOOmhi. The optimum duration of the process will depend on the
concentration of the materials in the solution, the conductivity of the silicon,
the temperature and the amount of etching solution used as compared to the
amount of granular silicon being etched. Process times of between 30 and 600
minutes, preferably between 30 and 400 minutes and especially between 60 and
300 minutes have been found to produce silicon fibres of an acceptable quality.
Since the reaction time depends upon factors such as the quantity and size of
the silicon particles or granules used, the reaction temperature and the
concentration of reagents in the treating solution, it will be appreciated that it
will be necessary on occasion to use process times outside those detailed
herein.
Depending upon the reaction conditions employed, the pillars may taper away
from their bases, i.e. where they are attached to the underlying silicon, and the
diameter of the pillars at their bases will generally be of the order of 0.02 to
0.70 mpi , e.g. 0.1 to 0.5m i, for example 0.1 to 0.25 mhi, preferably in the range
0.08 to 0.70mp . The pillars will thus generally have an aspect ratio in the range
5:1 to 100:1, preferably in the range 10:1 to 100:1. The pillars may be
substantially circular in cross-section but they need not be.
Where the granules or particles used as starting material have a principal
diameter in the range 800 mpi to 1.5mm, the etched particles produced by the
process according to the first aspect of the invention typically have a principal
diameter in the range 800 m h to 1.5mm, a core diameter in the range 500 to
800 m and pillar heights in the range 300 to 500 mh . Where the granules or
particles used as starting material have a principal diameter in the range 300 to
800 mh , the etched particles typically have a principle diameter in the range
300 to 800 m i, a core diameter in the range 100 to 700 m h and pillar heights in
the range 50 to 350 mhi. Where the granules or particles used as starting
material have a principal diameter in the range 100 to 300 m , the etched
particles typically have a principal diameter in the range 100 to 300 m , a core
diameter in the range 20 to 100 mih and pillar heights in the range 40 to 100
mhi. Where the granules or particles used as starting material have a principal
diameter in the range 10 to 1 0 mp , the etched particles typically have a
principle diameter in the range 10 to 100 mp , a core diameter in the range 3 to
30 m and pillar heights in the range 2 to 30 m . Pillared particles formed
from granules or particles having a principle diameter of less than IOmih tend to
form particles having a similar overall diameter, core diameters of between one
quarter and one half the diameter of that of the original particle and pillar
heights of between one tenth and one half of the diameter of the original
particle.
A pillar fractional surface density may be used to define the density of the
pillars on a surface or surfaces of the particle. Herein, this is defined as F = P /
[R + P] wherein: F is the pillar surface density; P is the total surface area of the
particle on the surface or surfaces occupied by pillars; and R is the total surface
area of the same surface or surfaces that is unoccupied by pillars. The term
surface can be considered to include planes, crystal faces and sides.
The larger the pillar surface density, the larger the lithium capacity per unit
area of a silicon particle electrode and the larger the amount of harvestable
pillars available to create fibres. A fractional pillar surface density, F, of 5-
80%, more typically 20% to 50% is preferred for pillared particles. For making
fibres, silicon substrates having a fractional surface density of between 40 and
80%, preferably between 40and 60% provide a good yield of silicon fibres. Not
all surfaces of a pillared particle may have pillars. Where there are surfaces
without pillars, the above values for F are calculated for only the surfaces with
pillars. For example, if only one surface of a wafer is etched to form pillars,
only the surface area of that surface is used in the calculation of F.
The rate at which the etching of the silicon materials takes place during the
etching step has been found to be influenced by factors such as the reaction
temperature, the concentration of silicon particles or granules (silicon loading),
the size and surface area of the particles or granules, the HF concentration, the
oxidant concentration and the illumination level. It has been found that a high
HF concentration of HF and/oxidant causes the etching reaction to occur too
quickly, which leads formation of products in which the silicon pillars have
been etched horizontally as well as vertically. If the silicon loading is too high,
the silicon pillars formed are of a poor quality. Additionally if the silicon
surface area is high a high HF concentration must be avoided to prevent the
rate of etching from proceeding too rapidly.
It has been found that for silicon particles or granules having a average
principle diameter of the order of 25m h, pillars and pillared particles of
acceptable quality have been obtained by loading silicon at a level of 15 to
40g/l in a treating solution having an HF concentration of 7.5M. For silicon
particles or granules having an average principle diameter of 12 m h, acceptable
results have been achieved using a silicon loading in the range 15 to 20g/l. A
silicon loading of 7 to lOg/l has been found to be acceptable for silicon
particles having an average principle diameter of 6 m h.
As will be appreciated from the foregoing, nucleation and dendrite growth
require the presence of silver in the solution, but once these stages are
completed, etching requires only the presence of an ion in solution that can be
reduced. This can be silver (half reaction 2) but equally it need not be and,
since silver is expensive, it is preferred to use some other counter reaction. In
WO2007/083 152 the present applicants have suggested the addition of ferric
nitrate to provide ferric ions that can be reduced to ferrous ions in a counter
reaction. However, we have found that the addition of ferric ions to the reaction
mixture adds to the complexity and cost of the process.
WO2007/083 152 also suggests the use of hydrogen ions to provide the counter
reaction but the hydrogen and fluoride ions concatenate in solution, reducing
the availability of hydrogen ions for this purpose.
We have found that the optimum counter reaction is the reduction of nitrate
ions in solution. The reduction of oxygen gas or ozone provides an alternative
counter reaction. The nitrate ion is preferred because it is already present in the
solution since silver will be added in the form of silver nitrate and also because
other anions may precipitate the silver. Although WO2007/083 152 suggests
that nitrate ions be added during the etching step, this is in the form of silver
nitrate or ferric nitrate. The former is expensive and in the latter, the ferric ions
will also be reduced with the disadvantages mentioned above. We therefore add
nitrate to the etching solution as an alkali metal nitrate, ammonium nitrate or
nitric acid, particularly sodium nitrate or ammonium nitrate because these
materials have a high solubility but are also cheaper than ferric nitrate and
have inert cations (Na+ and NH +) that are not detrimental in the solution.
The etching solution is preferably substantially free of iron ions (ferric or
ferrous). By "substantially free" we mean that there is an insufficient
concentration to have a material effect on the process and should generally be
less than 0.05% by weight and less than 5mM, e.g. less than 2mM.
It was a feature of WO2007/083152 that an alcohol should be present in the
nucleation stage and should be present in an amount of 1 to 40%. The process
of WO2007/083 52 was carried out on a chip or wafer and we have found that,
in the context of the present process carried out on silicon granules, the
presence of alcohol is not necessary and its presence complicates the process
since it is another ingredient that must be considered when controlling the
concentrations in the solution. Accordingly, the solution used in the present
invention is, in accordance with one embodiment of the present invention,
substantially free of an alcohol, by which is meant that the amount of any
alcohol is less than the concentration that has a material effect on the process
and may be less than 0.5% by volume.
If the solution is used for both nucleation and etching, the initial concentration
of HF is suitably in the range 0.01 to 5M, preferably 0.25 to 5M, more
preferably 0.1-4M, most preferably 1 to 4M, e.g. 2M to 4M and generally about
2M or 3M HF. Further HF can be added to the reaction mixture in order to
maintain the HF concentration at a predetermined level referred to above or to
increase HF to between 3 and 7.5M, should this HF concentration be required
for etching. The maintenance of a fixed HF concentration may be needed in the
course of the process if a large amount of material is etched compared to the
volume of the solution.
Alternatively, the treatment process according to the first aspect of the
invention may be allowed to continue until the concentration of HF is
insufficient to support further etching of the silicon substrate. By allowing the
HF concentration to drop over the course of the treatment process, handling
and disposal of the waste etchant solution is greatly simplified.
In order to deposit the islands of silver and the dendrites, the concentration of
Ag+ may be in the range 0.002M to 0.2M, e.g. 0.0 1M to 0.15M, generally
0.0 1M to 0.09M, especially 0.07M. The amount of Ag+ ions is preferably
insufficient to participate in the etching of all the silicon in the process but
rather should be limited to an amount sufficient only to form the islands and
dendrites. The concentration of silver ions used will depend in part on the
surface area of the silicon particles being etched as well as the silicon loading
of the solution. Smaller particles having a larger surface area will, in general,
require the use of higher concentrations of silver compared to larger particles
having a smaller surface area. The half reaction that counters the etching half
reaction is then provided by the reduction of nitrate ions. Silver is preferably
not added to the solution after the etching reaction has started.
As indicated, N0 3 may provide a counter reaction to the etching of the silicon
(half reaction (1)) and may be present at a concentration of 0.001 to 0.7M,
preferably 0.003M to 0.7M, e.g. 0.01M to 0.5M, e.g. about 0.3M. The silver
will generally be added to the etching solution in the form of its nitrate salt
since other salts are generally insoluble. This will provide some of the nitrate
ions required and any balance may be made up by adding alkali metal nitrate,
e.g. sodium or potassium nitrate or ammonium nitrate in the course of the
process. The N0 3 ions may be added in one or more steps; further N0 3 may
be added after 35% to 65% of the overall process time.
Although (as discussed above) other oxidants may be added to the solution, the
concentration of the other oxidants used will depend upon their strength.
Stronger oxidants (having a more positive reduction potential relative to
hydrogen) will tend to be employed at a lower concentration.
SiF 2 will be generated in the solution once etching has started.
It will be appreciated that the pH of the solution may change during the course
of the treatment process. This may be because of the generation of additional
hydrogen (H+) ions through the use etchant solutions having the concentrations
of hydrogen fluoride specified herein. In order to maintain the pH of the
reaction mixture, it may be necessary to add a base such as sodium hydroxide
(NaOH) or ammonium hydroxide (NH4OH) to remove the excess hydrogen
ions.
Nitrate ions in the form of nitric acid may also be added during the etching step
to maintain one or both of the solution pH or nitrate concentration, where
necessary.
It may also be necessary to add a base to remove any excess hydrogen ions
generated in solution upon addition of the nitric acid used to remove the
dendritic silver at the end of the etching step.
Apart from water, the solution according to an embodiment of the present
invention may contain no other ingredients. Such a solution would at the start
of the process consist essentially of:
0.01 to 5M HF
0.002 to 0.2M Ag+ ions
0.001 to 0.7M NO3 ions
water, and optionally
SiF 2 ions,
alkali metal or ammonium ions, and
incidental additions and impurities.
It is important to ensure that the amount of solution used relative to the amount
of silicon granules should be sufficient for both nucleation and etching. It has
been found, for example, that the concentration and amount of solution
required for etching the silicon substrate depends upon both the amount and
size of silicon granules used. Smaller granules having a larger surface area tend
to require either the use of an etching solution having a higher concentration of
HF or a larger volume of a fixed HF concentration etching solution. We have
found that where nucleation and etching are carried out simultaneously or in
the same bath, the best results have been obtained by using 1 to lOg, suitably 2
to 8g and preferably 4 to 8g of silicon granules of dimensions 15 to 25 h and
having a BET surface area of approximately 0.636m2/g for every litre of
etching solution having an HF concentration in the range 2 to 3.5M. Where
nucleation is carried out separately to etching it has been found that it is
possible to treat up to 30g/l of silicon granules of dimensions 15 to 25mp and
having a BET surface area of approximately 0.636m /g for every litre of
nucleating solution having an HF concentration of 2M; 60g/l of silicon
granules of dimensions 15 to 25m and having a BET surface area of
approximately 0.636m /g can be etched for every litre of etching solution
having an initial HF concentration of 7.5M. These relative proportions may
need to be adjusted as the quantities are scaled up or down.
Other aspects of the invention provide pillared particles or fibres made by the
process and a composite electrode, especially an anode, containing such
particles or fibres together with a current collector, which may optionally be
made of copper. The composite electrode may be made by preparing a solventbased
slurry containing pillared particles or fibres made by the above process,
coating the slurry onto a current collector and evaporating the solvent to create
a composite film.
The present invention further provides an electrochemical cell, e.g. a
rechargeable cell, containing an electrode as defined above and a cathode that
comprises a lithium-containing compound capable of releasing and reabsorbing
lithium ions as its active material. The cathode is typically prepared by
applying a mixture of a cathode active material, a conductive material and a
binder to a cathode current collector and drying. Examples of cathode active
materials that can be used together with the anode active materials of the
present invention include, but are not limited to, layered compounds such as
lithium cobalt oxide, lithium nickel oxide or compounds substituted with one or
more transition metals such as lithium manganese oxides, lithium copper
oxides and lithium vanadium oxides. Examples of suitable cathode materials
include LiCo0 2, LiCo 0 .99Al 0 .oi0 2 , LiNi0 2, LiMn0 2, LiCoo.5Nio.5O2,
LiCoo.-7Nio.3O2, LiCoo.8Nio.2O2, LiCoo.82 io. 2, LiCoo.8Nio.15Alo.05O2,
LiNi 0 . Co o.3 .3O ,LiNio.8Coo.i5Alo.o5 2 , LiMnxNi Co1-2x 0 2 or LiFePO4 and
LiNio.33Coo.33Mno.34O2. The cathode current collector is generally of a thickness
of between 3 to 500m h. Examples of materials that can be used as the cathode
current collector include aluminium, stainless steel, nickel, titanium and
sintered carbon.
Silicon fibres can be made by detaching the pillars from a product according to
the first aspect of the invention. One or more techniques such as scraping,
agitating (especially by ultrasonic vibration) or chemical etching can be used to
remove the pillars. Alternatively, the fibres can be made by completely or
partially etching away the particle core so that they become detached in the
treating solution. The silicon fibres thereby made are preferably at least 1mpi
long, more preferably at least 3m h long, most preferably at least 5mpi long,
especially at least IOm long. The lengths thereby produced are preferably in
the range of 1-500mh , more preferably I -IOOmpi, most preferably 5-80m ,
especially 10-50m .
The structured particles and fibres of the invention provide a good reversible
reaction of silicon with lithium in a rechargeable cell. In particular by arranging
the particles or fibres in a composite structure, that is a mixture of particles or
fibres, a polymer binder and a conductive additive, or by directly bonding the
particles or fibres to a current collector, the charge/discharge process becomes
reversible and repeatable and good capacity retention is achieved. See, for
example WO 2009/010757 and WO 2009/010759. This good reversibility is
considered by the present inventors to be due to the ability of both the silicon
pillars forming part of the structured silicon particle and the silicon fibres to
absorb the volumetric expansion/contraction associated with lithium
insertion/extraction from the host silicon without the pillars being broken up or
destroyed.
Importantly, the process described in this invention can use a low purity,
metallurgical grade silicon as the feedstock silicon granules and hence reduces
the cost of making silicon particles and fibres for use in electrodes of
rechargeable cells as compared to the prior art use of silicon wafers as
feedstock. As already mentioned, the silicon granules may be predominantly nor
p- type and may be etched on any exposed crystal face. Since the etching
proceeds along crystal planes, the resulting pillars are single crystals. Because
of this structural feature, the pillars will be substantially straight facilitating
length to diameter ratio of greater than 10: 1.
In overview the invention provides a safe and controllable process for making
pillared particles of silicon or silicon fibres that are of especial application for
use in rechargeable lithium ion cells
The invention will now be illustrated by reference to one or more of the
following non-limiting examples. Variations on these examples falling within
the scope of the invention will be apparent to a person skilled in the art. The
silicon based structures prepared according to the process of the present
invention can be used to fabricate devices such as fuel cells, field emitting
diodes, chromatographic materials, solar cells, solar capacitors, filters, sensors
and electrical capacitors.
Example 1 - to obtain pillared particles
The reaction was conducted in a light transmitting polyethylene container with
8 litre volume. Access is provided for introducing ingredients. A stirrer is also
provided. The following reactants were used:
The reaction was conducted at room temperature 15 to 30°C. 21g of AgN0 3 is
mixed with 3 litres 2M HF solution in the reaction chamber. 5.1 gram NaOH
dissolved in 30 ml water may be added if necessary. The resulting solution
contains 66mM AgN0 3.
24 gram sieved Si powder (<25mh ) is added through the hole in the lid of the
container by means of a funnel, and then the mass is gently stirred by hand,
through the hole in the lid using a rod, for 1 minute.
This reaction mixture is allowed to stand for 40 minutes. A "mat" of silicon
plus silver forms on the surface of the etch solution in the first 1-2 minutes.
After 40 minutes, 1 gram NaN0 3 (or 13 gram NH4N0 3) is added. The NaN0 3
or NH4NO3 is dissolved into 50 ml water and then added through the funnel.
The solution is then stirred for about 1 min after the NaN0 or NH4NO3
addition has been completed. The mixture is allowed to stand for a further 250
minutes. Then at 295 minutes from the start of the process, when the etching is
almost complete, the spent etching solution starts to be pumped into a storage
chamber, which takes about 4 - 5 minutes so the total etching time is about 300
minutes.
The mat is now washed with 3-4 litre water three times. The first two washes
are such that the water is in contact for five minutes, while the third wash is a
one minute wash. The wet mat, which is silicon and silver, should be promptly
treated with nitric acid to remove the silver. The etched silicon is further
washed and stored wet. The washing water contains silver and may be set aside
to recover the silver content.
Example 2 - to obtain detached fibres
36 g of AgN0 3 is added to 3 litres of a 2M HF solution.
12 gram Si powder (Elkem Silgrain™ 200-800mih) is added through a funnel at
top of the container and the mass is gently stirred by hand, through the hole in
the lid using a rod, for 1 minute. This reaction mixture is allowed to stand for
60 minutes. The concentration of HF in the etching solution is monitored
during the etching step and further HF is added to the solution to maintain the
concentration of HF at 2M. The "mat" of silicon plus silver forms on the
surface of the etch solution in the first 1-2 minutes.
At the end of the 60 minutes, 52 gram NaN0 3 (or 48 gram NH4N0 3) is added.
The NaNO3 or NH4NO3 is dissolved into 50 ml water and then added through
funnel at top. The mixture is gently stirred for a further 235 minutes. Then at
295 minutes from the start of the process, when the etching is almost
completed, the spent etching solution starts to be pumped into a storage
chamber, which takes about 4-5 minutes, and so the total etching time is about
300 minutes. Then the mat is washed with 3-4 litre water three times. The first
two washes are such that the water is in contact for five minutes, while the third
wash is a one minute wash.
The wet mat, which is composed of silicon and silver, should be promptly
treated with nitric acid for 5-10 min to remove silver. The silicon is further
washed and stored wet. The washing water contains silver and may be set aside
to recover the silver content.
Fibres can be harvested from the resulting particles, with pillars attached, by
ultrasonic vibration by placing the particles in a beaker or any appropriate
container, covering the particles with an inert liquid such as ethanol or water
and subjecting them to ultrasonic agitation. It is found that within several
minutes the liquid is seen to be turbid and it can be seen by electron
microscope examination that at this stage the pillars have been removed from
the particle.
The pillars may be removed from the particle in a two stage process. In the
first stage, the particles are washed several times in water and, if necessary,
dried in a low vacuum system to remove the water. In the second stage, the
particles are agitated in an ultrasonic bath to detach the pillars. These are
suspended in water and then separated using a centrifuge to collect the silicon
fibres.
Fibres prepared using an HF solution of concentration 2.5M are shown in
Figure 4.
Example 3 - Preparation of Silicon-containing Pillared Particles by
nucleating and etching at less than 5M HF
Silicon granules (ELKEM Silgrain HQ J318) having a particle size of less than
25mpi (as determined by sieve) and a surface area as determined by BET
surface area measurement of 0.638m2/g were mixed at a silicon loading of 8g/l
with a treating solution comprising HF at a concentration of 2M and AgNO3
(Johnson-Matthey) at a concentration of 23.5mM. The solution was gently
stirred for 15 to 30 minutes during which time nucleation of silver metal on the
surface of the silicon material was observed.
The nucleated silicon product was removed from the spent nucleation solution
and transferred to an etching bath. Ammonium nitrate (150mM) (Analytically
pure) was added to the solution in the etching bath in four separate portions
over a period of one hour (6g every 15 minutes) and the reaction was allowed
to proceed for a further 3.5 hours at a temperature of up to 40°C until the
etching step was complete (the HF concentration typically falls to 3M over this
period). The total reaction volume was 500ml; a llitre polyethylene reaction
vessel was used.
The product was removed from the reaction solution by filtering and nitric acid
was added thereto to remove the silver mat. The final product was washed with
water and stored under water to prevent the pillars fusing together at their ends.
The pillared particles thus obtained were characterised by a pillar length of
2.5m . Pillared particles prepared in accordance with example 3 are illustrated
in Figure 6.
Example 4 - Preparation of Silicon-containing Pillared Particles by
nucleating using a treatment solution having an HF concentration of less
than 5M and etching using a treatment solution having an HF
concentration of greater than 5M HF
Silicon granules (ELKEM Silgrain HQ J318) having a particle size of less than
5 (as determined by sieve) and a surface area as determined by BET
surface area measurement of 0.638m /g were mixed at a silicon loading of
30g/l with a treating solution comprising HF (Honeywell PURANAL,
semiconductor grade) at a concentration of 2M and AgN0 3 (Johnson-Matthey)
at a concentration of 44mM. The solution was gently stirred for 30 minutes
during which time nucleation of silver metal on the surface of the silicon
material was observed.
The nucleated silicon product was removed from the spent nucleation solution
and transferred to an etching bath. HF (7.5M) was added to the etching bath.
Sodium nitrate (Sigma-Aldrich ACS reagent, > 99.0%) (127.5g) was added to
the reaction chamber in eight portions over a period of .5 to 2 hours. The
reaction mixture was then gently stirred for a further 2.5 to 3 hours at a
temperature of not more than 45°C until the etching step was complete (the HF
concentration typically falls to 3M over this period). The total reaction volume
was 1000ml; a 21itre polyethylene reaction vessel was used.
The product was removed from the reaction solution by filtering and nitric acid
was added thereto to remove the silver mat. The final product was washed with
water and stored under water to prevent the pillars fusing together at their ends.
The pillared particles thus obtained were characterised by a pillar length of 2.5
to 3 pi. Pillared particles prepared in accordance with example 4 are illustrated
in Figure 7.
Example 5 - Preparation of Silicon-containing Fibres by nucleating using
a treatment solution having an HF concentration of less than 5M and
etching using a treatment solution having an HF concentration of greater
than 5M HF
Silicon granules (ELKEM Silgrain HQ 200-800m , Lot no. Breq7223) having
a particle size in the range 200-800mhi (as determined by sieve) were mixed at
a silicon loading of 2g/l with a treating solution comprising HF (Honeywell
PURANAL, semiconductor grade) at a concentration of 2.5M and AgNO3
(Johnson-Matthey) at a concentration of 11.8mM. The solution was gently
stirred for between 15 and 30 minutes during which time nucleation of silver
metal on the surface of the silicon material was observed.
The nucleated silicon product was removed from the spent nucleation solution
and transferred to an etching bath. HF (7.5M) was added to the etching bath.
Ammonium nitrate (Sigma-Aldrich ACS reagent, > 98.0%) (lg, 150mM) was
added to the reaction chamber in four portions over a period of one hour. The
reaction mixture was then gently stirred for a further 30 minutes to one hour at
a temperature of not more than 40°C until the etching step was complete (the
HF concentration typically falls to 3M over this period). The total reaction
volume was 500ml; a 1litre polyethylene reaction vessel was used.
The product was removed from the reaction solution by filtering and nitric acid
was added thereto to remove the silver mat. The final product was washed with
water and stored under water to prevent the pillars fusing together at their ends.
The fibres thus obtained were characterised by a pillar length of 30 to 40mhi.
Pillared particles prepared in accordance with example 5 are illustrated in
Figure 8.
Example 6 - making an anode
The pillared particles or fibres are used as the active material in a composite
anode for lithium-ion electrochemical cells. To fabricate a composite anode,
the pillared particles or fibres are mixed with polyvinylidene difluoride or
another suitable polymer binder, optionally together with other components, for
example, conductive particles, other active materials or fillers, and made into a
slurry with a casting solvent such as n-methyl pyrrolidinone. This slurry can
then be applied or coated onto a metal plate or metal foil or other conducting
substrate for example physically with a blade or in any other appropriate
manner to yield a coated film of the required thickness and the casting solvent
is then evaporated from this film using an appropriate drying system which
may employ elevated temperatures in the range of 50° C to 140°C to leave the
composite film free or substantially from casting solvent. The resulting
composite film has a porous structure in which the mass of silicon-based
pillared particles or fibres is typically between 5 percent and 95 percent. The
composite film preferably has a percentage pore volume of 10-70 percent, more
preferably 20-60%.
Electrodes can also be fabricated using, for example, polyacrylic acid or CMC
instead of polyvinylidene difluoride as the binder.
Fabrication of the lithium-ion battery cell thereafter can be carried out in any
appropriate manner for example following the general structure shown in Fig. 1
but with a silicon-comprising active anode material rather than a graphite
active anode material. For example the silicon particle-based composite anode
layer is covered by the porous spacer 18, the electrolyte added to the final
structure saturating all the available pore volume. The electrolyte addition is
done after placing the electrodes in an appropriate casing and may include
vacuum filling of the anode to ensure the pore volume is filled with the liquid
electrolyte.
Capacity retention is improved as the pillared structure of the silicon pillar
particles or fibres allows for accommodation of the volume expansion
associated with insertion/extraction (charging and discharging) of lithium,
without pulverisation or excessive swelling of the composite.
Large sheets of silicon-based anode can be fabricated and then rolled or
stamped out subsequently as is currently the case in graphite-based anodes for
lithium-ion battery cells meaning that the approach described herein can be
retrofitted with the existing manufacturing capability.

Claims
1. A process for treating silicon comprising the steps of exposing silicon
containing material to a solution comprising:
5 0.01 to 5 HF
0.002 to 0.2M of metal ions capable of nucleating on and forming a porous
layer comprising regions of elemental metal on the silicon surface;
0.001 to 0.7M of an oxidant selected from the group O2, 0 3, H20 2, the acid,
ammonium or alkali metal salt of NO3 , S20 2 , N0 2
~, B4O7
2 and C10 or a
0 mixture thereof.
2. A process according to claim 1, wherein the metal ions are selected from the
group silver, gold, platinum, copper, nickel, lead, cobalt, cadmium, chromium,
zinc and tin.
5
3. A process according to claim 2, wherein the metal ion is a silver ion (Ag+).
4. A process according to claim 1 or claim 2, wherein the oxidant is selected
from the group 0 2, 0 3, H20 2 and the acid, ammonium or alkali metal salt of
0 NO3
5. A process according to claim 4, wherein the oxidant is N0 3 .
6. A process according to any one of the preceding claims, which further
5 comprises the step of adding further oxidant to the treating solution to maintain
the concentration of oxidant within the above ranges.
7. A process according to any one of the preceding claims, which comprises the
steps of exposing silicon powder to a solution comprising
0 0.01 to 5 HF
2033440V1
0.002 to 0.2M Ag+ ions
0.001 to 0.7M of N0 3 ions;
and adding further NO ions to maintain the N0 3 concentration ranges within
the above ranges, wherein the NO3 ions are added in the form of an alkali
5 metal nitrate salt, ammonium nitrate or nitric acid, to thereby form silicon
pillars on the treated surfaces.
8. A process according to any one of the preceding claims which comprises the
steps of exposing silicon to a solution comprising:
0 0.25 to 5M HF
0.01 to 0.15M Ag+ ions
0.02 to 0.7M NO3
~ ions and
adding further N0 3 ions to maintain the N0 3 concentration ranges within the
above ranges, wherein the N0 3 ions are added in the form of an alkali metal
5 nitrate salt or ammonium nitrate, to thereby form silicon pillars on the treated
surfaces; and separating the treated silicon from the solution.
9. A process according to any one of the preceding claims, wherein the solution
contains less than 0.05% by weight of iron ions (ferric or ferrous).
0
10. A process according to any one of the preceding claims, wherein the
solution contains less than 0.5% by volume of alcohol.
11. A process according to any one of the preceding claims, wherein the silicon
5 has a purity of at least 90.00% by mass.
12. A process according to any one of the preceding claims wherein the silicon
comprises undoped silicon, doped silicon of either the p-type or n-type or a
mixture thereof.
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13. A process according to any one of the preceding claims, wherein the silicon
is in granular form, the granules having a particle size in the range 1mih to
1.5mm.
5 14. A process according to claim 13, wherein the silicon granules have a
particle diameter in the range IOmih to 800mpi.
15. A process according to claim 13 or claim 14, wherein the pillars formed on
a treated surface have a diameter at in the range 0.02 to 0.70mpi.
0
16. A process according to claim 15 wherein the pillars have a diameter in the
range 0.08 to 0.7m .
17. A process according to any one of claims 13 to 16, wherein the pillars
formed on a treated surface have an aspect ratio in the range 5:1 to 100:1.
18. A process according to claim 17 wherein the pillars have an aspect ratio in
the range 10:1 to 100:1
0 19. A process according to any one of the preceding claims, which is conducted
at a temperature of 0°C to 70°C.
20. A process according to any one of the preceding claims, wherein the
concentration of N0 3 ions is maintained by adding N0 3 ions to the solution in
5 one or more steps.
21. A process according to any one of claims 1 to 20, wherein the concentration
of N0 3
' is maintained by continuous addition of N0 3 ions to the solution.
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22. A process according to any one of the preceding claims, which includes the
step of adjusting the composition by adding a base selected from NaOH and/or
NH OH or nitric acid.
23. A process according to any one of the preceding claims, which further
comprises the step of detaching the pillars from the resulting etched silicon to
form silicon fibres.
24. A process according to claim 23, wherein the length of the fibres is at least
I , preferably in the range 5mh to 80m i
25. A process according to any one of the preceding claims, wherein the silicon
comprises granules having a principal diameter in the range I i to 1.5mm and
the product of the process comprises particles having pillars formed on their
surface, the pillars having a height in the range 1 to 500 h.
26. A process according to any one of the preceding claims, wherein the
concentration of HF in the treating solution is in the range 0.25 to 4M.
27. A process according to any one of the preceding claims, which comprises a
nucleation step and an etching step.
28. A process according to claim 27, in which the nucleation step is carried out
separately to the etching step.
29. A process according to claim 27 or claim 28, in which the nucleation step is
carried out in a separate bath.
30. A process according to any one of claims 27 or 28, in which the etching
step is carried out in the same bath as the nucleation step.
31. A process according to any one of claims 27 to 30, in which the nucleation
step is carried out at an HF concentration in the range 0.1 to 2M.
5 32. A process according to any one of claims 27 to 30, in which the etching
step is carried out at an HF concentration in the range 2 to 4M.
33. A process according to any one of claims 27 to 30, in which the etching
step is carried out at an HF concentration in the range 0.1 to 10M.
0
34. A process according to any one of claims 32 or 33 in which further HF is
added to the etching solution in one or more discrete steps or continuously over
the duration of the etching period to maintain the concentration of HF within
the specified concentration ranges.
5
35. A process according to any one of claims 27 to 34 in which the
concentration of HF in the treatment solution used for the nucleation step is
less than the concentration of HF in the treatment solution used for the etching
step.
0
36. A process according to claim 35, wherein the concentration of HF in the
treatment solution used for the nucleation step is less than or equal to 5M and
the concentration of HF in the treatment solution used for the etching step is
greater than or equal to 5M.
5
37. The process according to any one of the preceding claims, wherein the
silver ions are used at a concentration of 0.01M to 0.1 5M, preferably 0.10M.
38. The process according to any one of the preceding claims, wherein NO3 is
0 present in an amount of 0.2 to 0.5, e.g. about 0.4M.
20 334 1
39. The process according to any one of claims 27 to 36, which comprises the
steps of:
(a) exposing silicon-containing material to a solution comprising
0.01 to 5M HF
0.002 to 0.2 Ag+ ions,
and optionally NO3 ions to form a silver-coated silicon product;
and
(b)mixing the silver-coated silicon product of step (a) with HF to give a
solution comprising 0.1 to 10M HF, with the proviso that the concentration of
HF in the solution at the end of step (b) is greater than the concentration of HF
in the solution of step (a);
(c) adding N0 3 to the solution formed in (b) to maintain the concentration of
N0 3 within the concentration range 0.003 to 0.7M, wherein the N0 ion is in
the form of an alkali metal nitrate salt, ammonium nitrate or nitric acid.
40. A process according to claim 39, in which step (a) is carried out in the same
reaction chamber to steps (b) and (c).
41. A process according to claim 40, in which step (a) is carried out in a
separate reaction chamber to steps (b) and (c).
42. A process according to claim 41, wherein the silver-silicon product formed
in step (a) is separated from the solution used in step (a) and thereafter added to
a solution comprising 0.1 to 10M HF and 0.003 to 0.7M N0 3
~.
43. A process according to any one of the preceding claims wherein the silicon
material is provided at a silicon loading of between 2 and 60g/l.
44. An electrode containing etched particles or fibres made by the process as
defined in any of claims 1 to 43 as one of its active materials
45. An electrode according to claim 44, in which the particles or fibres are
5 provided in the form of a composite material.
46 An electrode according to claim 44 or claim 45, which comprises a copper
current collector.
0 47. An electrode according to any one of claims 44 to 46, in which the
electrode is an anode.
48. A cell containing an electrode as claimed in any one of claims 44 to 47.
5 49. A cell according to claim 48, which comprises an anode and a cathode
formed from a lithium-containing compound capable of releasing and
reabsorbing lithium ions as its active material.
50. A cell according to claim 48 or 49, which is an electrochemical cell.
0
51. A device comprising a cell as defined in any one of claims 48 to 50