DESCRIPTION
TITLE OF THE INVENTION:
ETCHING SOLUTION AND METHOD FOR PROCESSING SURFACE OF
SILICON SUBSTRATE
TECHNICAL FIELD
[0001]
The present invention relates to an etching solution for forming
pyramid-like depressions and protrusions on the surface of a silicon
substrate and a method for processing the surface of a silicon substrate using
the etching solution,
BACKGROUND ART
[0002]
Fine pyramid-like depressions and protrusions, which are referred to
as a textured structure, are formed on the surface of a silicon substrate used
in a crystal silicon solar cell. By this textured structure, radiated light
undergoes multiple reflection on the surface to have an increased
opportunity of being incident into the silicon substrate, and is absorbed
efficiently into the inside of the solar cell.
[0003]
A silicon substrate having a textured structure is produced by
etching a silicon substrate obtained by slicing a silicon ingot with a wire saw
or the like.
The etching of the silicon substrate can be carried out each by wet
etching using an alkaline etching solution. This etching proceeds by

reaction of the following reaction formulas (l), (2), (3) and the like in the case
of being within a sodium hydroxide solution.
Si + 2NaOH + H2O → Na2SiO3 + 2H2 reaction formula (1)
2Si + 2NaOH + 3H2O → Na2Si2O5 + 4H2 reaction formula (2)
3Si + 4NaOH + 4H2O → Na4Si3O8 + 6H2 reaction formula (3)
[0004]
Typically, in order to form a textured structure on the surface of a
silicon substrate,, anisotropic etching is carried out by using an etching
solution with controlled etching speed.
The purpose of etching lies in removing a damaged layer in which
distortions or damages caused by a slicing process that are present on the
surface of a silicon substrate after being sliced which is a source material
and in forming a textured structure. Removal of the damaged layer and
formation of the textured structure may be carried out using the same
solution, or alternatively, in view of productivity, an etching process in two
stages using different etching solutions for removal of the damaged layer and
formation of the texture may be carried out.
The etching process in two stages is a processing method in which
etching for removal of the damaged layer is carried out using an alkaline
etching solution having a comparatively larger etching speed and
subsequently anisotropic etching is carried out using an etching solution
with controlled etching speed as texture etching.
In any of the methods, formation of the textured structure on the
surface of the silicon substrate is based on the following mechanism.
The etching speed on the silicon substrate by an aqueous alkaline

solution is the largest on the (100) plane of silicon and is the smallest on the
(111) plane. For this reason, when the speed of texture etching is inhibited
by adding to the aqueous alkaline solution a specific additive (which may
hereafter be referred to as "etching inhibitor") that can reduce the etching
speed, a crystal plane that is more liable to be etched such as the (100) plane
of silicon is preferentially etched, and the (111) plane having a smaller
etching speed remains on the surface. This (111) plane has an inclination of
about 54 degrees, relative to the (100) plane and therefore, pyramid-like
depressions and protrusions constituted of the (111) plane and equivalent
planes thereof are formed at the final stage of the process.
[0005]
For etching to remove the damaged layer, a general etching solution
made of a strong alkali chemical liquid can be used; however, in texture
etching, the etching speed must be controlled by adding the aforementioned
etching inhibitor and controlling various conditions such as the solution
temperature.
[0006]
Typically, as an etching solution for texture etching, an etching
solution obtained by adding isopropyl alcohol (which may hereafter be
referred to as "IPA") as an etching inhibitor to an aqueous solution of sodium
hydroxide (NaOH) is used. A method of heating this etching solution to
about 60 to 80°C and immersing a silicon substrate of the (100) plane for 10
to 30 minutes has been adopted (for example, see the patent document 1 and
the non-patent document l).
Further, there is disclosed a method of performing texture etching by

using an etching solution obtained by adding IPA as an etching inhibitor to
an aqueous solution of potassium hydroxide (KOH) after removing the
damaged layer by heating a liquid obtained by diluting 45% potassium
hydroxide (KOH) with water at 1:1 to 85°C and immersing the silicon
substrate for 30 minutes (for example, see the non-patent document 2).
[0007]
On the other hand, IPA has a high volatility, so that IPA
corresponding to the amount of volatilization must be added into the texture
etching solution at appropriate times, thereby raising a problem of increase
in the cost of etching caused by increase in the amount of IPA consumption.
Furthermore, use of a large amount of IPA having a high volatility is not
desirable also from the viewpoint of safety and environment protection.
Even if an apparatus for collecting the volatilized IPA is attached, there are
'problems of increase in the cost of fabricating the etching processing
equipment and increase in the cost of equipment operation.
[0008]
For this reason, development of a texture etching solution containing
an etching inhibitor serving as a substitute for IPA is carried out. For
example, the patent documents 2 and 3 disclose a texture etching solution to
which aliphatic carboxylic acid or a salt thereof has been added. Also, the
patent document 4 discloses a texture etching solution containing an
inorganic salt.
Also, the patent document 5 discloses an etching solution containing
a compound having a benzene ring as an etching inhibitor.
Also, the patent document 6 discloses an etching solution containing

alkyl sulfonate having 12 carbon atoms (C12H25-O-SO3Na).
PRIOR ART DOCUMENTS
PATENT DOCUMENTS
[0009]
Patent document 1: Japanese Patent Application Laid-open (JP_A)
No. 61-96772
Patent document 2: Japanese Patent Application Laid-open (JP_A)
No. 2002-57139
Patent document 3: International Publication No. 06/046601
Pamphlet
Patent document 4: Japanese Patent Application Laid-open (JP'A)
No. 2000-183378
Patent document 5: Japanese Patent Application Laid-open (JP-A)
No. 2007-258656
Patent document 6: Chinese Patent No. CN10157089
NON-PATENT DOCUMENTS
[0010]
Non-Patent document 1: "Uniform Pyramid Formation on
Alkaline-etched Polished Monocrystalline (100) Silicon Wafers", Progress in
Photovoltaics, Vol.4, 435-438 (1996)
Non-Patent document 2- "EXPERIMENTAL OPTIMIZATION OF
AN ANISOTROPIC ETCHING PROCESS FOR RANDOM
TEXTURIZATION OF SILICON SOLAR CELLS", CONFERENCE
RECORD OF THE IEEE PHOTOVOLTAIC SPECIALISTS CONFERENCE,
P303-308(1991)

DISCLOSURE OF THE INVENTION
PROBLEM TO BE SOLVED BY THE INVENTION
[0011]
According to the method of using aliphatic carboxylic acid disclosed
in the patent documents 2 and 3, the source material cost is high and, when
neutralization is carried out during the waste liquid processing, the aliphatic
carboxylic acid is liberated, thereby raising a problem of inviting the need for
separately providing an oil-water separation step and generating a specific
odor. Also, there are problems in that the waste liquid processing requires
costs, and this may also lead to rise in the production costs.
Also, according to the method of the patent document 4, expensive
Na2CO3 must be used in order to inhibit the impurity concentration of heavy
metals or salts to a needed level. Also, the salt concentration within the
system becomes high, and the amount of dissolution of silicate produced as a
byproduct in etching the silicon decreases, so that the texture etching
solution must be exchanged frequently.
[0012]
Also, the etching inhibitor containing a compound having a benzene
ring of the patent document 5 is inferior in toxicity and biodegradability as
compared with compounds having a simple chain structure, and hence is not
preferable from the viewpoint of wastewater treatment and environmental
protection.
[0013]
Also, although the patent document 6 discloses addition of alkyl
sulfonate having 12 carbon atoms (C12H25-O-SO3Na), the ester moiety

gradually undergoes hydrolysis in a strong alkali environment as described
also in the patent document 2, whereby an alcohol having 12 carbon atoms
and sodium hydrogensulfate are produced, so that the inherent function as a
surfactant cannot be expected for a long term, and a fine textured structure
cannot be formed with a good reproducibility. Due to these reasons, it is not
preferable to industrially use a surfactant having an ester structure.
[0014]
As shown above, with respect to conventional etching solutions, as it
stands now, an etching solution being capable of forming a fine textured
structure on a silicon substrate with a good reproducibility and having a
performance that is industrially satisfactory in view of waste liquid
processing and working environment as well has not yet been found out.
Under such circumstances, an object of the present invention is to
provide an etching solution capable of forming a silicon substrate having a
fine textured structure in a steady manner without requiring the use of any
conventional etching inhibitor such as IPA.
MEANS FOR SOLVING THE PROBLEM
[0015]
As a result of repeated eager researches in order to solve the
aforementioned problems, the present inventors have found out that the
following inventions meet the aforementioned object, thereby arriving at the
. present invention.
[0016]
In other words, the present invention pertains to the following
inventions.

<1> An etching solution in which a silicon substrate is to be
immersed to form pyramid-like depressions and protrusions on the surface of
the substrate, and which comprises at least one component selected from
compound (A) represented by the following general formula (l) and an alkali
salt thereof and an alkali hydroxide (B) at a concentration of 0.1 wt% or more
and 30 wt% or less,
[chemical formula l]
R-X (1)
(in the formula, R represents one of an alkyl group, an alkenyl group, and an
alkynyl group each having 4 or more and 15 or less carbon atoms; and X
represents a sulfonic acid group.)
<2> The etching solution according to the aforesaid <1>, wherein R
in the general formula (1) in the compound (A) is an alkyl group having 5 or
more and 12 or less carbon atoms," and the concentration of the alkali
hydroxide (B) is 0.5 wt% or more and 20 wt% or less.
<3> The etching solution according to the aforesaid <1> or <2>,
wherein the concentration of the compound (A) is within a range of 0.0001
wt% or more and 10 wt% or less.
<4> The etching solution according to any one of the aforesaid <1> to
<3>, wherein the alkali hydroxide (B) is sodium hydroxide and/or potassium
hydroxide.
<5> The etching solution according to any one of the aforesaid <1> to
<4>, further containing a silicate compound (C).
<6> The etching solution according to the aforesaid <5>, wherein the
silicate compound (C) is silicate of sodium or potassium.

<7> The etching solution according to the aforesaid <5> or <6>,
wherein the concentration of the silicate compound (C) is 10 wt% or less as
an Si-onverted concentration.
<8> A method for processing the surface of a silicon substrate
comprising a step of immersing a silicon substrate into an etching solution as
described in any one of the aforesaid <1> to <7>, so as to form pyramid-like
depressions and protrusions on the surface of the substrate.
EFFECTS OF THE INVENTION
[0017]
When an etching solution of the present invention is used, a fine
textured structure suitable for light confinement for use in a solar cell can be
formed on the surface of a silicon substrate with a good reproducibility.
BRIEF EXPLANATION OF DRAWINGS
[0018]
FIG. 1 is an electron microscope image of the surface of a silicon
substrate after etching is carried out using an etching solution of Example 1.
FIG. 2 is an electron microscope photograph of the surface of a silicon
substrate after etching is carried out using an etching solution of Example 2.
FIG. 3 is an electron microscope photograph of the surface of a silicon
substrate after etching is carried out using an etching solution of Example 3.
FIG. 4 is an electron microscope photograph of the surface of a silicon
substrate after etching is carried out using an etching solution of Example 4.
FIG. 5 is an electron microscope photograph of the surface of a silicon
substrate after etching is carried out using an etching solution of Example 5.
FIG. 6 is an electron microscope photograph of the surface of a silicon

substrate after etching is carried out using an etching solution of Example 6.
FIG. 7 is an electron microscope photograph of the surface of a silicon
substrate after etching is carried out using an etching solution of Example 7.
FIG. 8 is an electron microscope photograph of the surface of a silicon
substrate after etching is carried out using an etching solution of Example 9.
FIG. 9 is an electron microscope photograph of the surface of a silicon
substrate after etching is carried out using an etching solution of
Comparative Example 1.
FIG. 10 is an electron microscope photograph of the surface of a
silicon substrate after etching is carried out using an etching solution of
Comparative Example 2.
FIG. 11 is an electron microscope photograph of the surface of a
silicon substrate after etching is carried out using an etching solution of
Comparative Example 3.
FIG. 12 is an electron microscope photograph of the surface of a
silicon substrate after etching is carried out using an etching solution of
Reference Example 1.
MODE FOR CARRYING OUT THE INVENTION
[0019]
Hereafter, the present invention will be described in detail.
The present invention relates to an etching solution in which a
silicon wafer is to be immersed to form pyramid-like depressions and
protrusions (which may be hereafter referred to as "textured structure") on
the surface of the substrate, and which comprises at least one component
selected from compound (A) represented by the following general formula (1)

and an alkali salt thereof and an alkali hydroxide (B) at a concentration of
0.1 wt% or more and 30 wt% or less,
[chemical formula 2]
R-X (1)
(In the formula, R represents one of an alkyl group, an alkenyl group, and an
alkynyl group each having 4 or more and 15 or less carbon atoms; and X
represents a sulfonic acid group.)
[0020]
In the present invention, the "silicon substrates" include
single-crystal silicon substrates and polycrystalline silicon substrates. The
etching solution of the present invention is suitable for etching a
single-crystal silicon substrate, in particular, a single-crystal silicon
substrate having a (100) plane on the surface.
[0021]
The compound (A) and the alkali salt thereof have an advantage of
exhibiting an etching inhibition effect equivalent to or more than that of IPA
which is a conventional etching inhibitor and also having a wide applicable
concentration range as will be described later. For this reason, by using the
etching solution of the present invention, the size and shape of the
pyramid-like depressions and protrusions on the surface of the silicon
substrate can be controlled to be within a suitable range.
The compound (A) is a compound in which R in the general formula
(1) is one of an alkyl group, an alkenyl group, and an alkynyl group each
having 4 or more and 15 or less carbon atoms. For example, specifically,
butyl(C:4)sulfonic acid, pentyl(C:5)sulfonic acid, hexyl(C:6)sulfonic acid,

heptyl(C:7)sulfonic acid, octyl(C:8)sulfonic acid, nonyl(C:9)sulfonic acid,
decyl(C: 10)sulfonic acid, undecyl(C:11)sulfonic acid, dodecyl(C:12)sulfonic
acid, tridecyl(C:13)sulfonic acid, tetradecyl(C:14)sulfonic acid, and
pentadecane(C:15)sulfonic acid as compounds having an alkyl group
structure;
butene(C:4)sulfonic acid, pentene(C:5)sulfonic acid,
hexene(C:6)sulfonic acid, heptene(C:7)sulfonic acid, octene(C:8)sulfonic acid,
nonene(C:9)sulfonic acid, decene(C:10)sulfonic acid, undecene(C:11)sulfonic
acid, dodecene(C:12)sulfonic acid, tridecene(C:13)sulfonic acid,
tetradecene(C:14)sulfonic acid, andpentadecene(C:15)sulfonic acid as
compounds having an alkenyl group structure;
butyne(C:4)sulfonic acid, pentyne(C:5)sulfonic acid,
hexyne(C:6)sulfonic acid, heptyne(C:7)sulfonic acid, octyne(C:8)sulfonic acid,
nonyne(C:9)sulfonic acid, decyne(C:10)sulfonic acid, undecyne(C:11l)sulfonic
acid, dodecyne(C:12)sulfonic acid, tridecyne(C:13)sulfonic acid,
tetradecyne(C:14)sulfonic acid, and pentadecyne(C:15)sulfonic acid as
compounds having an alkynyl group structure; and others can be raised as
examples.
[0022]
Here, as the alkali component in the alkali salt of the compound (A),
Group I elements and Group II elements can be used. Among these, lithium
hydroxide, sodium hydroxide, and potassium hydroxide in particular are
suitable because they can be easily obtained and are excellent also in view of
costs.
[0023]

The compound (A) is suitably a compound in which R in the general
formula (1) is an alkyl group having 5 or more and 12 or less carbon atoms.
Specifically, pentyl(C:5)sulfonic acid, hexyl(C:6)sulfonic acid,
heptyl(C:7)sulfonic acid, octyl(C:8)sulfonic acid, nonyl(C:9)sulfonic acid,
decyl(C:10)sulfonic acid, undecyl(C:11)sulfonic acid, and
dodecyl(C:12)sulfonic acid can be raised as examples.
Among these, particularly from the viewpoint of being capable of
obtaining a uniform textured structure, a compound in which R is an alkyl
group having 6 or more and 10 or less carbon atoms is preferable.
Specifically, they are hexyl(C:6)sulfonic acid, heptyl(C:7)sulfonic acid,
octyl(C:8)sulfonic acid, nonyl(C:9)sulfonic acid, and decyl(C:10)sulfonic acid.
[0024]
The concentration of the compound (A) is selected within a range of
an industrially effective etching speed such that a fine textured structure
can be formed on the surface of a silicon substrate, and is preferably 0.0001
wt% or more and 10 wt% or less, more preferably 0.0005 wt% or more and 10
wt% or less, still more preferably 0.001 wt% or more and 5 wt% or less.
Within the above range, a fine textured structure can be formed on
the surface of the substrate by anisotropic etching of the surface of the
substrate.
When the concentration of the compound (A) is less than 0.0001 wt%,
there is a fear that the effect of inhibiting the etching may become
insufficient. Also, the concentration is too low, so that the management of
the concentration within the etching solution is difficult, making it difficult
to produce a silicon substrate having a fine textured structure with a good

reproducibility. On the other hand, when the concentration is more than 10
wt%, the effect of inhibiting the etching becomes too strong, so that it is not
preferable because it requires a long period of time and also the chemical
agent costs, the number of times for washing with water, and the waste
liquid processing costs increase.
[0025]
As the alkali hydroxide (B) used in the present invention, hydroxide
of a Group I element and hydroxide of a Group II element can be used. For
example, lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium
hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH),
beryllium hydroxide (Be(OH) 2), magnesium hydroxide (Mg(OH) 2), calcium
hydroxide (Ca(OH) 2), strontium hydroxide (Sr(OH) 2), barium hydroxide
(Ba(OH) 2), ammonium hydroxide (NH4OH), and the like can be raised as
examples, and these can be used either singly or as a mixture of two or more
kinds. Among these, lithium hydroxide, sodium hydroxide, and potassium
hydroxide in particular are suitable because they can be easily obtained and
are excellent also in view of costs. Also, these alkali hydroxides can be used
by being mixed in an arbitrary ratio.
[0026]
In the etching solution of the present invention, the concentration of
the alkali hydroxide (B) in the etching solution is essentially 0.1 wt% or more
and 30 wt% or less, preferably 0.5 wt% or more and 20 wt% or less.
Within this range, the etching proceeds suitably, and a fine textured
structure can be formed on the surface of a silicon substrate. When the
alkali concentration is lower than 0.1 wt%, the etching speed is not

sufficient, whereas when the concentration is higher than 30 wt%, the
etching speed becomes considerably fast, making it difficult to form a
texture.
[0027]
Here, in the etching solution of the present invention, a silicate
compound (C) can be contained in addition to the compound (A) and the
alkali hydroxide (B).
As the silicate compound (C), specifically, lithium orthosilicate
(Li4SiO4-nH2O), lithium metasilicate (Li2SiO3-nH2O), lithium pyrosilicate
(Li6Si2O7-nH2O), lithium metadisilicate (Li2Si2O5.nH2O), lithium
metatrisilicate (Li4Si3O8.nH2O), sodium orthosilicate (Na4SiO4.nH2O),
sodium metasilicate (Na2SiO3.nH2O), sodium pyrosilicate (Na6Si2O7.nH2O),
sodium metadisilicate (Na2Si2O5.nH2O), sodium metatrisilicate
(Na4Si3O8.nH2O), potassium orthosilicate (K4SiO4.nH2O), potassium
metasilicate (Na2SiO3.nH2O), potassium pyrosilicate (K6Si2O7.nH2O),
potassium metadisilicate (K2Si2O5.nH2O), and potassium metatrisilicate
(K4Si3O8.nH2O) can be raised as examples.
With respect to these silicate compounds (C), the compound itself
may be added into the etching solution for use, or alternatively, a silicate
compound obtained as a reaction product by etching a silicon material such
as a silicon wafer, a silicon ingot, or a silicon cut powder, or silicon dioxide
directly into the alkali hydroxide (B) may be used as the silicate compound
(C).
The silicate compound (C) has a function of inhibiting the etching of
silicon, so that, by dosing the silicate compound (C) to the etching solution of

the present invention, the function of the compound (A) inhibiting the
etching can be aided, whereby control of the etching speed suitable for
forming the textured structure can be carried out more appropriately.
When the concentration of the silicate compound (C) is too high, the
etching speed considerably decreases, and the liquid viscosity increases and
moreover deposition of the silicate compound (C) are liable to occur, whereby
a normal textured structure cannot be formed on the surface of the
substrate, making it difficult to use it as a substrate for a solar cell. For
this reason, the silicate concentration in the etching solution is suitably
within a range of 10 wt% or less as an Si-converted concentration. Here,
the "Si-converted concentration" means a concentration as converted in
terms of silicon (Si) atoms contained in the silicate.
Here, the silicate compound (C) is produced also as a byproduct at
the time of etching the silicon substrate for a solar cell, so that, by repeated
etching operations, the concentration of the silicate compound (C) in the
etching solution increases in accordance with the number of processing the
silicon substrate. At this time, when the concentration of the silicate
compound (C) in the etching solution exceeds 10 wt% as an Si-converted
concentration, it is preferable to dilute the solution by replenishing it with
other components such as water or to exchange the solutions.
[0028]
As described above, the etching solution of the present invention
contains the compound (A), the alkali hydroxide (B), and the silicate
compound (C) within the above concentration ranges (including a case in
which the silicate compound (C) is not contained), and each concentration

can be suitably set within a range that can form a normal textured structure
on the intended surface of a silicon substrate for a solar cell.
[0029]
Here, the etching solution of the present invention may contain
components other than the compound (A), the alkali hydroxide (B), and the
silicate compound (C) as other components within a range that does not
deteriorate the objects and effects of the present invention.
As such components, a buffering agent, a pH adjusting agent, a
viscosity adjusting agent, a surface tension adjusting agent, and the like can
be raised as examples.
[0030]
The etching solution of the present invention can be obtained by
dissolving the compound (A) and the alkali hydroxide (B) described above,
and the optional silicate compound (C) in accordance with the needs into
water serving as a solvent by a conventional method. Here, the
temperature for producing the etching solution is 0°C or higher and 100°C or
lower, preferably 20°C or higher and 40QC or lower, and typically room
temperature.
Here, water serving as a solvent of the etching solution of the present
invention is not particularly limited as long as a normal textured structure
can be formed; however, water from which impurities have been removed is
preferable, and typically ion exchange water or distilled water is suitably
used. Specifically, ion exchange water or distilled water having an electric
conductivity of 1 mS/cm or lower (in particular, 100 u-S/cm or lower) as
measured at 25°C is suitable.

[0031]
Hereafter, a method of forming a textured structure on a silicon
substrate by using the etching solution of the present invention will be
described.
[0032]
As the silicon substrate, a single-crystal or polycrystalline silicon
substrate made by any production method may be used; however, a
single-crystal silicon substrate is preferable, and in particular a
single-crystal silicon substrate in which the crystal orientation of the surface
is (100) is preferable. This is due to the following reason. As described
above, because the etching of the silicon substrate by an aqueous alkali
solution is anisotropic etching, a silicon substrate in which the plane
direction of the surface is (100) forms a fine textured structure and one
having a low reflectivity can be obtained, so that the energy conversion
efficiency when the substrate is made into a cell will be high.
[0033]
With respect to the etching solution of the present-invention, the
etching method is not particularly limited, so that a fine textured structure
can be formed on the surface of a silicon substrate by a process such as
immersing the silicon substrate for a predetermined period of time using the
etching solution that has been heated and held at a predetermined
temperature.
[0034]
The temperature for using the etching solution is not particularly
limited; however, the etching solution can be used in a temperature range of

0°C or higher and 100°C or lower, and a range of 80°C or higher and 100°C or
lower is preferable from the viewpoint of etching efficiency. The etching
time is not particularly limited, either; however, it is typically 1 minute or
more and 120 minutes or less (suitably 20 minutes or more and 40 minutes
or less).
[0035]
A silicon substrate having a fine textured structure on the surface of
the silicon substrate can be obtained by a method of processing the surface of
the silicon substrate using the above-described etching solution of the
present invention.
EXAMPLES
[0036]
Hereafter, the present invention will be described in more detail by
way of Examples; however, the present invention is not limited to the
following Examples as long as the gist thereof is not altered.
[0037]
(1) Preparation of etching solution
The composition of the prepared etching solutions is shown in Table
1.
. With respect to the etching solutions of Examples 1, 2, 4 to 6, 8, and
9, first a predetermined amount of NaOH (alkali hydroxide (B)) was
dissolved into water at room temperature, and thereafter a single-crystal
silicon substrate was immersed and dissolved while being heated at 90°C so
as to produce a silicate compound (C). For each of the etching solutions, the
etching was repeated until the Si-converted concentration in the solution

became the concentration shown in Table 1, and thereafter the solution was
cooled to room temperature. Subsequently, a sodium salt of the compound
(A) shown in Table 1 was added so as to attain the concentration shown in
Table 1 and mixed until the solution became homogeneous, whereby each of
the etching solutions was fabricated. Here, the amount of dissolved Si was
determined by decrease in the weight before and after the etching of the
silicon substrate. Also, the Si concentration in the etching solution in which
Si had been dissolved was measured by ICP optical emission spectrometry,
where the obtained Si concentration showed a good conformity to the value
calculated from the aforesaid weights before and after the etching of the
silicon substrate.
Here, in Table 1, the concentration of NaOH in the etching solution is
a value calculated by assuming the following conditions as a premise for
convenience's sake.
Namely, the mode of the silicate compound (C) obtained by the
etching was assumed to be "Na2Si2O5" produced by the above"described
reaction shown in the reaction formula (2), and a value obtained by
subtracting the amount of NaOH consumed by the reaction shown in the
reaction formula (2) from the amount of NaOH initially introduced was
regarded as the NaOH concentration in the etching solution.
The etching solutions of Examples 3 and 7 and Comparative
Example 1 that do not contain the silicate compound (C) were fabricated by
adding a sodium salt of the compound (A) shown in Table 1 so as to attain a
concentration shown in Table 1 into a solution obtained by dissolving NaOH
(alkali hydroxide (B)) at a concentration shown in Table 1 into water at room

temperature, and stirring until the sodium salt was completely dissolved.
The etching solution of Comparative Example 2 that does not contain
the compound (A) and the silicate compound (C) was fabricated by dissolving
NaOH (alkali hydroxide (B)) at a concentration shown in Table 1 into water
at room temperature.
The etching solution of Comparative Example 3 that does not contain
the compound (A) was fabricated by heating to 90° C a solution obtained by
dissolving a predetermined amount of NaOH (alkali hydroxide (B)) into
water at room temperature, so as to dissolve the silicon substrate to attain
an Si-converted concentration shown in Table 1 to produce the silicate
compound (C).
The etching solution of Reference Example 1 was fabricated by using
conventional isopropyl alcohol (IPA) instead of the compound (A) as an
etching inhibitor and adding NaOH (alkali hydroxide (B)) and IPA into water
at room temperature so as to attain a composition shown in Table 1.
The etching solution of Reference Example 2 was fabricated by using
IPA instead of the compound (A) as an etching inhibitor, heating to 90° C a
solution obtained by dissolving NaOH (alkali hydroxide (B)) into water at
room temperature so as to dissolve the silicon substrate to attain an
Si-converted concentration shown in Table 1 to produce the silicate
compound (C), and thereafter adding a predetermined amount of IPA.


(2) Etching of silicon substrate
Table 2 shows processing conditions for forming a textured structure
and results such as properties of a silicon substrate for a solar cell obtained
in accordance therewith.
(Example 1, Reference Example l)
By using a single-crystal silicon substrate (surface crystal plane:
(100) plane) sliced by cutting process on a P'type single-crystal silicon ingot
and having a size of 50 x 50 mm and a thickness of about 180 fam, immersion
into an etching solution having a composition shown in Table 1 was carried
out so as to perform texture etching under the conditions shown in Table 2.
(Examples 2 to 7, Comparative Examples 1 to 3)
Immersion into an etching solution having a composition shown in
Table 1 was carried out so as to perform texture etching under the conditions
shown in Table 2 in the same manner as in Example 1 except that the

substrate was immersed for about 15 minutes into a 25-wt% sodium
hydroxide solution heated to 80° C so as to remove the deposit and the
process_damaged layer on the surface of the silicon substrate and thereafter
wash with water.
(Example 8)
Immersion into an etching solution having a composition shown in
Table 1 was carried out so as to perform texture etching under the conditions
shown in Table 2 in the same manner as in Example 1 except that the
substrate was immersed for about 10 minutes into a 48~wt% sodium
hydroxide solution heated to 80°C so as to remove the adherent substance
and the process "denatured layer on the surface of the silicon substrate and
thereafter wash with water.
(Example 9)
Immersion into an etching solution having a composition shown in
Table 1 was carried out so as to perform texture etching under the conditions
shown in Table 2 in the same manner as in Example 1 except that a silicon
substrate having a size of 156 x 156 mm was used.
(Reference Example 2)
Immersion, into an etching solution having a composition shown in
Table 1 was carried out so as to perform texture etching under the conditions
shown in Table 2 in the same manner as in Example 9 except that the
substrate was immersed for about 2 minutes into a 3.5_wt% sodium
hydroxide solution heated to 80°C so as to remove the adherent substance
and the process-denatured layer on the surface of the silicon substrate and
thereafter wash with water.

Here, the etching amount in Table 2 is an etching thickness per one
side obtained by measuring the weight of the silicon substrate before and
after the texture etching and calculating from the weight difference thereof,
and the etching rate denotes the etching speed obtained by dividing the
aforesaid etching amount by the etching time.
[0040]
(3) Evaluation of silicon substrate after etching
On the silicon substrate after the texture etching, evaluation of the
outer appearance by eye inspection, observation by an electron microscope,
measurement of surface reflectivity, and measurement of conversion
efficiency were carried out. Here, for the observation by an electron
microscope, a scanning-type electron microscope (JSM-6510, manufactured
by Japan Electron Optics Laboratory Co., Ltd.) was used. For the
measurement of surface reflectivity, an UV7VIS/NIR spectrophotometer
(UV-3150, manufactured by Shimadzu Corporation) was used.
The evaluation of the outer appearance and the result of reflectivity
at a wavelength of 600 nm of each of the silicon substrates are shown in
Table 2, and the electron microscope photographs are shown in FIGS. 1 to
12. Here, the standard for evaluation of the outer appearance by eye
inspection is as follows.
O" the whole surface of the substrate is uniformly etched.
A: the etching uniformity as the whole surface of the substrate is
high, though few spots or unevennesses are present.
x: spots or unevennesses are recognized.
[0041]

Also, regarding the silicon substrates on which texture etching was
carried out using the etching solutions of Example 9 and Reference Example
2, a result of measuring the conversion efficiency after fabricating a solar cell
is shown together in Table 2. Here, the solar cell used for the measurement
was fabricated by the following procedure.
With respect to each of the silicon substrates, an n+ layer was formed
on the surface of the substrate by using phosphorous oxychloride (POCI3) as
a dopant in a diffusion furnace. Subsequently, after the end surface of the
substrate was etched using a corrosive gas excited by plasma so as to
perform PN separation, PSG on the surface of the substrate was removed by
using hydrofluoric acid, and a silicon nitride film was formed to a thickness
of 90 nm by CVD on the surface that would become a photoreception surface.
Finally, a comb_shaped grid electrode was formed using a silver paste on the
surface that would become the photoreception surface, and a back surface
electrode was formed on the back surface of the photoreception surface by
printing and applying an aluminum paste or aluminum-silver paste and
calcine the resultant at 840° C, whereby a solar cell was obtained.


The uniformity of the outer appearance of the silicon substrate that
had been etched using the etching solutions of Examples 1 to 8 was
equivalent to or more than that of the case (Reference Example l) of the
conventional etching solution using IPA. Further, by electron microscope
observation, it was confirmed that a fine textured structure had been formed
on the surface of these silicon substrates. Also, the reflectivity of each had a
sufficient value enabling use as a solar cell.
Furthermore, the conversion efficiency of the silicon substrate that
had been etched using the etching solution of Example 9 as a solar cell was,
as a result, more excellent as compared with the case (Reference Example 2)
of the conventional etching solution using IPA.
On the other hand, regarding the etching solution of Comparative
Example 1 in which sodium dodecylbenzenesulfonate was used as the

sodium salt of the compound (A), the etching speed was extremely slow, and
the outer appearance of the substrate after the etching showed a noticable
white unevenness. Also, regarding Comparative Examples 2 and 3 in which
the compound (A) had not been added, the substrate had an outer
appearance that was close to a mirror surface, and a fine textured structure
was not confirmed even by electron microscope observation.
INDUSTRIAL APPLICABILITY
[0044]
According to the present invention, fine depressions and protrusions
can be formed on the surface of a silicon substrate, whereby a higher
efficiency of a solar cell using the silicon substrate can be realized, and also
reduction of the load imposed upon the environment in view of discharged
gas and waste water processing and reduction of the costs can be made, so
that it is industrially promising.

CLAIMS
1. An etching solution in which a silicon substrate is to be immersed to
form pyramid-like depressions and protrusions on the surface of the
substrate, and which comprises at least one component selected from
compound (A) represented by the following general formula (1) and an alkali
salt thereof and an alkali hydroxide (B) at a concentration of 0.1 wt% or more
and 30 wt% or less.
[chemical formula 1]
R-X (1)
(In the formula, R represents one of an alkyl group, an alkenyl group, and an
alkynyl group each having 4 or more and 15 or less carbon atoms; and X
represents a sulfonic acid group.)
2. The etching solution according to claim 1, wherein R in the general
formula (1) in the compound (A) is an alkyl group having 5 or more and 12 or
less carbon atoms; and the concentration of the alkali hydroxide (B) is 0.5
wt% or more and 20 wt% or less.
3. The etching solution according to claim 1 or 2, wherein the
concentration of the compound (A) is within a range of 0.0001 wt% or more
and 10 wt% or less.
4. The etching solution according to any one of claims 1 to 3, wherein
the alkali hydroxide (B) is sodium hydroxide and/or potassium hydroxide.
5. The etching solution according to any one of claims 1 to 4, further
comprising a silicate compound (C).
6. The etching solution according to claim 5, wherein the silicate
compound (C) is silicate of sodium or potassium.

7. The etching solution according to claim 5 or 6, wherein the
concentration of the silicate compound (C) is 10 wt% or less as an-
Sixonverted concentration.
8. A method for processing the surface of a silicon substrate comprising
a step of immersing a silicon substrate into an etching solution as claimed in
any one of claims 1 to 7, so as to form pyramid-like depressions and
protrusions on the surface of the substrate.