Field of the Invention
The present invention relates to a chemical mechanical
polishing pad and a chemical mechanical polishing method.
Description of the Prior Art
In the manufacture of a semiconductor device, chemical
mechanical polishing (generally abbreviated as CMP) is now often used as a polishing
technique capable of forming an extremely flat surface for a silicon substrate or
a silicon substrate having wirings and electrodes thereon. Chemical mechanical polishing
is a technique for polishing by letting an aqueous dispersion for chemical mechanical
polishing (aqueous dispersion containing abrasive grains dispersed therein) flow
down over the surface of a chemical mechanical polishing pad while the polishing
pad and the surface to be polished are brought into slide contact with each other.
It is known that the polishing result is greatly affected by the shape and properties
of the chemical mechanical polishing pad in this chemical mechanical polishing.
A wide variety of chemical mechanical polishing pads have been proposed up till
now.
For example,
JP-A 8-500622
and
JP-A 2000-34416
investigate materials constituting the chemical mechanical polishing pad.
It is known that the polishing rate and the surface state of the polished product
can be improved by forming grooves in the surface (polishing surface) of the chemical
mechanical polishing pad, and many studies have been made on the design of grooves
(refer to
JP-A 11-70463
,
JP-A 8-216029
and
JP-A 2004-507077
, for example).
Out of these,
JP-A 2004-507077
makes a detailed investigation into the relationship between the density
of grooves in the polishing surface and polishing efficiency. According to this
publication, concentrically circular grooves serve to trap an aqueous dispersion
for chemical mechanical polishing which is introduced into the center of the pad
at the time of polishing and moved toward the periphery of the pad by centrifugal
force, and the appropriate value of the density of grooves depends on the characteristic
properties of the material constituting the surface to be polished and the size
of the pad. That is, when an oxide insulating material or tungsten in which a mechanical
factor is predominant is used as the object to be polished in chemical mechanical
polishing, the density of grooves is preferably low and when copper or aluminum
in which a chemical factor is predominant is used as the object to be polished,
the density of grooves is preferably high. A larger pad preferably has a higher
density of grooves. Meanwhile, it is acknowledged in the above publication that
the amount of polishing of the surface to be polished becomes nonuniform only when
the density of grooves is made uniform over the entire surface of the pad. It is
proposed that the density of grooves in an area of the polishing surface of the
pad corresponding to the tracks of a portion where a higher polishing rate is desired
of the surface to be polished should be made lower than that in the other area so
as to make uniform the entire polishing rate for the surface to be polished. This
shows that there is a trade-off relationship between a demand for the improvement
of the supply of the aqueous dispersion for chemical mechanical polishing to the
interface between the surface to be polished and the polishing surface of the pad
(a demand for increasing the density of grooves) and a demand for the improvement
of the contact area between the surface to be polished and the polishing surface
of the pad (a demand for reducing the density of grooves).
JP-A 11-70463
proposes that the width, pitch, depth or shape (circular grooves and meandering
grooves) of grooves should be changed for each area of the polishing surface of
the polishing pad to improve the polishing uniformity of the surface to be polished.
The above publication is also aimed to balance between the supply of the aqueous
dispersion to the interface between the polishing surface and the surface to be
polished and the contact area between the polishing surface and the surface to be
polished. However, the above publication presents some groove design ideas conceivable
from the above concept and does not give any specific guide to find which groove
pattern is actually useful in the real production scene.
Meanwhile, in the current situation where the cost competition
of semiconductor products is becoming keener and keener, the reduction of the amount
of the aqueous dispersion for chemical mechanical polishing to be supplied for chemical
mechanical polishing is one of the effective means of cutting costs. However, there
is unknown a prior art which investigates the design of grooves so as to supply
the aqueous dispersion to the entire surface of the polishing surface of the pad
efficiently and achieve a high polishing rate and the high uniformity of the polished
surface even when the amount of the aqueous dispersion for chemical mechanical polishing
is made small.
Summary of the Invention
It is an object of the present invention which has been
made in view of the above situation to provide a chemical mechanical polishing pad
which has a high polishing rate and excellent in-plane uniformity in the amount
of polishing of the surface to be polished even when the amount of an aqueous dispersion
for chemical mechanical polishing is made small as well as a chemical mechanical
polishing method.
According to the present invention, firstly, the above
object of the present invention is attained by a chemical mechanical polishing pad
having a polishing surface and a non-polishing surface on the opposite side, wherein
the polishing surface has at least two groups of grooves;
- (i) a group of first grooves intersect a single virtual straight line extending
from the center toward the periphery of the polishing surface, do not intersect
one another and have a land ratio represented by the following equation (1) of 6
to 30:
(P is the distance between adjacent intersections between the virtual straight line
and the first grooves, and W is the width of the first grooves); and
- (ii) a group of second grooves extend from the center portion toward the peripheral
portion of the polishing surface, intersect the first grooves, consist of second
grooves which are in contact with one another in the area of the center portion
and second grooves which are not in contact with any other second grooves in the
area of the center portion, and do not intersect one another.
Secondly, the above object of the present invention is
attained by a chemical mechanical polishing pad having a polishing surface and a
non-polishing surface on the opposite side, wherein
the polishing surface has one first groove and a group of second grooves:
- (i) the first groove is one spiral groove which expands gradually from the center
portion toward the peripheral portion of the polishing surface and has a land ratio
represented by the following equation (2) of 6 to 30:
(P' is the distance between adjacent intersections between a single virtual straight
line extending from the center toward the periphery of the polishing pad and the
first groove, and W' is the width of the first groove); and
- (ii) the group of second grooves extend from the center portion toward the peripheral
portion of the polishing surface, intersect the first groove, consist of second
grooves which are in contact with one another in the area of the center portion
and second grooves which are not in contact with any other second grooves in the
area of the center portion, and do not intersect one another.
Thirdly, the above object of the present invention is attained
by a method of chemically mechanically polishing an object to be polished by using
any one of the above chemical mechanical polishing pads.
According to the present invention, there are provided
a chemical mechanical polishing pad which has a high polishing rate and excellent
in-plane uniformity in the amount of polishing of the surface to be polished even
when the amount of an aqueous dispersion for chemical mechanical polishing is made
small and a chemical mechanical polishing method using the polishing pad.
Brief Description of the Drawings
- Fig. 1 is a schematic diagram showing an example of the configuration of the
grooves of the chemical mechanical polishing pad of the present invention;
- Fig. 2 is a schematic diagram showing another example of the configuration of
the grooves of the chemical mechanical polishing pad of the present invention;
- Fig. 3 is a schematic diagram showing still another example of the configuration
of the grooves of the chemical mechanical polishing pad of the present invention;
- Fig. 4 is a schematic diagram showing a further example of the configuration
of the grooves of the chemical mechanical polishing pad of the present invention;
- Fig. 5 is a schematic diagram showing a still further example of the configuration
of the grooves of the chemical mechanical polishing pad of the present invention;
Explanation of reference numerals
- 1: chemical mechanical polishing pad
- 2: second groove
- 3: first groove
Best Mode For the Embodiments of the Invention
The first chemical mechanical polishing pad (may be referred
to as "first polishing pad" hereinafter) of the present invention has a polishing
surface and a non-polishing surface on the opposite side, wherein the above polishing
surface has at least two groups of grooves:
- (i) a group of first grooves intersect a single virtual straight light extending
from the center toward the periphery of the polishing surface, do not intersect
one another and have a land ratio represented by the following equation (1) of 6
to 30:
(P is the distance between adjacent intersections between the virtual straight line
and the first grooves, and W is the width of the first grooves); and
- (ii) a group of second grooves extend from the center portion toward the peripheral
portion of the polishing surface, intersect the first grooves, consist of second
grooves which are in contact with one another in the area of the center portion
and second grooves which are not in contact with any other second grooves in the
area of the center portion, and do not intersect one another.
Although the first grooves formed in the polishing surface
are not limited to a particular shape, they may be, for example, two or more spiral
grooves which expand gradually from the center portion toward the peripheral portion
of the polishing surface, or a plurality of annular or polygonal grooves which do
not intersect one another and are arranged concentrically or eccentrically. The
annular grooves may be circular or elliptic, and the polygonal grooves may be tetragonal,
pentagonal, etc.
The first grooves do not intersect one another.
The first grooves are formed in the polishing surface in
such a manner that they intersect a single virtual straight line extending from
the center portion toward the peripheral portion of the polishing surface a plurality
of times. For example, when the grooves are annular and the number of the annular
grooves is 2, the number of intersections is 2, when the number of the annular grooves
is 3, the number of intersections is 3, and when the number of the annular grooves
is "n", the number of intersections is "n". When the grooves are polygonal, the
same can be said. When there are two spiral grooves, based on the condition that
one turn is 360°, the number of intersections is 2 before the second turn,
3 after the start of the second turn, (2n-2) before the "n"-th turn and (2n-1) after
the start of the "n"-th turn.
When the first grooves are annular or polygonal, they are
arranged not to intersect one another and may be arranged concentrically or eccentrically
but preferably concentrically. A polishing pad having grooves which are arranged
concentrically is superior in the above functions to other polishing pads. The annular
grooves are preferably circular grooves, more preferably circular grooves concentric
with one another. When the circular grooves are concentric with one another, they
are much superior in the above functions and easily formed.
The sectional form in the width direction, that is, the
normal direction of the grooves is not particularly limited. It may be, for example,
polygonal with three or more sides including flat sides and a bottom side, U-shaped
or V-shaped. The polygonal grooves may be such as tetragonal, pentagonal.
The first grooves have a land ratio represented by the
following equation (1) of 6 to 30.
(P is the distance between adjacent intersections between the above virtual straight
line and the first grooves (may be referred to as "pitch" hereinafter), and W is
the width of the first grooves)
The land ratio represented by the above equation (1) is
preferably 6 to 20, more preferably 6 to 15.
The width (W) of the first grooves is preferably 0.1 mm
or more, more preferably 0 .1 to 5 . 0 mm, much more preferably 0.1 to 1.0 mm, particularly
preferably 0.1 to 0.375 mm, ideally 0.1 to 0.35 mm. When the width (W) of the first
grooves is 0.375 mm or less, particularly 0.35 mm or less, the effect of the present
invention is exhibited most effectively. The pitch (P) of the first grooves is preferably
0.6 mm or more, more preferably 1.0 to 30 mm, much more preferably 1.5 to 10 mm,
particularly preferably 3.8 to 10 mm. When the pitch of the first grooves is 3.8
mm or more, the effect of the present invention is exhibited most effectively. The
depth of the first grooves is preferably 0.1 mm or more, more preferably 0.1 to
2.5 mm, much more preferably 0.2 to 2.0 mm. Due to the above first grooves, there
can be easily manufactured a chemical mechanical polishing pad which has a high
polishing rate and excellent in-plane uniformity in the amount of polishing of the
surface to be polished even when the amount of the aqueous dispersion for chemical
mechanical polishing is made small.
The surface roughness (Ra) of the inner wall of each of
the first grooves is preferably 20 µm or less, more preferably 0.05 to 15 µm,
much more preferably 0.05 to 10 µm. A scratch which may be produced on the
polished surface in the chemical mechanical polishing step can be prevented more
effectively by setting this surface roughness to 20 µm or less.
The above surface roughness (Ra) is defined by the following
equation (3):
(N is the number of measurement points, Z is the height of a roughness profile,
and Zav is the average height of the roughness profile)
The above second grooves consist of a plurality of grooves
extending from the center portion toward the peripheral portion of the polishing
surface. The expression "center portion" as used herein means an area surrounded
by a circle having a radius of 50 mm from the center of gravity on the surface of
the chemical mechanical polishing pad as the center thereof. The second grooves
may extend from any point within this "center portion" toward the peripheral portion
and may be linear, arcuate or a combination thereof.
The second grooves may or may not reach the peripheral
end. Preferably, at least one of them reaches the peripheral end. For example, the
second grooves may consist of a plurality of linear grooves extending from the center
portion toward the peripheral portion and at least one of them may reach the side
surface of the pad, or the second grooves may consist of a plurality of linear grooves
extending from the center portion toward the peripheral portion and a plurality
of linear grooves extending from a halfway portion between the center portion and
the peripheral portion toward the peripheral portion and at least one of them may
reach the peripheral end of the pad. Further, the second grooves may consist of
pairs of parallel linear grooves.
The second grooves consist of second grooves which are
in contact with one another in the area of the center portion and second grooves
which are not in contact with any other second grooves in the area of the center
portion. The second grooves which are not in contact with any other second grooves
in the area of the center portion are existent between adjacent second grooves which
are in contact with one another in the area of the center portion. The second grooves
do not intersect one another even when they are in contact with other second grooves.
Preferably, the total number of the second grooves is 6
to 96, the number of the second grooves which are in contact with one another is
2 to 32, and the number of the second grooves which not in contact with any other
second grooves is 4 to 64. More preferably, the total number of the second grooves
is 6 to 48, the number of the second grooves which are in contact with one another
is 2 to 16, and the number of the second grooves which are not in contact with any
other second grooves is 4 to 32 . Most preferably, the total number of the second
grooves is 6 to 36, the number of the second grooves which are in contact with one
another is 2 to 4, and the number of the second grooves which are not in contact
with any other second grooves is 4 to 32.
Out of the second grooves, the number of the second grooves
which are not in contact with any other second grooves in the area of the center
portion is preferably larger than the number of the second grooves which are in
contact with one another in the area of the center portion. The same number of second
grooves which are not in contact with any other second grooves are preferably existent
between every adjacent pair of the second grooves which are in contact with one
another.
When all the second grooves extend from the center portion
toward the peripheral portion, the second grooves which are not in contact with
any other second grooves in the area of the center portion preferably start from
positions 10 to 50 mm away from the center of the pad and extend toward the peripheral
portion from there, more preferably start from positions 20 to 50 mm from the center
of the pad and extend toward the peripheral portion from there. The second grooves
which are in contact with one another in the area of the center portion preferably
start from the center of the pad and extend toward the peripheral portion.
Meanwhile, when the second grooves consist of a plurality
of linear grooves extending from the center portion toward the peripheral portion
and a plurality of linear grooves extending from a halfway portion between the center
portion and the peripheral portion, the grooves which start from a halfway portion
between the center portion and the peripheral portion start from points which are
existent on a virtual straight line connecting the center and the periphery of the
pad and preferably 20 to 80 % of the distance from the center to the periphery of
the pad, more preferably 40 to 60 % of the distance from the center to the periphery
of the pad. Also in this case, the plurality of linear grooves extending from the
center portion toward the peripheral portion consist of second grooves which are
not in contact with any other second grooves in the area of the center portion and
second grooves which are in contact with one another in the area of the center portion.
The preferred configuration of the second grooves starting from the center portion
is the same as the configuration of second grooves all of which extend from the
center portion toward the peripheral portion.
The width of the second grooves is preferably 0.1 to 5.0
mm, more preferably 0.1 to 4.0 mm, much more preferably 0.2 to 3.0 mm. The depth
of the second grooves is the same as the depth of the first grooves. The preferred
range of the surface roughness (Ra) of the inner wall of each of the second grooves
is the same as that of the above surface roughness (Ra) of the inner wall of each
of the first grooves.
The second grooves are preferably spaced apart from one
another as equally as possible on the surface of the chemical mechanical polishing
pad.
The second chemical mechanical polishing pad of the present
invention (may be referred to as "second polishing pad" hereinafter) has a single
spiral groove which expands gradually from the center portion toward the peripheral
portion of the polishing surface in place of the first grooves of the above first
polishing pad.
The number of turns of the first spiral groove may be 20
to 400, preferably 20 to 300, more preferably 20 to 200. 360° corresponds to
one turn.
The first groove of the second polishing pad has a land
ratio represented by the following equation (2) of 6 to 30.
(P' is the distance between adjacent intersections between a single virtual straight
line extending from the center toward the periphery of the polishing surface and
the first groove (may be referred to as "pitch" hereinafter), and W' is the width
of the first groove.)
The land ratio represented by the above equation (2) is
preferably 6 to 20, more preferably 6 to 15.
The width W', pitch P' and depth of the first grooves of
the second polishing pad are the same as the width W, pitch P and depth of the first
grooves of the above first polishing pad. The preferred range of the surface roughness
(Ra) of the inner wall of the first groove of the second polishing pad is the same
as that of the surface roughness (Ra) of the inner wall of each of the first grooves
of the above first polishing pad. As for what is not described of the second polishing
pad, it should be understood that what has been described of the first polishing
pad can be applied to the second polishing pad directly or with modifications obvious
to a person having ordinary skill in the art.
The chemical mechanical polishing pad of the present invention
has the above specific grooves on the polishing surface and may have a groove, grooves
or other recessed portion having a desired shape on the non-polishing surface. When
the chemical mechanical polishing pad has such a groove, grooves or other recessed
portion, the surface state of the polished surface can be further improved. As for
the shape of the grooves on the non-polishing surface, they may include a plurality
of concentrically circular grooves, a plurality of concentrically elliptic grooves,
a plurality of polygonal grooves with the same center of gravity, two or more spiral
grooves, a plurality of grooves extending from the center portion toward the peripheral
portion of the pad, or a plurality of linear grooves forming a triangle lattice,
square lattice or hexagonal lattice. As for the shape of the groove on the non-polishing
pad, it may be, for example, one spiral groove. As for the shape of the other recessed
portion on the non-polishing surface, it consists of a circle and the inside surrounded
by the circle, or a polygon and the inside surrounded by the polygon.
The groove, grooves or other recessed portion on the non-polishing
surface preferably does not reach the peripheral end of the pad.
The chemical mechanical polishing pad preferably has a
recessed portion consisting of a circle and the inside surrounded by the circle,
or a polygon and the inside surrounded by the polygon at the center of the non-polishing
surface. The expression "at the center" is a concept including a case where the
center of gravity of the recessed portion matches the center of gravity of the non-polishing
surface in a mathematically strict sense and also a case where the center of gravity
of the non-polishing surface of the pad is located within the area of the above
recessed portion.
The shape of the chemical mechanical polishing pad of the
present invention is not particularly limited but may be disk-like or polygonal
column-like. It may be suitably selected according to the polishing machine which
is used in combination with the chemical mechanical polishing pad of the present
invention.
For example, when the chemical mechanical polishing pad
of the present invention has a disk-like shape, the opposite circular top surface
and circular bottom surface become the polishing surface and the non-polishing surface,
respectively.
The size of the chemical mechanical polishing pad is not
particularly limited. For example, a disk-like chemical mechanical polishing pad
has a diameter of 150 to 1,200 mm, particularly preferably 500 to 800 mm and a thickness
of 0.5 to 5.0 mm, preferably 1.0 to 3 . 0 mm, particularly preferably 1.5 to 3.0
mm.
The chemical mechanical polishing pad of the present invention
may have a light transmitting area which optically communicates from the polishing
surface to the non-polishing surface. When the pad having such a light transmitting
area is set in a chemical mechanical polishing machine having an optical polishing
end-point detector, the polishing end point can be detected optically. The plane
shape of the light transmitting area is not particularly limited and may be circular,
elliptic, fan-shaped or polygonal (square or rectangular) . The position of the
light transmitting area should be a position corresponding to the position of the
optical polishing end-point detector of the chemical mechanical polishing machine
having the chemical mechanical polishing pad of the present invention. The number
of light transmitting areas may be one or more. When more than one light transmitting
area is formed, their positions are not particularly limited if they satisfy the
above position relationship.
Any method may be employed to form the light transmitting
area. For example, the area having light transmitting properties of the pad is composed
of a light transmitting member. When the pad is made of a material having a certain
level of light transmission, a recessed portion is formed at a position corresponding
to the area which should have light transmission properties of the non-polishing
surface of the pad and the area is made thin to ensure light transmission properties
required for the detection of the polishing end point. In the latter method, the
light transmitting area can serve as the recessed portion for improving the above
surface state of the polished surface.
Examples of the configuration of the grooves of the above
chemical mechanical polishing pad will be described with reference to the accompanying
drawings.
In Figs. 1 to 5, the number of the first grooves is about
10. These figures are schematic and it should be understood that the number of the
first grooves calculated from the diameter of the polishing surface of the pad and
the above pitch is preferred. Figs. 1 to 5 show examples of the first polishing
pad and it should be understood that these figures also show examples of the second
polishing pad in which the first grooves of the illustrated first polishing pad
are replaced by a single spiral groove.
In Fig. 1, the pad 1 has second grooves which are 32 linear
grooves 2 and first grooves which are 10 concentrically circular grooves 3 different
from one another in diameter. 4 out of the 32 linear grooves start from the center
and are in contact with one another whereas the other 28 linear grooves start from
a portion slightly away from the center toward the periphery (it can be judged from
the fact the these linear grooves intersect the smallest circular groove out of
the first grooves that this portion is the center portion) and are not in contact
with any other second grooves. In the pad of Fig. 1, 7 second grooves which are
not in contact with any other second grooves in the area of the center portion are
existent between every adjacent pair of the 4 second grooves which are in contact
with one another in the area of the center portion. All of the 32 linear grooves
of the pad of Fig. 1 reach the peripheral end of the pad.
In Fig. 2, the pad 1 has second grooves which are 64 linear
grooves 2 and first grooves which are 10 concentrically circular grooves 3 different
from one another in diameter. 8 out of the 64 linear grooves start from the center
and are in contact with one another whereas the other 56 linear grooves start from
a portion slightly away from the center toward the periphery and are not in contact
with any other second grooves. In the pad of Fig. 2, 7 second grooves which are
not in contact with any other second grooves in the area of the center portion are
existent between every adjacent pair of the 8 second grooves which are in contact
with one another in the area of the center portion. All of the 64 linear grooves
of the pad of Fig. 2 reach the peripheral end of the pad.
In Fig. 3, the pad 1 has 16 second grooves 2 which extend
from the center portion toward the peripheral portion. 4 out of the 16 grooves start
from the center and are in contact with one another whereas the other 12 grooves
start from a portion slightly away from the center toward the periphery and are
not in contact with any other second grooves. The 16 grooves curve to the left halfway
from the center toward the periphery as shown in the figure but extend almost linearly
excluding the curved portion. In the pad of Fig. 3, 3 second grooves which are not
in contact with any other second grooves in the area of the center portion are existent
between every adjacent pair of the 4 second grooves which are in contact with one
another in the area of the center portion. In the pad of Fig. 3, all of the 16 linear
grooves reach the peripheral end of the pad as well.
In Fig. 4, the pad has 32 linear grooves starting from
a halfway portion between the center portion and the peripheral portion, each one
of which is existent between every adjacent pair of the 32 linear grooves in Fig.
1. All of the 32 linear grooves start from the fourth concentrically circular groove
from the center in the figure.
In Fig. 5, the pad has 28 linear grooves in Fig. 1 which
start from a portion slightly away from the center toward the periphery, each consisting
of a pair of parallel linear grooves.
The chemical mechanical polishing pad of the present invention
may be made of any material if it has the above requirements and can serve as a
chemical mechanical polishing pad. It is particularly preferred that pores having
the function of holding slurry during chemical mechanical polishing and the function
of retaining substances which are generated by polishing and of the surface to be
polished temporarily out of the functions of the chemical mechanical polishing pad
should be formed by the time of polishing. Therefore, the polishing pad preferably
comprises a material containing a water-insoluble matrix and water-soluble particles
dispersed in the water-insoluble matrix, or a material containing a water-insoluble
matrix and voids dispersed in the water-insoluble matrix (for example, foam).
In the former material out of these, the water-soluble
particles dissolve or swell upon their contact with an aqueous medium contained
in the aqueous dispersion for chemical mechanical polishing at the time of polishing
to be eliminated, and slurry can be held in pores formed by the elimination. In
the latter material, the slurry can be held in pores formed as the voids in advance.
In the former material, the material constituting the above
water-insoluble matrix is not particularly limited but an organic material is preferably
used because it can be easily molded into a predetermined shape and can easily provide
desired properties such as suitable hardness and suitable elasticity. Examples of
the organic material include thermoplastic resins, elastomers, rubbers and cured
resins (resins obtained by curing thermally or optically curable resins by heat
or light). They may be used alone or in combination.
Out of these, the thermoplastic resins include 1,2-polybutadiene
resin, polyolefin resins, polystyrene resins, polyacrylic resins, vinyl ester resins
(excluding polyacrylic resins), polyester resins, polyamide resins, fluororesins,
polycarbonate resins and polyacetal resins. The above polyolefin resins include
polyethylene, the above polyacrylic resins include (meth)acrylate-based resins,
and the above fluororesins include polyvinylidene fluoride.
The elastomers include diene elastomers, polyolefin elastomers
(TPO), styrene-based elastomers, thermoplastic elastomers, silicone resin elastomers
and fluororesin elastomers. The above diene elastomers include 1,2-polybutadiene.
The above styrene-based elastomers include styrene-butadiene-styrene block copolymer
(SBS) and hydrogenated block copolymers thereof (SEBS). The above thermoplastic
elastomers include thermoplastic polyurethane elastomers (TPU), thermoplastic polyester
elastomers (TPEE) and polyamide elastomers (TPAE).
The above rubbers include conjugated diene rubbers, nitrile
rubbers, acrylic rubber, ethylene-&agr;-olefin rubbers and others. The above conjugated
diene rubbers include butadiene rubber (high-cis butadiene rubber and low-cis butadiene
rubber), isoprene rubber, styrene-butadiene rubber and styrene-isoprene rubber.
The above nitrile rubbers include acrylonitrile-butadiene rubber. The above ethylene-&agr;-olefin
rubbers include ethylene-propylene rubber and ethylene-propylene-non-conjugated
diene rubber. The other rubbers include butyl rubber, silicone rubber and fluorine
rubber.
The above cured resins include urethane resins, epoxy resins,
acrylic resins, unsaturated polyester resins, polyurethane-urea resins, urea resins,
silicon resins, phenolic resins and vinyl ester resins.
These organic materials may be modified by an acid anhydride
group, carboxyl group, hydroxyl group, epoxy group or amino group. The affinity
for the water-soluble particles to be described hereinafter and slurry can be adjusted
by modification.
These organic materials may be used alone or in combination
of two or more.
The organic material may be a partially or wholly crosslinked
polymer or non-crosslinked polymer. That is, the water-insoluble matrix may be made
of a crosslinked polymer alone, a mixture of a crosslinked polymer and a non-crosslinked
polymer, or a non-crosslinked polymer alone. It is preferably made of a crosslinked
polymer alone or a mixture of a crosslinked polymer and a non-crosslinked polymer.
When a crosslinked polymer is contained, elastic recovery force is provided to the
water-insoluble matrix and displacement caused by shear stress applied to the chemical
mechanical polishing pad during polishing can be reduced. Further, it is possible
to effectivelyprevent the pores from being filled by the plastic deformation of
the water-insoluble matrix when it is excessively stretched at the time of polishing
and dressing and the surface of the chemical mechanical polishing pad from being
excessively fluffed. Therefore, the pores are formed efficiently even at the time
of dressing, whereby the deterioration of the holding properties of the slurry during
polishing can be suppressed, and further the polishing pad is rarely fluffed, thereby
making it possible to realize excellent polishing flatness.
The method of crosslinking the above material is not particularly
limited. For example, chemical crosslinking making use of an organic peroxide, sulfur
or a sulfur compound, or radiation crosslinking by applying an electron beam may
be employed.
Out of the above organic materials, a crosslinked rubber,
cured resin, crosslinked thermoplastic resin or crosslinked elastomer may be used
as the crosslinked polymer. A crosslinked thermoplastic resin and/or crosslinked
elastomer all of which are stable to a strong acid or strong alkali contained in
most of aqueous dispersions for chemical mechanical polishing and are rarely softened
by water absorption are/is preferred. Out of the crosslinked thermoplastic resin
and the crosslinked elastomer, what is crosslinked with an organic peroxide is more
preferred, and crosslinked 1,2-polybutadiene is particularly preferred.
The amount of the crosslinked polymer is not particularly
limited but preferably 30 vol% or more, more preferably 50 vol% or more, particularly
preferably 70 vol% or more and may be 100 vol% of the water-insoluble matrix. When
the amount of the crosslinked polymer contained in the water-insoluble matrix is
30 vol% or more, the effect obtained by containing the crosslinked polymer in the
water-insoluble matrix can be fully obtained.
The above water-insoluble matrix material may contain a
compatibilizing agent which differs from the above water-insoluble matrix material
to control its affinity for the water-soluble particles and the dispersibility of
the water-soluble particles in the water-insoluble matrix material. Examples of
the compatibilizing agent include homopolymers, block copolymers and random copolymers
modified by an acid anhydride group, carboxyl group, hydroxyl group, epoxy group,
oxazoline group or amino group, nonionic surfactants and coupling agents.
The above water-soluble particles in the former material
are particles which are eliminated from the water-insoluble matrix upon their contact
with an aqueous medium contained in the aqueous dispersion for chemical mechanical
polishing during chemical mechanical polishing. This elimination may occur when
they dissolve upon their contact with the aqueous medium or when they swell and
become colloidal by absorbing water contained in the aqueous medium. Further, this
dissolution or swelling is caused not only by their contact with water but also
by their contact with an aqueous mixed medium containing an alcohol-based solvent
such as methanol.
The material constituting the water-soluble particles is
not particularly limited. They are, for example, organic water-soluble particles
or inorganic water-soluble particles. Examples of the material of the organic water-soluble
particles include saccharides (polysaccharides such as starch, dextrin and cyclodextrin,
lactose, mannitol), celluloses (such as hydroxypropyl cellulose, methyl cellulose),
protein, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyethylene
oxide, water-soluble photosensitive resins, sulfonated polyisoprene and sulfonated
isoprene copolymers. Examples of the material of the inorganic water-soluble particles
include potassium acetate, potassium nitrate, potassium carbonate, potassium hydrogencarbonate,
potassium chloride, potassium bromide, potassium phosphate and magnesium nitrate.
The above materials may be used alone or in combination of two or more for these
water-soluble particles. The water-soluble particles may be made of one predetermined
material, or two or more different materials.
The water-soluble particles contained in the former material
are particularly preferably solid because they can set the hardness of the pad to
an appropriate value.
The water-soluble particles have an average particle diameter
of preferably 0.1 to 500 µm, more preferably 0.5 to 100 µm. The pores
formed by the elimination of the water-soluble particles are as big as preferably
0.1 to 500 µm, more preferably 0.5 to 100 µm. When the average particle
diameter of the water-soluble particles is within the above range, a chemical mechanical
polishing pad having a high polishing rate and excellent mechanical strength can
be obtained.
The amount of the water-soluble particles is preferably
1 to 90 vol%, more preferably 1 to 60 vol%, much more preferably 1 to 40 vol% based
on 100 vol% of the total of the water-insoluble matrix and the water-soluble particles.
When the amount of the water-soluble particles is within the above range, a chemical
mechanical polishing pad having a high polishing rate, appropriate hardness and
mechanical strength can be obtained.
It is preferred that the water-soluble particles should
dissolve in water or swell only when they are exposed to the surface layer of the
polishing pad and should not absorb moisture or swell when they are existent in
the inside of the polishing pad. Therefore, the water-soluble particles may have
an outer shell for suppressing moisture absorption on at least part of their outermost
portion. This outer shell may be physically adsorbed to the water-soluble particle,
chemically bonded to the water-soluble particle, or in contact with the water-soluble
particle by physical adsorption and chemical bonding. The outer shell is made of
an epoxy resin, polyimide, polyamide, polysilicate or silane coupling agent. In
this case, the water-soluble particles may consist of water-soluble particles having
an outer shell and water-soluble particles having no outer shell. Even when surface
of the water-soluble particles having an outer shell are not entirely covered with
the outer shell, the above effect can be fully obtained.
The water-insoluble matrix material constituting the chemical
mechanical polishing pad which comprises the latter material containing a water-insoluble
matrix and voids dispersed in the water-insoluble matrix is, for example, a polyurethane,
melamine resin, polyester, polysulfone or polyvinyl acetate.
The average size of the voids dispersed in the above water-insoluble
matrix is preferably 0.1 to 500 µm, more preferably 0.5 to 100 µm as an
average value.
The chemical mechanical polishing pad of the present invention
may optionally contain abrasive grains, oxidizing agent, alkali metal hydroxide,
acid, pH controller and surfactant besides the above materials. It is preferred
that abrasive grains and an oxidizing agent out of these be not contained.
The Shore D hardness of the chemical mechanical polishing
pad of the present invention is preferably 35 or more, more preferably 35 to 100,
much more preferably 50 to 90, particularly preferably 50 to 75. When the Shore
D hardness is 35 or more, pressure which can be applied to the object to be polished
can be increased, and the polishing rate can be thereby improved. In addition, high
polishing flatness is obtained.
The process for manufacturing the chemical mechanical polishing
pad of the present invention is not particularly limited, and the method of forming
a groove or grooves on the polishing surface of the chemical mechanical polishing
pad are not particularly limited as well. For example, after a composition for forming
a chemical mechanical polishing pad which will become a chemical mechanical polishing
pad is prepared and molded into a desired rough form, a groove or grooves can be
formed by cutting. Alternatively, a metal mold having a recessed portion (s) corresponding
to the groove or grooves to be formed is used to mold the composition for forming
a chemical mechanical polishing pad, thereby making it possible to form the groove
or grooves simultaneously with the manufacture of a rough form of the chemical mechanical
polishing pad. After a metal mold having a recessed portion(s) corresponding to
part of the groove or grooves to be formed is used to form a rough pad form having
part of a desired groove or grooves, the other part of the groove or grooves may
be formed by cutting.
When the chemical mechanical polishing pad of the present
invention has a groove, grooves or other recessed portion on the non-polishing surface,
the groove, grooves or other recessed portion may be formed similarly as described
above.
The method of obtaining the composition for forming a chemical
mechanical polishing pad is not particularly limited. For example, the composition
can be obtained by kneading together essential materials including a predetermined
organic material by means of a kneader. A conventionally known kneader may be used,
such as a roll, kneader, Banbury mixer or extruder (single-screw, multiple-screw).
The composition for forming a chemical mechanical polishing
pad, which comprises water-soluble particles for obtaining a chemical mechanical
polishing pad containing the water-soluble particles, can be obtained, for example,
by kneading together a water-insoluble matrix, water-soluble particles and other
optional additives. Preferably, they are kneaded together under heating so that
they can be easily processed at the time of kneading. The water-soluble particles
are preferably solid at this kneading temperature. When water-soluble particles
classified by the above preferred range of average particle diameter are used and
kneaded under the condition that they are solid, they can be dispersed with the
above preferred average particle diameter irrespective of their compatibility with
the water-insoluble matrix.
Therefore, the type of the water-soluble particles is preferably
selected according to the processing temperature of the water-insoluble matrix in
use.
The chemical mechanical polishing pad of the present invention
may be a multi-layer pad having a support layer on the non-polishing surface of
the above pad.
The above support layer is a layer formed on the rear surface
to support the chemical mechanical polishing pad. Although the characteristic properties
of this support layer are not particularly limited, the support layer is preferably
softer than the pad body. When the pad has a soft support layer, if the pad body
is thin, it is possible to prevent the pad body from rising during polishing or
the surface of the polishing layer from curving, whereby polishing can be carried
out stably. The hardness of the support layer is preferably 90 % or less, more preferably
50 to 90 %, much more preferably 50 to 80 %, particularly preferably 50 to 70 %
of the shore D hardness of the pad body.
The support layer may be made of a porous material (foam)
or a non-porous material. Although the plane shape of the support layer may be circular
or polygonal, the support layer preferably has the same plane shape and size as
those of the polishing pad. The thickness of the support layer is not particularly
limited but preferably 0. 1 to 5 mm, more preferably 0.5 to 2 mm.
Although the material of the support layer is not particularly
limited, an organic material is preferably used because it can be easily molded
to have a predetermined shape and predetermined properties and can provide suitable
elasticity. Organic materials enumerated as the material constituting the water-insoluble
matrix of the chemical mechanical polishing pad of the present invention can be
used as the organic material.
The chemical mechanical polishing method of the present
invention is characterized by chemically mechanically polishing the surface to be
polished by using the above chemical mechanical polishing pad of the present invention.
The chemical mechanical polishing method of the present invention can be carried
out in accordance with a known method except that the chemical mechanical polishing
pad of the present invention is set in a commercially available chemical polishing
machine.
The material constituting the surface to be polished is
a metal which is a wiring material, barrier metal, insulating material or a combination
thereof. Examples of the above metal as the wiring material include tungsten, aluminum,
copper and an alloy containing at least one of them. Examples of the above barrier
metal include tantalum, tantalum nitride, niobium and niobium nitride. Examples
of the above insulating material include SiO2, boron phosphorus silicate
(BPSG) obtained by adding small amounts of boron and phosphorus to SiO2,
insulating material called "FSG (Fluorine-Doped silicate Glass) " obtained by doping
SiO2 with fluorine, and silicon oxide-based insulating materials having
a low dielectric constant. Examples of SiO2 include a thermally oxidated
film, PETEOS (Plasma Enhanced-TEOS), HDP (High Density Plasma Enhanced-TEOS) and
SiO2 obtained by thermal CVD.
The object to be polished by the chemical mechanical polishing
method of the present invention is preferably an object made of copper or copper
alloy, object made of copper or a copper alloy and an insulating material, or object
made of copper or a copper alloy, a barrier metal and an insulating material.
As obvious from the following examples, the chemical mechanical
polishing pad and chemical mechanical polishing method of the present invention
are excellent in terms of polishing rate and in-plane uniformity in the amount of
polishing of the surface to be polished even when the amount of an aqueous dispersion
for chemical mechanical polishing is made small. The mechanism that the above excellent
performance is obtained is not made clear yet. It is assumed that this is because
the aqueous dispersion is efficiently supplied to the interface between the polishing
surface and the surface to be polished and the contact area between the polishing
surface and the surface to be polished is ensured during chemical mechanical polishing
by employing the above specific groove design.
Examples
Example 1
(1) manufacture of chemical mechanical polishing pad
80 parts by volume (equivalent to 72 parts by mass) of
1,2-polybutadiene (manufactured by JSR Corporation, trade name of "JSR RB830") which
would be crosslinked to become a water-insoluble matrix and 20 parts by volume (equivalent
to 28 parts by mass) of &bgr;-cyclodextrin (manufactured by Bio Research Corporation
of Yokohama, trade name of "Dexy Pearl &bgr;-100", average particle diameter of
20 µm) as water-soluble particles were kneaded together by an extruder set
at 160°C. Thereafter, 0.24 part by mass of dicumyl peroxide (manufactured by
NOF Corporation, trade name of "Percumyl D") was added to and kneaded with the above
kneaded product at 120°C to obtain a pellet. The resulting kneaded product
was then heated in a metal mold at 170°C for 18 minutes to be crosslinked so
as to obtain a disk-like molded product having a diameter of 508 mm and a thickness
of 2.8 mm. Concentrically circular grooves having a width of 0.5 mm, a pitch of
3.5 mm (land ratio of 6.0) and a depth of 2.2 mm with the center of the polishing
surface of this molded product as the center thereof were formed in the polishing
surface of this molded product by using a cutting machine manufactured by Kato Machine
Corporate (first grooves). Out of the first grooves, the radius of the smallest
circular groove was 25 mm and the radius of the largest circular groove was 252.5
mm. Further, 64 linear grooves (having a width of 3.0 mm and a depth of 2.2 mm)
extending from the center portion to the peripheral end of the pad were formed in
the polishing surface at an angle between adjacent linear grooves of 5.625°
(second grooves). Out of the 64 linear grooves, 32 were in contact with one another
at the center of the polishing surface of the pad, the other 32 started from points
25 mm away from the center of the polishing surface, and each one of the linear
grooves starting from points 25 mm away from the center of the polishing surface
was existent between every adjacent pair of the 32 second grooves which were in
contact with one another at the center of the polishing surface of the pad.
(2) Polishing test on PETEOS film without a pattern
The above manufactured chemical mechanical polishing pad
was set on the platen of the "Mirra/Mesa" polishing machine (trade name, manufactured
by Applied Materials Inc.). and a wafer having a PETEOS film without a pattern (a
PETEOS film (SiO2 film formed from tetraethyl orthosilicate (TEOS) by
chemical vapor deposition using plasma as a promoting condition) having a thickness
of 10,000 Å formed on an 8-inch silicon substrate) was polished by using the
"SS-25" (trade name, manufactured by CABOT Corporation) diluted 2 times with ion
exchange water as an aqueous dispersion for chemical mechanical polishing under
the following conditions.
Head revolution: 63 rpm
Platen revolution: 57 rpm
Head pressure: 5 psi
flow rate of aqueous dispersion for chemical mechanical
polishing: 100 ml/min
Polishing time: 1 minute
The flow rate of the aqueous dispersion for chemical mechanical
polishing used in this example was about half of the standard flow rate in the polishing
machine in use.
(3) evaluation of polishing rate of PETEOS film without a pattern
49 points spaced equally in the diameter direction of the
8-inch wafer having a PETEOS film which is the above material to be polished excluding
a 5 mm portion from the periphery were determined as specified points so as to calculate
the polishing rate at each point from the difference in the thickness of the PETEOS
film before and after polishing and the polishing time.
The average value of the polishing rates at the 49 points
was taken as the polishing rate. The results are shown in Table 1.
The thickness of the PETEOS film at each point was measured
by an optical film thickness meter.
(4) evaluation of in-plane uniformity in the amount of polishing
of PETEOS film without a pattern
In-plane uniformity in the amount of polishing was calculated
from the difference in the thickness of the PETEOS film before and after polishing
at the above 49 points (this value is taken as "the amount of polishing") based
on the following equation. In-plane uniformity in the amount of polishing (%) =
(standard deviation of the amount of polishing ÷ average value of the amount
of polishing) x 100
The results are shown in Table 1. When this value is 5
% or less, it can be said that the in-plane uniformity is satisfactory and when
this value is 3 % or less, it can be said that the in-plane uniformity is excellent.
Examples 2 to 12 and Comparative Examples 1 and 2
Disk-like molded products having the same composition and
size as those of Example 1 were fabricated in the same manner as in Example 1 in
order to manufacture chemical mechanical polishing pads having first grooves (concentrically
circular grooves) and second grooves (linear grooves which extended from the center
portion and reached the peripheral end of the pad) as shown in Table 1. The PETEOS
film was polished in the same manner as in Example 1 to evaluate the chemical mechanical
polishing pads. The results are shown in Table 1.
In Examples 2 to 8, out of the formed first grooves, the
radius of the smallest circular groove was 25 mm and the radius of the largest circular
groove was 252.5 mm. In Examples 9 to 12, the radius of the smallest circular groove
was 25 mm and the radius of the largest circular groove was 253 mm. In Examples
2 to 12, the second grooves which were not in contact with any other second grooves
started from points 25 mm away from the center of the polishing surface.
The configuration of the second grooves in Example 2 was
the same as that of Example 1, the configuration of the second grooves in Example
3 was the same as that of Example 1 except that the depth of the grooves differed
from that of Example 1, the angle between every adjacent pair of 32 second grooves
in Example 4 to 12 was 11.25°, each one linear groove starting from a point
25 mm away from the center of the polishing surface was existent between every adjacent
pair of 16 second grooves which were in contact with one another at the center of
the polishing surface of the pad out of the second grooves in Example 4, 3 linear
grooves starting from points 25 mm away from the center of the polishing surface
were existent between every adjacent pair of 8 second grooves which were in contact
with one another at the center of the polishing surface of the pad out of the second
grooves in Example 5, and 7 linear grooves starting from points 25 mm away from
the center of the polishing surface were existent between every adjacent pair of
4 second grooves which were in contact with one another at the center of the polishing
surface of the pad out of the second grooves in Examples 6 to 12 and Comparative
Example 1. The second grooves were not formed in the pad of Comparative Example
2.
Table 1
First grooves
Second grooves
Polishing results
Depth (mm)
Pitch (mm)
Width (mm)
Land ratio
Depth (mm)
Width (mm)
Number of grooves
Number of grooves in contact with one another
Polishing rate (nm/min)
In-plane uniformity (%)
Ex. 1
2.2
3.5
0.500
6.0
2.2
3.0
64
32
340
4.70
Ex.2
1.4
3.5
0.500
6.0
2.2
3.0
64
32
350
4.65
Ex.3
1.4
3.5
0.500
6.0
1.4
3.0
64
32
370
4.53
Ex.4
1.4
3.5
0.500
6.0
1.4
3.0
32
16
390
4.10
Ex.5
1.4
3.5
0.500
6.0
1.4
3.0
32
8
410
3.87
Ex.6
1.4
3.5
0.500
6.0
1.4
3.0
32
4
430
3.01
Ex.7
1.4
3.5
0.500
6.0
1.4
2.0
32
4
450
2.84
Ex.8
1.4
3.5
0.500
6.0
1.4
0.5
32
4
510
2.61
Ex.9
1.4
4.0
0.500
7.0
1.4
0.5
32
4
540
2.31
Ex. 10
1.4
4.0
0.375
9.7
1.4
0.5
32
4
550
1.89
Ex. 11
1.4
4.0
0.350
10.4
1.4
0.5
32
4
580
1.00
Ex.12
1.4
4.0
0.250
15.0
1.4
0.5
32
4
600
0.94
C.Ex.1
1.4
2.0
0.500
3.0
1.4
0.5
32
4
320
7.30
C.Ex.2
1.4
3.5
0.500
6.0
None
None
None
None
270
10.5
Ex.: Example C.Ex.: Comparative
Example
Example 13
(1) Polishing test on copper (Cu) film without a pattern
A chemical mechanical polishing pad manufactured in the
same manner as in Example 1 was set on the platen of the "Mirra/Mesa" polishing
machine (of Applied Materials Inc.) to polish a wafer having a copper film without
a pattern (a copper film having a thickness of 15,000 Å on an 8-inch silicon
substrate having a thermally oxidated film) under the following conditions.
Head revolution: 103 rpm
Platen revolution: 97 rpm
Head pressure: 3 psi
flow rate of aqueous dispersion for chemical mechanical
polishing: 100 ml/min
Polishing time: 1 minute
An aqueous dispersion for chemical mechanical polishing
having a pH of 2.5 and containing 1.0 mass% of silica, 0.5 mass% of malic acid,
7.0 mass% of hydrogen peroxide (concentration of 30 mass%) and 0.2 mass% of benzotriazole
was used. The flow rate of the aqueous dispersion for chemical mechanical polishing
used in this example was about half of the standard flow rate in the polishing machine
in use.
(2) evaluation of polishing rate of copper film without a pattern
49 points equally in the diameter direction of the 8-inch
wafer having a copper film which is the above material to be polished excluding
a 5 mm portion from the periphery were determined as specified points so as to calculate
the polishing rate at each point from the difference in the thickness of the copper
film before and after polishing and the polishing time.
The average value of the polishing rates at the 49 points
was taken as the polishing rate. The results are shown in Table 2.
The thickness of the copper film at each point was measured
by "Omnimap RS75" electroconductive film thickness meter (of KLA-Tencor Corporation).
(3) evaluation of in-plane uniformity in the amount of polishing
of copper film without a pattern
The in-plane uniformity was calculated from the difference
in the thickness of the Cu film before and after polishing at the above 49 points
(this value is taken as "the amount of polishing") based on the following equation.
In-plane uniformity in the amount of polishing (%) = (standard deviation of the
amount of polishing ÷ average value of the amount of polishing) x 100
The results are shown in Table 2. When this value is 5
% or less, it can be said that the in-plane uniformity is satisfactory and when
this value is 3 % or less, it can be said that the in-plane uniformity is excellent.
Examples 14 to 24 and Comparative Examples 3 and 4
A polishing test was made on a copper film without a pattern
in the same manner as in Example 13 except that chemical mechanical polishing pads
manufactured in the same manner as in Examples 2 to 13 and Comparative Examples
1 and 2 were used to evaluate the polishing rate and the in-plane uniformity in
the amount of polishing. The evaluation results are shown in Table 2.
Table 2
First grooves
Second grooves
Polishing results
Depth (mm)
Pitch (mm)
Width (mm)
Land ratio
Depth (mm)
Width (mm)
Number of grooves
Number of grooves in contact with one another
Polishing rate (nm/min)
In-plane uniformity (%)
Ex. 13
2.2
3.5
0.500
6.0
2.2
3.0
64
32
550
4.80
Ex. 14
1.4
3.5
0.500
6.0
2.2
3.0
64
32
560
4.75
Ex. 15
1.4
3.5
0.500
6.0
1.4
3.0
64
32
590
4.57
Ex. 16
1.4
3.5
0.500
6.0
1.4
3.0
32
16
600
4.00
Ex.17
1.4
3.5
0.500
6.0
1.4
3.0
32
8
620
3.50
Ex.18
1.4
3.5
0.500
6.0
1.4
3.0
32
4
650
2.68
Ex.19
1.4
3.5
0.500
6.0
1.4
2.0
32
4
690
2.01
Ex.20
1.4
3.5
0.500
6.0
1.4
0.5
32
4
720
1.97
Ex.21
1.4
4.0
0.500
7.0
1.4
0.5
32
4
750
1.65
Ex.22
1.4
4.0
0.375
9.7
1.4
0.5
32
4
760
1.55
Ex.23
1.4
4.0
0.350
10.4
1.4
0.5
32
4
800
1.10
Ex.24
1.4
4.0
0.250
15.0
1.4
0.5
32
4
830
0.65
C.Ex.3
1.4
2.0
0.500
3.0
1.4
0.5
32
4
500
8.60
C.Ex.4
1.4
3.5
0.500
6.0
None
None
None
None
480
11.3
Ex.: Example C.Ex.: Comparative
Example
Example 25
(1) manufacture of chemical mechanical polishing pad
95 parts by volume (equivalent to 92.5 parts by mass) of
a mixture obtained by dry blending together 30 parts by mass of polystyrene (manufactured
by PS Japan Corporation, trade name of "HF55") and 70 parts by mass of 1,2-polybutadiene
(manufactured by JSR Corporation, trade name of "JSR RB830") and 5 parts by volume
(equivalent to 7.5 parts by mass) of &bgr;-cyclodextrin (manufactured by Bio Research
Corporation of Yokohama, trade name of "Dexy Pearl &bgr;-100") were kneaded together
at 150°C and 120 rpm by an extruder heated at 120°C. Thereafter, 0.12
part by mass (equivalent to 0.03 part by mass in terms of pure dicumyl peroxide)
of "Percumyl D40" (trade name, manufactured by NOF Corporation, containing 40 mass%
of dicumyl peroxide) was added to and kneaded with the above kneaded product at
120°C and 60 rpm. The resulting kneaded product was then heated in a metal
mold at 175°C for 12 minutes to be crosslinked so as to obtain a disk-like
molded product having a diameter of 508 mm and a thickness of 2.8 mm. The same grooves
as in Example 7 were formed in the polishing surface of this molded product to manufacture
a chemical mechanical polishing pad.
(2) polishing test on PETEOS film without a pattern
A polishing test was made on a PETEOS film without a pattern
in the same manner as in Example 1 except that the above manufactured polishing
pad was used to evaluate the polishing rate and the in-plane uniformity in the amount
of polishing. The results are shown in Table 3.
Examples 26 to 28 and Comparative Examples 5 and 6
Disk-like molded products having the same composition and
size as those of Example 25 were fabricated in the same manner as in Example 25
and the same grooves as in Example 8, 9 and 12 were formed to manufacture chemical
mechanical polishing pads, and the PETEOS film was polished in the same manner as
in Example 1 to evaluate the manufactured chemical mechanical polishing pads. The
results are shown in Table 3.
Table 3
First grooves
Second grooves
Polishing results
Depth (mm)
Pitch (mm)
Width (mm)
Land ratio
Depth (mm)
Width (mm)
Number of grooves
Number of grooves in contact with one another
Polishing rate (nm/min)
In-plane uniformity (%)
Ex.25
1.4
3.5
0.500
6.0
1.4
2.0
32
4
450
2.89
Ex.26
1.4
3.5
0.500
6.0
1.4
0.5
32
4
480
1.50
Ex.27
1.4
4.0
0.500
7.0
1.4
0.5
32
4
530
1.20
Ex.28
1.4
4.0
0.250
15.0
1.4
0.5
32
4
570
0.87
C.Ex.5
1.4
2.0
0.500
3.0
1.4
0.5
32
4
350
6.70
C.Ex.6
1.4
3.5
0.500
6.0
None
None
None
None
300
8.90
Ex.: Example C.Ex.: Comparative
Example
Example 29
(1) manufacture of chemical mechanical polishing pad
98 parts by volume (equivalent to 97 parts by mass) of
1,2-polybutadiene (manufactured by JSR Corporation, trade name of "JSR RB830") which
would be crosslinked to become a water-insoluble matrix and 2 parts by volume (equivalent
to 3 parts by mass) of &bgr;-cyclodextrin (manufactured by Bio Research Corporation
of Yokohama, trade name of "Dexy Pearl &bgr;-100", average particle diameter of
20 µm) as water-soluble particles were kneaded together by an extruder set
at 120°C. Thereafter, 0.37 part by mass of dicumyl peroxide (manufactured by
NOF Corporation, trade name of "Percumyl D") was added to and kneaded with the above
kneaded product at 120°C to obtain a pellet. The resulting kneaded product
was then heated in a metal mold at 175°C for 12 minutes to be crosslinked so
as to obtain a disk-like molded product having a diameter of 508 mm and a thickness
of 2.8 mm. The same grooves as in Example 7 were formed in the polishing surface
of this molded product to manufacture a chemical mechanical polishing pad.
(2) polishing test on PETEOS film without a pattern
A polishing test was made on a PETEOS film without a pattern
in the same manner as in Example 1 except that the above manufactured polishing
pad was used to evaluate the polishing rate and the in-plane uniformity in the amount
of polishing. The results are shown in Table 4.
Examples 30 to 32 and Comparative Examples 7 and 8
Disk-like molded products having the same composition and
size as those of Example 29 were fabricated in the same manner as in Example 29
and the same grooves as in Example 8, 9 and 12 were formed to manufacture chemical
mechanical polishing pads, and the PETEOS film was polished in the same manner as
in Example 1 to evaluate the manufactured chemical mechanical polishing pads. The
results are shown in Table 4.
Table 4
First grooves
Second grooves
Polishing results
Depth (mm)
Pitch (mm)
Width (mm)
Land ratio
Depth (mm)
Width (mm)
Number of grooves
Number of grooves in contact with one another
Polishing rate (nm/min)
In-plane uniformity (%)
Ex.29
1.4
3.5
0.500
6.0
1.4
2.0
32
4
370
2.50
Ex.30
1.4
3.5
0.500
6.0
1.4
0.5
32
4
430
1.35
Ex.31
1.4
4.0
0.500
7.0
1.4
0.5
32
4
480
1.10
Ex. 32
1.4
4.0
0.250
15.0
1.4
0.5
32
4
530
0.98
C.Ex.7
1.4
2.0
0.500
3.0
1.4
0.5
32
4
320
6.40
C.Ex.8
1.4
3.5
0.500
6.0
None
None
None
None
270
8.70
Ex.: Example C.Ex.: Comparative
Example
Example 33
(1) manufacture of chemical mechanical polishing pad
58 parts by mass of 4,4'-diphenylmethane diisocyanate (manufactured
by Sumika Bayer Urethane Co. , Ltd., trade name of "Sumidule 44S") was fed to a
reactor, and 5.1 parts by mass of polytetramethylene glycol having two hydroxyl
groups at both terminals of the molecule and a number average molecular weight of
650 (manufactured by Mitsubishi Chemical Corporation, trade name of "PTMG650") and
17.3 parts by mass of polytetramethylene glycol having a number average molecular
weight of 250 (manufactured by Mitsubishi Chemical Corporation, trade name of "PTMG250")
were added to the reactor at 60°C under agitation, maintained at 90°C
for 2 hours under agitation to carry out a reaction, and then cooled to obtain an
isocyanate terminated prepolymer. This isocyanate terminated prepolymer was a mixture
of 21 mass% of unreacted 4,4'-diphenylmethane diisocyanate and 79 mass% of a prepolymer
having an isocyanate group at both terminals.
80.4 parts by mass of the above isocyanate terminated prepolymer
was fed to a stirring container and maintained at 90°C, 14.5 parts by mass
of &bgr;-cyclodextrin (manufactured by Bio Research Corporation of Yokohama, trade
name of "Dexy Pearl &bgr;-100") was added under agitation at 200 rpm to be mixed
and dispersed in the above prepolymer for 1 hour, and the obtained dispersion was
vacuum defoamed to obtain an isocyanate terminated prepolymer containing water-soluble
particles dispersed therein.
12.6 parts by mass of 1,4-bis(&bgr;-hydroxyethoxy)benzene
having two hydroxyl groups at a terminal (manufactured by Mitsui Fine Chemicals
Inc . , trade name of "BHEB") was heated at 120°C for 2 hours in a stirring
container to be molten, and 7 parts by mass of trimethylolpropane having three hydroxyl
groups (manufactured by BASF Japan Ltd., trade name of TMP) was added under agitation
to be mixed and dissolved in the above molten product for 10 minutes so as to obtain
a chain extender mixture.
94.9 parts by mass of the obtained isocyanate terminated
prepolymer containing water-soluble particles dispersed therein was heated at 90
°C and stirred in an AJITER (registered trademark) mixer, and 19.6 parts by
mass of the obtained chain extender mixture heated at 120°C was added to and
mixed with the prepolymer for 1 minute to obtain a raw material mixture.
The above raw material mixture was injected into a metal
mold with a disk-like cavity having a diameter of 508 mm and a thickness of 2.8
mm to an extent that the cavity was filled and maintained at 110°C for 30 minutes
to carry out a polyurethanation reaction, and then the mold was removed. Further,
the molded product was post-cured in a gear oven at 110°C for 16 hours to obtain
a polyurethane sheet having a diameter of 508 mm and a thickness of 2.8 mm and containing
water-soluble particles dispersed therein. The volume fraction of the water-soluble
particles to the entire sheet, that is, the volume fraction of the water-soluble
particles to the total of the polyurethane matrix and the water-soluble particles
was 10 %.
The same grooves as in Example 7 were formed in the entire
polishing surface of the molded sheet excluding a 30 mm center portion by using
a cutting machine to manufacture a chemical mechanical polishing pad.
(2) polishing test on PEETOS film without a pattern
A polishing test was made on a PETEOS film without a pattern
in the same manner as in Example 1 except that the above manufactured polishing
pad was used to evaluate the polishing rate and the in-plane uniformity in the amount
of polishing. The results are shown in Table 5.
Examples 34 to 36 and Comparative Examples 9 and 10
Disk-like molded products having the same composition and
size as those of Example 33 were fabricated in the same manner as in Example 33
and the same grooves as in Example 8, 9 and 12 were formed to manufacture chemical
mechanical polishing pads, and the PETEOS film was polished in the same manner as
in Example 1 to evaluate the manufactured chemical mechanical polishing pads. The
results are shown in Table 5.
Table 5
First grooves
Second grooves
Polishing results
Depth (mm)
Pitch (mm)
Width (mm)
Land ratio
Depth (mm)
Width (mm)
Number of grooves
Number of grooves in contact with one another
Polishing rate (nm/ min)
In-plane uniformity (%)
Ex.33
1.4
3.5
0.500
6.0
1.4
2.0
32
4
350
2.30
Ex.34
1.4
3.5
0.500
6.0
1.4
0.5
32
4
370
1.90
Ex.35
1.4
4.0
0.500
7.0
1.4
0.5
32
4
390
1.75
Ex.36
1.4
4.0
0.250
15.0
1.4
0.5
32
4
420
1.20
C.Ex.9
1.4
2.0
0.500
3.0
1.4
0.5
32
4
300
6.80
C.Ex.10
1.4
3.5
0.500
6.0
None
None
None
None
260
9.20
Ex.: Example C.Ex.: Comparative
Example
As obvious from the results of the above Examples and Comparative
Examples, the chemical mechanical polishing pad of the present invention having
first grooves with a land ratio of 6 to 30 and second grooves consisting of second
grooves which are not in contact with any other second grooves in the area of the
center portion and second grooves which are in contact with one another in the area
of the center portion in the polishing surface can achieve a high polishing rate
and excellent in-plane uniformity in the amount of polishing even when the flow
rate of an aqueous dispersion for chemical mechanical polishing is small.
A chemical mechanical polishing pad of the present invention
has the following two groups of grooves on the polishing surface:
- (i) a group of first grooves intersect a single virtual straight light extending
from the center toward the periphery of the polishing surface and have a land ratio
represented by the following equation of 6 to 30:
(P is the distance between adjacent intersections between the virtual straight line
and the first grooves, and W is the width of the first grooves); and
- (ii) a group of second grooves extend from the center portion toward the peripheral
portion of the polishing surface and consist of second grooves which are in contact
with one another in the area of the center portion and second grooves which are
not in contact with any other second grooves in the area of the center portion.
The chemical mechanical polishing pad of the present invention
has a high polishing rate and excellent in-plane uniformity in the amount of polishing
of the surface to be polished even when the amount of an aqueous dispersion for
chemical mechanical polishing is made small.