U.S. patent application number 17/735026 was filed with the patent office on 2022-08-18 for pattern formation method and material for manufacturing semiconductor devices.
The applicant listed for this patent is TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY, LTD.. Invention is credited to Ching-Yu CHANG, Shang-Wern CHANG, Yen-Hao CHEN, Chien-Wei WANG.
Application Number | 20220260918 17/735026 |
Document ID | / |
Family ID | |
Filed Date | 2022-08-18 |
United States Patent
Application |
20220260918 |
Kind Code |
A1 |
WANG; Chien-Wei ; et
al. |
August 18, 2022 |
PATTERN FORMATION METHOD AND MATERIAL FOR MANUFACTURING
SEMICONDUCTOR DEVICES
Abstract
In a pattern formation method, a bottom layer is formed over an
underlying layer. A middle layer is formed over the bottom layer. A
resist pattern is formed over the middle layer. The middle layer is
patterned by using the resist pattern as an etching mask. The
bottom layer is patterned by using the patterned middle layer. The
underlying layer is patterned. The middle layer contains silicon in
an amount of 50 wt % or more and an organic material. In one or
more of the foregoing and following embodiments, an annealing
operation is further performed after the middle layer is
formed.
Inventors: |
WANG; Chien-Wei; (Zhubei
City, TW) ; CHANG; Ching-Yu; (Yuansun Village,
TW) ; CHANG; Shang-Wern; (Zhubei City, TW) ;
CHEN; Yen-Hao; (New Taipei City, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY, LTD. |
Hsinchu |
|
TW |
|
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Appl. No.: |
17/735026 |
Filed: |
May 2, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16366290 |
Mar 27, 2019 |
11320738 |
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17735026 |
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62690846 |
Jun 27, 2018 |
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International
Class: |
G03F 7/38 20060101
G03F007/38; G03F 7/095 20060101 G03F007/095; G03F 7/11 20060101
G03F007/11 |
Claims
1. A pattern formation method comprising: forming a bottom layer
over an underlying layer; forming a photo sensitive layer over the
bottom layer; patterning the photo sensitive layer by using a
lithographic technique; patterning the bottom layer by using the
patterned photo sensitive layer; and patterning the underlying
layer, wherein: the photo sensitive layer contains silicon in an
amount of 50 wt % or more with respect to an entire weight of the
photo sensitive layer and a photo active compound (PAC).
2. The pattern formation method of claim 1, wherein the photo
sensitive layer includes a silicon particle having a silicon core
surrounded by a plurality of ligands.
3. The pattern formation method of claim 2, wherein a diameter of
the silicon core is in a range from 2 nm to 10 nm.
4. The pattern formation method of claim 2, wherein each of the
plurality of organic ligands has a chemical structure R-Lp, which
includes at least a first spacer group R and a polar group Lp
linked to the silicon core.
5. The pattern formation method of claim 4, wherein: the first
spacer group R include one or more of hydrogen, aromatic carbon
ring, or straight or cyclic alkyl, alkoxyl, fluoroalkyl,
fluoroalkoxyl, alkene, alkyne, hydroxyl, ketone, aldehyde,
carbonate, carboxylic acid, ester, ether, amide, amine, imine,
imide, azide, nitrate, nitrile, nitrite or thiol spacer group with
the chain carbon 1.about.12, and the polar group Lp includes one or
more of --Cl, --Br, --I, --NO.sub.2, --SO.sub.3--, --H, --CN,
--NCO, --OCN, --CO.sub.2--, --OH, --OR*, --OC(O)CR*, --SR*,
--SO.sub.2N(R*).sub.2, --SO.sub.2R*, --SOR*, --OC(O)R*, --C(O)OR*;
--C(O)R*; --Si(OR*).sub.3; --Si(R*).sub.3; epoxyl groups, where R*
is H, an unbranched or branched, cyclic or noncyclic saturated or
unsaturated alkyl or alkenyl or alkynyl groups.
6. The pattern formation method of claim 1, wherein the photo
sensitive layer contains silicon in an amount of 50 wt % or more
and 80 wt % or less with respect to the entire weight of the photo
sensitive layer.
7. The pattern formation method of claim 1, wherein a thickness of
the photo sensitive layer is in a range from 30 nm to 80 nm.
8. The pattern formation method of claim 1, wherein the bottom
layer is made of an organic material.
9. The pattern formation method of claim 8, wherein a thickness of
the bottom layer is in a range from 50 nm to 200 nm.
10. A pattern formation method comprising: forming a Si-containing
layer over an underlying layer; patterning the Si-containing layer;
and patterning the underlying layer by using the patterned
Si-containing layer, wherein: the Si-containing layer contains
silicon particles in an amount of 50 wt % or more with respect to
an entire weight of the Si-containing layer, and each of the
silicon particles includes a silicon core surrounded by a plurality
of organic ligands.
11. The pattern formation method of claim 10, wherein each of the
plurality of organic ligands has a chemical structure R-Lp, which
includes at least a first spacer group R and a polar group Lp
linked to the silicon core.
12. The pattern formation method of claim 11, wherein the first
spacer group R include one or more of hydrogen, aromatic carbon
ring, or straight or cyclic alkyl, alkoxyl, fluoroalkyl,
fluoroalkoxyl, alkene, alkyne, hydroxyl, ketone, aldehyde,
carbonate, carboxylic acid, ester, ether, amide, amine, imine,
imide, azide, nitrate, nitrile, nitrite or thiol spacer group with
the chain carbon 1.about.12, and the polar group Lp includes one or
more of --Cl, --Br, --I, --NO.sub.2, --SO.sub.3--, --H, --CN,
--NCO, --OCN, --CO.sub.2--, --OH, --OR*, --OC(O)CR*, --SR*,
--SO.sub.2N(R*).sub.2, --SO.sub.2R*, --SOR*, --OC(O)R*, --C(O)OR*;
--C(O)R*; --Si(OR*).sub.3; --Si(R*).sub.3; epoxyl groups, where R*
is H, an unbranched or branched, cyclic or noncyclic saturated or
unsaturated alkyl or alkenyl or alkynyl groups.
13. The pattern formation method of claim 10, wherein the
Si-containing layer contains silicon particles in an amount of 50
wt % or more and 70 wt % or less with respect to the entire weight
of the Si-containing layer.
14. The pattern formation method of claim 10, wherein the
Si-containing layer is patternable by ultra violet light.
15. A pattern formation method comprising: forming an underlying
device over a substrate; forming a first interlayer dielectric
(ILD) layer over the underlying device; forming an etch-stop layer
over the first ILD layer; forming a second ILD layer over the
etch-stop layer; forming a hard mask layer over the second ILD
layer; forming a bottom layer over the hard mask layer; forming a
Si-containing layer over the bottom layer; patterning the
Si-containing layer; patterning the bottom layer and hard mask
layer by using the patterned Si-containing layer as an etching
mask; removing the patterned Si-containing layer and the bottom
layer; and patterning the second ILD layer, the etch-stop layer and
the first ILD layer by using the hard mask layer as an etching
mask, wherein: the Si-containing layer silicon particles or silicon
clusters, and each of the silicon particles or the silicon clusters
includes a silicon core surrounded by a plurality of organic
ligands.
16. The pattern formation method of claim 15, wherein the silicon
particles or the silicon clusters include silicon in an amount of
50 wt % or more and 80 wt % or less with respect to an entire
weight of the Si-containing layer.
17. The pattern formation method of claim 16, wherein each of the
plurality of organic ligands has a chemical structure R-Lp, which
includes at least a first spacer group R and a polar group Lp
linked to the silicon core.
18. The pattern formation method of claim 17, wherein the first
spacer group R include one or more of hydrogen, aromatic carbon
ring, or straight or cyclic alkyl, alkoxyl, fluoroalkyl,
fluoroalkoxyl, alkene, alkyne, hydroxyl, ketone, aldehyde,
carbonate, carboxylic acid, ester, ether, amide, amine, imine,
imide, azide, nitrate, nitrile, nitrite or thiol spacer group with
the chain carbon 1.about.12, and the polar group Lp includes one or
more of --Cl, --Br, --I, --NO.sub.2, --SO.sub.3--, --H, --CN,
--NCO, --OCN, --CO.sub.2--, --OH, --OR*, --OC(O)CR*, --SR*,
--SO.sub.2N(R*).sub.2, --SO.sub.2R*, --SOR*, --OC(O)R*, --C(O)OR*;
--C(O)R*; --Si(OR*).sub.3; --Si(R*).sub.3; epoxyl groups, where R*
is H, an unbranched or branched, cyclic or noncyclic saturated or
unsaturated alkyl or alkenyl or alkynyl groups.
19. The pattern formation method of claim 15, wherein the hard mask
layer includes TiN.
20. The pattern formation method of claim 15, further comprising
forming an antireflection coating layer over the hard mask layer.
Description
RELATED APPLICATION
[0001] This application is continuation of U.S. patent application
Ser. No. 16/366,290 filed Mar. 27, 2019, now U.S. Pat. No.
11,320,738, which claims priority to U.S. Provisional Patent
Application No. 62/690,846 filed on Jun. 27, 2018, the entire
contents of each of which are incorporated herein by reference.
BACKGROUND
[0002] As the semiconductor industry has progressed into nanometer
technology process nodes in pursuit of higher device density,
higher performance, and lower costs, challenges from both
fabrication and design issues become greater. Lithography
operations to form patterns are one of the key operations in the
semiconductor manufacturing process.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] The present disclosure is best understood from the following
detailed description when read with the accompanying figures. It is
emphasized that, in accordance with the standard practice in the
industry, various features are not drawn to scale and are used for
illustration purposes only. In fact, the dimensions of the various
features may be arbitrarily increased or reduced for clarity of
discussion.
[0004] FIG. 1 shows one of the various stages of manufacturing
operations of semiconductor devices according to an embodiment of
the present disclosure.
[0005] FIG. 2 shows one of the various stages of manufacturing
operations of semiconductor devices according to an embodiment of
the present disclosure.
[0006] FIG. 3 shows one of the various stages of manufacturing
operations of semiconductor devices according to an embodiment of
the present disclosure.
[0007] FIG. 4 shows one of the various stages of manufacturing
operations of semiconductor devices according to an embodiment of
the present disclosure.
[0008] FIG. 5 shows one of the various stages of manufacturing
operations of semiconductor devices according to an embodiment of
the present disclosure.
[0009] FIG. 6 shows one of the various stages of manufacturing
operations of semiconductor devices according to an embodiment of
the present disclosure.
[0010] FIG. 7 shows a schematic view of a silicon particle or
cluster.
[0011] FIG. 8 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0012] FIG. 9 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0013] FIG. 10 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0014] FIG. 11 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0015] FIG. 12 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0016] FIG. 13 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0017] FIG. 14 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0018] FIG. 15 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0019] FIG. 16 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0020] FIG. 17 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0021] FIG. 18 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0022] FIG. 19 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0023] FIG. 20 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0024] FIG. 21 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0025] FIG. 22 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0026] FIG. 23 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0027] FIG. 24 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
[0028] FIG. 25 shows one of the various stages of manufacturing
operations of semiconductor devices according to another embodiment
of the present disclosure.
DETAILED DESCRIPTION
[0029] It is to be understood that the following disclosure
provides many different embodiments, or examples, for implementing
different features of the invention. Specific embodiments or
examples of components and arrangements are described below to
simplify the present disclosure. These are, of course, merely
examples and are not intended to be limiting. For example,
dimensions of elements are not limited to the disclosed range or
values, but may depend upon process conditions and/or desired
properties of the device. Moreover, the formation of a first
feature over or on a second feature in the description that follows
may include embodiments in which the first and second features are
formed in direct contact, and may also include embodiments in which
additional features may be formed interposing the first and second
features, such that the first and second features may not be in
direct contact. Various features may be arbitrarily drawn in
different scales for simplicity and clarity.
[0030] Further, spatially relative terms, such as "beneath,"
"below," "lower," "above," "upper" and the like, may be used herein
for ease of description to describe one element or feature's
relationship to another element(s) or feature(s) as illustrated in
the figures. The spatially relative terms are intended to encompass
different orientations of the device in use or operation in
addition to the orientation depicted in the figures. The device may
be otherwise oriented (rotated 90 degrees or at other orientations)
and the spatially relative descriptors used herein may likewise be
interpreted accordingly. In addition, the term "made of" may mean
either "comprising" or "consisting of."
[0031] Examples of devices that can benefit from one or more
embodiments of the present disclosure are semiconductor devices.
The semiconductor devices include a fin field effect transistor
(FinFET) and other MOS transistors. Other types of transistors,
such as a gate-all-around (GAA) FET, also benefit from the present
embodiments. Semiconductor devices may further include a static
random access memory (SRAM) and/or other logic circuits, passive
components such as resistors, capacitors, and inductors, and active
components. The semiconductor device may include a plurality of
semiconductor devices (e.g., transistors), which may be
interconnected. It is understood, however, that the application
should not be limited to a particular type of device, except as
specifically claimed.
[0032] When a FinFET, which includes a three dimensional fin
structure, is utilized, unevenness is caused on an interlayer
dielectric (ILD) layer, which affects performance of lithography
operations. To address these issues, a multi-layer resist
patterning system has been developed.
[0033] In the multi-layer resist patterning system, for example, a
tri-layer resist patterning system employs a bottom layer, a middle
layer and a photo resist layer. In the tri-layer resist patterning
system, the middle layer is etched by using the photo resist
pattern as an etching mask, and the bottom layer is etched by using
the patterned middle layer as an etching mask. Finally, the
underlying layer to be patterned is etched by using the patterned
middle and/or bottom layer. In these etching operations, however,
pattern width (critical dimensions "CD") varies from the intended
or designed value. As the critical dimension of the patterns
continues to shrink, this CD variation becomes more critical.
[0034] In the present disclosure, in a tri-layer or a bi-layer
resist system, a layer on which a photo resist pattern is formed
includes Si in an amount of 50 wt % or more, to suppress the CD
variation during the etching operations of the tri-layer or
bi-layer resist system.
[0035] FIGS. 1-6 show various stages of manufacturing a
semiconductor device according to an embodiment of the present
disclosure. It is understood that additional operations can be
performed before, during, and after processes shown by FIGS. 1-6,
and some of the operations described below can be replaced or
eliminated for additional embodiments of the method. The order of
the operations/processes may be interchangeable.
[0036] As shown in FIG. 1, an underlying layer 20 to be patterned
is formed over a substrate 10. One or more layers or structures are
provided between the underlying layer 20 and the substrate 10 in
some embodiments. In one embodiment, the substrate 10 is a silicon
substrate. Alternatively, the substrate may comprise another
elementary semiconductor, such as germanium; a compound
semiconductor including Group IV-IV compound semiconductors such as
SiC and SiGe, Group III-V compound semiconductors such as GaAs,
GaP, GaN, InP, InAs, InSb, GaAsP, AlGaN, AlInAs, AlGaAs, GaInAs,
GaInP, and/or GaInAsP; or combinations thereof. Amorphous
substrates, such as amorphous Si or amorphous SiC, or an insulating
material, such as silicon oxide may also be used as the substrate.
The substrate may include various regions that have been suitably
doped with impurities (e.g., p-type or n-type conductivity).
[0037] The underlying layer 20 includes one or more layers of
dielectric material or conductive material. The dielectric material
includes silicon oxide, silicon nitride, silicon oxynitride (SiON),
SiOCN, SiCO, SiCN, fluorine-doped silicate glass (FSG), or a low-k
dielectric material, or any other suitable dielectric material. The
dielectric material layer may be formed by chemical vapor
deposition (CVD), physical vapor deposition (PVD), atomic layer
deposition (ALD), or other suitable film forming processes. In some
embodiments, after the dielectric layer is formed, a planarization
process, such as an etch back process and/or a chemical mechanical
polishing (CMP) process is performed on the dielectric layer.
[0038] The conductive material includes a semiconductor material,
such as an elementary semiconductor including silicon or germanium;
Group IV-IV compound semiconductors; or Group III-V compound
semiconductors as set forth above. The semiconductor material can
be poly crystalline, amorphous or crystalline. The conductive
material also includes metallic material, such as Al, Cu, AlCu, W,
Co, Ti, Ta, Ni, silicide, TiN or TaN, or any suitable material. The
conductive material can be formed by CVD, PVD, ALD, molecular beam
epitaxy (MBE), electro plating, or other suitable film forming
processes.
[0039] Further, as shown in FIG. 1, a bottom layer 30 is formed
over the underlying layer 20. In some embodiments, the bottom layer
30 is made of an organic material. The organic material may include
a plurality of monomers or polymers that are not cross-linked.
Generally, the bottom layer 30 may contain a material that is
patternable and/or have a composition tuned to provide
anti-reflection properties. Exemplary materials for the bottom
layer 30 include carbon backbone polymers, such as
polyhydroxystyrene (PHS), poly methyl methacrylate (PMMA),
polyether, and combinations thereof, and other organic polymers
containing aromatic rings. The bottom layer 30 is used to planarize
the structure, as the underlying structure may be uneven. In some
embodiments, the bottom layer 30 is formed by a spin coating
process. In other embodiments, the bottom layer 30 is formed by
another suitable deposition process. The thickness of the bottom
layer 30 is in a range from about 50 nm to about 200 nm in some
embodiments and is in a range from about 80 nm to about 120 nm in
other embodiments. In some embodiments, after the bottom layer 30
is formed, an annealing operation is performed.
[0040] Then, as shown in FIG. 2, a middle layer 40 is formed over
the bottom layer 30. In some embodiments, the middle layer 40 is
formed by spin-coating a silicon containing solution over the
bottom layer, and the coated layer is baked at 80-120.degree. C.
for 30 sec to 120 sec. In some embodiments, the baking of the
coated layer is performed on a baking plate. The thickness of the
middle layer 40 is in a range from about 20 nm to about 100 nm in
some embodiments, and is in a range from about 30 nm to about 80 nm
in other embodiments.
[0041] The middle layer 40 is a silicon containing layer including
silicon and organic material. In the present disclosure, the middle
layer 40 after the plate-baking contains silicon in an amount of 50
wt % or more. In some embodiments, the middle layer 40 contains
silicon in an amount of 60 wt % or more. In some embodiments, the
Si amount of the middle layer 40 is up to 70 wt % and in up to 80
wt % in other embodiments.
[0042] As set forth above, the silicon containing middle layer is
formed from a silicon containing solution. The silicon containing
solution includes silicon particles and solvent. In some
embodiments, each of the silicon particles includes a silicon core
C surrounded by a plurality of ligands L as shown in FIG. 7. In
some embodiments, a size W1 of the silicon particle is in a range
from 1 nm to 20 nm, and is in a range from about 2 nm to about 15
nm in other embodiments. The silicon core C is a solid crystalline
or non-crystalline silicon, a cluster (secondary particle) of
silicon primary particles, a silicon ring, or a porous silicon. In
some embodiments, a diameter W2 of the silicon core C is in a range
from about 1 nm to about 20 nm, and is in a range from about 2 nm
to about 15 nm in other embodiments. In some embodiments, the core
C is made of one of Ti, Sn, Al, T and Au and has a diameter W2 in a
range from about 1 nm to about 20 nm. The diameter is in a range
from about 2 nm to about 15 nm in other embodiments.
[0043] In some embodiments, each of the plurality of ligands L is
an organic ligand. The organic ligand is one or more of styrene,
1-decene, 1-vinylnaphtharene, alkyl group (e.g., methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, . . . ;
the number of carbon is up to 20), alkynyl group (e.g., the number
of carbon is up to 20), alkenyl groups (e.g., the number of carbon
is up to 20). The ligand L has a chemical structure R-Lp, where R
represents a first spacer group, and Lp represents a polar group
linked to the silicon core C. The first spacer group R may include
hydrogen, aromatic carbon ring, or straight or cyclic alkyl,
alkoxyl, fluoroalkyl, fluoroalkoxyl, alkene, alkyne, hydroxyl,
ketone, aldehyde, carbonate, carboxylic acid, ester, ether, amide,
amine, imine, imide, azide, nitrate, nitrile, nitrite or thiol
spacer group with the chain carbon 1.about.12. The first spacer
group R links with polar groups Lp. The polar group Lp may include
--Cl, --Br, --I, --NO.sub.2, --SO.sub.3--, --H--, --CN, --NCO,
--OCN, --CO.sub.2--, --OH, --OR*, --OC(O)CR*, --SR,
--SO.sub.2N(R*).sub.2, --SO.sub.2R*, SOR, --OC(O)R*, --C(O)OR*;
--C(O)R*; --Si(OR*).sub.3; --Si(R*).sub.3; epoxyl groups, where R*
is H, an unbranched or branched, cyclic or noncyclic saturated or
unsaturated alkyl or alkenyl or alkynyl groups.
[0044] The silicon particles are mixed with a solvent to form the
silicon containing solution. The solvents include, for example:
glycol ethers such as 2-methoxyethyl ether(diglyme), ethylene
glycol monomethyl ether, and propylene glycol monomethyl ether;
propylene glycol monomethyl ether acetate; lactates such as methyl
lactate and ethyl lactate; propionates such as methyl propionate,
ethyl propionate, ethyl ethoxy propionate and methyl-2-hydroxy
isobutyrate; cellosolve esters such as methyl cellosolve acetate;
aromatic hydrocarbons such as toluene and xylene; and ketones such
as acetone, methylethyl ketone, cyclohexanone and 2-heptanone. Two
or more kinds of solvents can be used. The viscosity of the silicon
containing solution is in a range from about 0.2 centipoise to
about 3000 centipoise in some embodiments. The silicon containing
solution can be spin-coated over the bottom layer by using a
photo-resist coating apparatus, or other suitable coating
apparatus. The silicon containing solution may further contain
stabilizer. The stabilizer adjusts pH to suitable value to
stabilize the silicon containing solution. The pH value ranges from
2 to 12. The stabilizer includes organic acid or base.
[0045] In some embodiments, the silicon particle or the silicon
cluster include silicon in an amount of 50 wt % or more. In other
embodiments, the silicon particle or the silicon cluster contains
silicon in an amount of 60 wt % or more. In some embodiments, the
Si amount of the silicon particle or the silicon cluster is up to
70 wt % and in up to 80 wt % in other embodiments. If any
additional solid additive is mixed with the silicon containing
solution, the silicon amount is calculated based on the total
weight of solid elements of the silicon solution other than the
solvent.
[0046] In some embodiments, the middle layer 40 further includes an
organic polymer. The organic polymer includes a silicon containing
polymer. The silicon containing polymer includes an organic polymer
and a cross-linker. In certain embodiments, the silicon containing
polymer further includes a chromophore (dye), a photo acid
generator, a base quencher and/or fluorocarbon. The organic polymer
backbone can be polyhydroxystyrene (PHS), poly methyl methacrylate
(PMMA), polyether, and combinations thereof, and other organic
polymers containing aromatic rings.
[0047] In some embodiments, after the middle layer 40 is formed, a
thermal operation, such as an annealing operation is performed. The
annealing operation is performed in addition to or instead of the
baking operation as set forth above. The annealing operation makes
the surface of the coated middle layer 40 smooth or flat. After the
annealing, the surface roughness Ra of the middle layer 40 is more
than 0 nm and less than 5 nm in some embodiments.
[0048] In some embodiments, a temperature of the annealing
operation is in a range from about 250.degree. C. to about
1000.degree. C. as a substrate temperature, and is in a range from
about 300.degree. C. to about 500.degree. C. in other embodiments.
In some embodiments, the annealing operation is thermal baking on a
baking plate. In such a case, a process time of the thermal baking
is in a range from about 30 sec to about 600 sec in some
embodiments, and is in a range from about 60 sec to about 300 sec
in other embodiments.
[0049] In other embodiments, the annealing operation utilizes
electromagnetic waves having a wavelength in a range from about 120
nm to about 12,000 nm. In certain embodiments, the annealing
operation is lamp annealing. In such a case, a process time of the
lamp annealing is in a range from about 1 sec to about 180 sec in
some embodiments, and is in a range from about 10 sec to about 60
sec in other embodiments. In other embodiments, the annealing
operation is laser annealing. In such a case, a process time of the
laser annealing is in a range from about 0.1 msec to about 10 sec
in some embodiments, and is in a range from about 10 msec to about
1 sec in other embodiments.
[0050] In some embodiments, the annealing operation includes 2
steps including a first step at a first temperature and a second
step at a second temperature higher than the first temperature. The
first temperature is in a range from about 80.degree. C. to about
200.degree. C. and the second temperature is in a range from about
250.degree. C. to about 1000.degree. C. in some embodiments.
[0051] After the annealing operation, the thickness of the middle
layer 40 is in a range from about 15 nm to about 90 nm in some
embodiments, and is in a range from about 20 nm to about 70 nm on
other embodiments.
[0052] Further, as shown in FIG. 3, a photo resist pattern 50 is
formed over the middle layer. A photo resist layer is spin-coated
on the middle layer, and the photo resist layer is exposed with an
exposure light/beam through a photo mask. The exposure light/beam
can be deep ultra violet (DUV) light, such as KrF excimer laser
light and ArF excimer laser light, extreme ultra violet (EUV) light
having a wavelength around 13.5 nm, an X-ray, and/or electron beam.
In some embodiments, multiple exposure processes are applied. After
development of the exposed photo resist, the resist pattern 50 is
obtained.
[0053] In some embodiments, an adhesion layer is disposed between
the middle layer 40 and the photo resist layer 50.
[0054] Then, as shown in FIG. 4, the middle layer 40 is patterned
to form a patterned middle layer 42 by using the photo resist
pattern 50 as an etching mask. Since the middle layer 40 is mainly
made of silicon, one or more dry etching operations using Cl.sub.2,
HBr, SF.sub.6 and/or other suitable etching gas are employed to
pattern the middle layer 40. A CD variation between the photo
resist pattern 50 and the patterned middle layer 42 is within .+-.2
nm in some embodiments, and is within .+-.1.5 nm in other
embodiments.
[0055] Further, as shown in FIG. 5, the bottom layer 30 is
patterned to form a patterned bottom layer 32 by using the
patterned middle layer 42 as an etching mask. When the bottom layer
30 is made of organic material, one or more dry etching operations
using O.sub.2, SO.sub.2, CO.sub.2 and/or other suitable etching gas
are employed to pattern the bottom layer 30. A CD variation between
the patterned middle layer 42 and the patterned bottom layer 32 is
within .+-.2 nm in some embodiments, and is within .+-.1.5 nm in
other embodiments. A CD variation between the resist pattern 50 and
the patterned bottom layer 32 is within .+-.3 nm in some
embodiments, and is within .+-.2 nm in other embodiments.
[0056] Subsequently, as shown in FIG. 6, the underlying layer 20 is
patterned to form a target pattern 22 by using the patterned middle
layer 42 and the patterned bottom layer 32 as an etching mask.
Depending on the material of the underlying layer 20, an
appropriate etching gas is elected.
[0057] A CD variation between the resist pattern 50 and the target
pattern 22 is within .+-.4 nm in some embodiments, and is within
.+-.3 nm in other embodiments. After the target pattern 22 is
formed, the patterned middle layer 42 and the patterned bottom
layer 32 are removed.
[0058] In some embodiments, the patterned middle layer 42 is
removed before patterning the underlying layer 20 and the
underlying layer 20 is patterned by using the patterned bottom
layer 32 as an etching mask.
[0059] As a middle layer of a tri-layer resist system, a silicon
containing polymer, such as polysiloxane has been used. A silicon
amount of polysiloxane is less than 50 wt %. In contrast, the
middle layer of the present disclosure includes silicon in an
amount of 50 wt % or more. Accordingly, a higher etching
selectivity and a lower CD variation between the middle layer 40
and bottom layer 30 are obtained. In some embodiments, the middle
layer 40 is free from silicon polymer such as polysiloxane. In
other embodiments, the middle layer 40 contains silicon polymer,
such as polysiloxane, and silicon particles or clusters as set
forth above, such that the silicon amount in the middle layer 40 is
50 wt % or more.
[0060] FIGS. 8-12 show various stages of manufacturing a
semiconductor device according to another embodiment of the present
disclosure. It is understood that additional operations can be
performed before, during, and after processes shown by FIGS. 8-12,
and some of the operations described below can be replaced or
eliminated, for additional embodiments of the method. The order of
the operations/processes may be interchangeable. Materials,
configurations, dimensions, structures, conditions and operations
the same as or similar to those explained with respect to FIGS. 1-7
may be employed in the following embodiments, and some of the
explanations may be omitted.
[0061] FIGS. 8-12 show a bi-layer resist system, in which the
bottom layer 30 is not used. As shown in FIG. 8, an underlying
layer 20 to be patterned is formed over a substrate 10. One or more
layers or structures are provided between the underlying layer 20
and the substrate 10 in some embodiments.
[0062] Then, as shown in FIG. 9, a silicon containing layer 40 is
formed on the underlying layer 20. Further, similar to FIG. 3, a
photo resist pattern 50 is formed over the middle layer, as shown
in FIG. 10. Subsequently, the silicon containing layer 40 is
patterned as shown in FIG. 11. Then, the underlying layer 20 is
patterned by one or more etching operations using the patterned
silicon containing layer 42 as an etching mask, as shown in FIG.
12. In some embodiments, the patterned silicon containing layer 42
is removed thereafter.
[0063] FIGS. 13-15 show various stages of manufacturing a
semiconductor device according to another embodiment of the present
disclosure. It is understood that additional operations can be
performed before, during, and after processes shown by FIGS. 13-15,
and some of the operations described below can be replaced or
eliminated for additional embodiments of the method. The order of
the operations/processes may be interchangeable. Materials,
configurations, dimensions, structures, conditions and operations
the same as or similar to those explained with respect to FIGS.
1-12 may be employed in the following embodiments, and some of the
explanations may be omitted.
[0064] In this embodiment, the silicon containing layer (middle
layer 40 in the foregoing embodiments) is photo sensitive, and can
be patterned by one or more lithography operation. In some
embodiments, the silicon containing layer includes a photo active
compound (PAC). The PACs are photoactive components, such as
photoacid generators, photobase generators, free-radical
generators, or the like. The PACs may be positive-acting or
negative-acting. In some embodiments in which the PACs are a
photoacid generator, the PACs include halogenated triazines, onium
salts, diazonium salts, aromatic diazonium salts, phosphonium
salts, sulfonium salts, iodonium salts, imide sulfonate, oxime
sulfonate, diazodisulfone, disulfone, o-nitrobenzylsulfonate,
sulfonated esters, halogenated sulfonyloxy dicarboximides,
diazodisulfones, .alpha.-cyanooxyamine-sulfonates, imidesulfonates,
ketodiazosulfones, sulfonyldiazoesters,
1,2-di(arylsulfonyl)hydrazines, nitrobenzyl esters, and the
s-triazine derivatives, combinations of these, or the like. The
group which will decompose, otherwise known as a leaving group or,
in some embodiments in which the PAC is a photoacid generator, an
acid labile group, is attached to the hydrocarbon structure so
that, it will react with the acids/bases/free radicals generated by
the PACs during exposure. In some embodiments, the group which will
decompose is a carboxylic acid group, a fluorinated alcohol group,
a phenolic alcohol group, a sulfonic group, a sulfonamide group, a
sulfonylimido group, an (alkylsulfonyl) (alkylcarbonyl)methylene
group, an (alkylsulfonyl)(alkyl-carbonyl)imido group, a
bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imido group,
a bis(alkylsylfonyl)methylene group, a bis(alkylsulfonyl)imido
group, a tris(alkylcarbonyl methylene group, a
tris(alkylsulfonyl)methylene group, combinations of these, or the
like. Specific groups that are used for the fluorinated alcohol
group include fluorinated hydroxyalkyl groups, such as a
hexafluoroisopropanol group in some embodiments. Specific groups
that are used for the carboxylic acid group include acrylic acid
groups, methacrylic acid groups, or the like. Other suitable
materials are included in a photo sensitive silicon containing
layer.
[0065] When the silicon containing layer is photo sensitive, no
additional photo resist, such as photo resist pattern 50 in the
foregoing embodiments, is necessary.
[0066] As shown in FIG. 13, a photo sensitive silicon containing
layer 41 is formed over the underlying layer 20 including one or
more layers of dielectric material or conductive material. The
thickness of the photo sensitive silicon containing layer 41 is in
a range from about 20 nm to about 100 nm in some embodiments, and
is in a range from about 30 nm to about 80 nm in other embodiments.
Then, a baking operation and/or an annealing operation as set forth
above are performed. In some embodiments, the silicon containing
layer 41 after the baking and/or annealing contains silicon in an
amount of 50 wt % or more. In other embodiments, the silicon
containing layer 41 contains silicon in an amount of 60 wt % or
more. In certain embodiments, the Si amount of the silicon
containing layer 41 is up to 70 wt % and in up to 80 wt % in other
embodiments.
[0067] Then, as shown in FIG. 14, the photo sensitive silicon
containing layer 41 is exposed to an exposure light/beam through a
photo mask. The exposure light/beam can be deep ultra violet (DUV)
light, such as KrF excimer laser light and ArF excimer laser light,
extreme ultra violet (EUV) light having a wavelength around 13.5
nm, an X-ray, and/or electron beam. In some embodiments, multiple
exposure processes are applied. After development of the exposed
photo resist, the pattern silicon containing layer 43 is
obtained.
[0068] Subsequently, as shown in FIG. 15, the underlying layer 20
is patterned to form a target pattern 22 by using the patterned
silicon containing layer 43 as an etching mask. Depending on the
material of the underlying layer 20, an appropriate etching gas is
elected.
[0069] A CD variation between the pattern silicon containing layer
43 and the target pattern 22 is within .+-.4 nm in some
embodiments, and is within .+-.3 nm in other embodiments. After the
target pattern 22 is formed, the pattern silicon containing layer
43 are removed in some embodiments.
[0070] FIGS. 16-20 show various stages of manufacturing a
semiconductor device according to another embodiment of the present
disclosure. It is understood that additional operations can be
performed before, during, and after processes shown by FIGS. 16-20,
and some of the operations described below can be replaced or
eliminated for additional embodiments of the method. The order of
the operations/processes may be interchangeable. Materials,
configurations, dimensions, structures, conditions and operations
the same as or similar to those explained with respect to FIGS.
1-15 may be employed in the following embodiments, and some of the
explanations may be omitted.
[0071] Similar to FIG. 1, a bottom layer 30 is formed over the
underlying layer 20, as shown in FIG. 16. Then, as shown in FIG.
17, a photo sensitive silicon containing layer 41 is formed over
the bottom layer 30. The thickness of the photo sensitive silicon
containing layer 41 is in a range from about 20 nm to about 100 nm
in some embodiments, and is in a range from about 30 nm to about 80
nm in other embodiments.
[0072] Then, a baking operation and/or an annealing operation as
set forth above are performed. In some embodiments, the silicon
containing layer 41 after the baking and/or annealing contains
silicon in an amount of 50 wt % or more. In other embodiments, the
silicon containing layer 41 contains silicon in an amount of 60 wt
% or more. In certain embodiments, the Si amount of the silicon
containing layer 41 is up to 70 wt % and in up to 80 wt % in other
embodiments.
[0073] Then, as shown in FIG. 18, the photo sensitive silicon
containing layer 41 is exposed to an exposure light/beam through a
photo mask. The exposure light/beam can be deep ultra violet (DUV)
light, such as KrF excimer laser light and ArF excimer laser light,
extreme ultra violet (EUV) light having a wavelength around 13.5
nm, an X-ray, and/or electron beam. In some embodiments, multiple
exposure processes are applied. After development of the exposed
photo resist, the pattern silicon containing layer 43 is
obtained.
[0074] Further, as shown in FIG. 19, the bottom layer 30 is
patterned to form a patterned bottom layer 32 by using the
patterned silicon containing layer 43 as an etching mask. When the
bottom layer 30 is made of organic material, one or more dry
etching operations using O.sub.2, SO.sub.2, CO.sub.2 and/or other
suitable etching gas are employed to pattern the bottom layer 30. A
CD variation between the patterned silicon containing layer 43 and
the patterned bottom layer 32 is within .+-.2 nm in some
embodiments, and is within .+-.1.5 nm in other embodiments.
[0075] Subsequently, as shown in FIG. 20, the underlying layer 20
is patterned to form a target pattern 22 by using the patterned
silicon containing layer 43 and the patterned bottom layer 32 as an
etching mask. Depending on the material of the underlying layer 20,
an appropriate etching gas is elected.
[0076] A CD variation between the patterned silicon containing
layer 43 and the target pattern 22 is within .+-.4 nm in some
embodiments, and is within .+-.3 nm in other embodiments. After the
target pattern 22 is formed, the patterned silicon containing layer
43 and the patterned bottom layer 32 are removed. In some
embodiments, the patterned silicon containing layer 43 is removed
before patterning the underlying layer 20 and the underlying layer
20 is patterned by using the patterned bottom layer 32 as an
etching mask.
[0077] FIGS. 21-25 show various stages of manufacturing a
semiconductor device according to another embodiment of the present
disclosure. It is understood that additional operations can be
performed before, during, and after processes shown by FIGS. 21-25,
and some of the operations described below can be replaced or
eliminated for additional embodiments of the method. The order of
the operations/processes may be interchangeable. Materials,
configurations, dimensions, structures, conditions and operations
the same as or similar to those explained with respect to FIGS.
1-20 may be employed in the following embodiments, and some of the
explanations may be omitted.
[0078] The semiconductor devices include interconnect structures
that include a plurality of interconnect pattern (line) layers
having conductive patterns and a plurality of contact holes/vias
for connecting various features in one portion/feature of a
semiconductor chip (die) to other portions/features of the chip.
The interconnect and via structures are formed of conductive
materials such as metal, and the semiconductor devices include
several interconnect layers in various embodiments.
[0079] The interconnect layer patterns in different layers are also
coupled to one another through vias that extend vertically between
one or several interconnect layers. The interconnect layer patterns
are coupled to external features and can represent bit lines,
signal lines, word lines, and various input/output connections in
some embodiments. In some embodiments of the disclosure, each of
the interconnect structures is formed by a damascene process, in
which a layer of inter-metal dielectric (IMD) material is
deposited, trenches and vias are formed and filled with conductive
material (e.g., copper or aluminum or various alloys) and the
surface is planarized by chemical mechanical polishing (CMP),
although other patterning techniques are used in other
embodiments.
[0080] As shown in FIG. 21, underlying structures 115 are disposed
over an underlying layer and covered by a multilayer structure 120.
In some embodiments, the underlying layer is a substrate 110. In
one embodiment, the substrate 110 is a silicon substrate. The
underlying structures 115 include various devices, structures,
layers and/or elements. Examples of the underlying devices may
include static random access memories (SRAMs) and/or other logic
circuits, passive components such as resistors, capacitors, and
inductors, and active components such as P-channel field effect
transistors (PFET), N-channel FET (NFET), metal-oxide semiconductor
field effect transistors (MOSFET), complementary metal-oxide
semiconductor (CMOS) transistors, such as a FinFET, bipolar
transistors, high voltage transistors, high frequency transistors,
other memory cells, and combinations thereof. The semiconductor
device may include a plurality of semiconductor devices (e.g.,
transistors), which may be interconnected. It is understood,
however, that this disclosure is not limited to a particular type
of device.
[0081] These underlying devices 115 are covered by one or more of
first interlayer dielectric (ILD) layers 122. The first interlayer
dielectric layer 122 includes silicon oxide, silicon nitride,
silicon oxynitride (SiON), SiOCN, fluorine-doped silicate glass
(FSG), or a low-k dielectric material, or any other suitable
dielectric material. The first interlayer dielectric layer may be
formed by chemical vapor deposition (CVD) or other suitable film
forming processes. The formed first interlayer dielectric layer may
be subjected to a planarization process, such as an etch back
process and/or a chemical mechanical polishing process.
[0082] After the first interlayer dielectric layer 122 is formed,
an etch stop layer 124 is formed over the first interlayer
dielectric layer 122. The etch stop layer 124 includes any known
etch stop material, including, but not limited to, a silicon oxide,
silicon nitride, silicon oxynitride, aluminum oxide, aluminum
nitride, aluminum fluoride, titanium nitride, tantalum oxide,
magnesium fluoride, and titanium silicon nitride. The thickness of
the etch stop layer 124 is in a range from about 1 nm to about 10
nm in some embodiments. The etch stop layer 124 can be formed by
CVD, atomic layer deposition (ALD) or any other suitable film
forming methods.
[0083] Further, a second interlayer dielectric layer 126 is formed
over the etch stop layer 124. The second interlayer dielectric 126
is made of a low-k dielectric material in some embodiments. The
expression "low-k" material refers to materials with a dielectric
constant less than that of SiO.sub.2 (about 3.9). Suitable low-k
dielectric materials include flowable oxides which are basically
ceramic polymers, such as hydrogen silsesquioxane (HSQ). HSQ-type
flowable oxides are used for gap filling between metal lines
because of their flowability and ability to fill small openings.
Additional low-k dielectrics include organic low-k materials,
typically having a dielectric constant of about 2.0 to about 3.8.
Organic low-k materials include a poly(arylene) ether, BCB
(divinylsiloxane bis-benzocyclobutene), and organic-doped silica
glasses (OSG) (also known as carbon-doped glasses). Other suitable
types of low-k dielectrics are fluorine-doped silicate glasses
(FSG) and SiCOH. FSG include dielectrics formed from precursor
gases SiF.sub.4, SiH.sub.4, and N.sub.2O and dielectrics formed
from the precursors SiF.sub.4, tetraethylorthosilicate (TEOS), and
O.sub.2. Dielectrics formed from TEOS and SiF.sub.4 are known as
fluorinated TEOS or FTEOS. The thickness of the second interlayer
dielectric layer 126 is in a range from about 10 nm to about 100 nm
in some embodiments.
[0084] Further, a hard mask layer 128 is formed over the second
inter layer dielectric layer 126. The hard mask layer 128 includes
an insulating material, such as a silicon oxide, silicon nitride or
a metal based material, such as a TiN or TaN. The thickness of the
hard mask layer 128 is in a range from about 1 nm to about 10 nm in
some embodiments.
[0085] In addition, in some embodiments, an antireflection coating
layer (not shown) is formed over the hard mask layer 128 to improve
photolithographic pattern fidelity during a subsequent process
step. In certain embodiments, the antireflection coating layer is a
nitrogen-free anti-reflection material comprising an organic
material. In other embodiments, the antireflection coating layer
includes TiN. The thickness of the antireflection coating layer is
in a range from about 1 nm to about 10 nm in some embodiments. In
some embodiments, a TiN layer is used as the hard mask layer and
the antireflection layer.
[0086] After the hard mask layer 128 (and antireflection coating
layer) is formed, a multilayer structure 130 is formed over the
hard mask layer 128 (and antireflection coating layer), as shown in
FIG. 21. The multilayer structure 130 includes a bottom layer 132
and a middle layer 134, similar to the bottom layer 30 and the
middle layer 40. The bottom layer 132 is used to planarize the
structure, as the underlying structure may be uneven depending on
the structure of the devices 115 formed on the substrate 110.
[0087] The bottom layer 132 and the middle layer 134 are made of
different materials such that the optical properties and/or etching
properties of the bottom layer 132 and the middle layer 134 are
different from each other.
[0088] After the middle layer 134 is formed, a photo resist layer
136 is formed over the middle layer 134, as shown in FIG. 21. The
photo resist for the photo resist layer 136 is a chemically
amplified photo resist and can be a positive tone photo resist or a
negative tone photo resist. After the photo resist is spin coated
on the middle layer 134, a baking operation at a substrate
temperature in a range from about 80.degree. C. to 120.degree. C.
is performed in some embodiments.
[0089] Next, the photo resist layer 136 is exposed with an exposure
light/beam through a photo mask. The exposure light/beam can be
deep ultra violet (DUV) light, such as KrF excimer laser light and
ArF excimer laser light, extreme ultra violet (EUV) light having a
wavelength around 13.5 nm, an X-ray, and/or electron beam. In some
embodiments, multiple exposure processes are applied.
[0090] FIG. 22 shows a cross section after the exposed resist is
baked (post-exposure bake) and developed by a developing solution
and a post-baking process is performed. When a positive tone
chemically amplified resist is used, acid generated by the exposure
light from a photo acid generator (PAG) in the photo resist cleaves
acid-cleavable polymers in the photo resist during the
post-exposure baking. After the acid cleaves the polymer, the
polymer becomes more hydrophilic (i.e., soluble in an aqueous
developer). After the polymer becomes more hydrophilic, the polymer
cannot be dissolved by organic solvent, for example, normal butyl
acetate, but can be dissolved by a basic solution, for example,
2.38% tetramethylammonium hydroxide (TMAH) solution.
[0091] When a negative tone chemically amplified resist is used,
acid generated by the exposure light from a photo acid generator
(PAG) in the photo resist catalyzes a cross-linking reaction of
acid catalyzed cross linkable polymer in the photo resist or causes
polymeric pinacol in the photo resist to undergo pinacol
rearrangement, during the post-exposure baking. After the polymer
cross linking or the undergoing of pinacol rearrangement, the
polymers become more hydrophobic. After the polymer become more
hydrophobic, the polymers are not dissolved by a basic developing
solution, for example, 2.38% TMAH solution.
[0092] Since the middle layer 134 is not photo-sensitive (not a
photo resist), the developed patterns of the photo resist layer 136
are formed on the middle layer and upper surfaces of the middle
layer 134 are exposed where no resist patterns exist.
[0093] After the photo resist layer is patterned, the middle layer
134 are patterned by using one or more etching operations, using
the patterned photo resist layer 136 as an etching mask, as shown
in FIG. 23. After the patterning operation(s), the photo resist
layer 136 is removed.
[0094] Further, in some embodiments, as shown in FIG. 24, the
bottom layer 132 and the hard mask layer 128 are patterned using
appropriate etchants and etching operations for each layer. After
the patterning operation(s), the middle layer 134 and the bottom
layer 132 are removed.
[0095] Subsequently, by using the patterned hard mask 128 as an
etching mask, the second interlayer dielectric layer 126, the etch
stop layer 124 and the first interlayer dielectric layer 122 are
patterned by appropriate etching operations, as shown in FIG. 25.
After the patterning operation(s), the hard mask layer 128 is
removed.
[0096] Then, the patterns (e.g., through-hole patterns) are filled
with conductive material, such as Al, Cu, W, Co, or Ni. The
conductive material is deposited by CVD, ALD, PVD, electroplating
or any other suitable film formation method, and the deposited
conductive material is subsequently planarized by a CMP operation
or etch-back operation. It is understood that the structure shown
in FIG. 25 undergoes further CMOS processes to form various
features such as interconnect vias, interconnect metal layers,
passivation layers, etc.
[0097] The various embodiments or examples described herein offer
several advantages over the existing art. In the present
disclosure, by using a silicon containing middle layer as set forth
above, it is possible to improve pattern size control in the
lithographic and etching operations.
[0098] According to one aspect of the disclosure, in a pattern
formation method, a bottom layer is formed over an underlying
layer. A middle layer is formed over the bottom layer. A resist
pattern is formed over the middle layer. The middle layer is
patterned by using the resist pattern as an etching mask. The
bottom layer is patterned by using the patterned middle layer. The
underlying layer is patterned. The middle layer contains silicon in
an amount of 50 wt % or more and an organic material. In one or
more of the foregoing and following embodiments, an annealing
operation is further performed after the middle layer is formed. In
one or more of the foregoing and following embodiments, a
temperature of the annealing operation is in a range from
200.degree. C. to 500.degree. C. In one or more of the foregoing
and following embodiments, the annealing operation is thermal
baking on a baking plate. In one or more of the foregoing and
following embodiments, a process time of the thermal baking is in a
range from 30 sec to 300 sec. In one or more of the foregoing and
following embodiments, the annealing operation is lamp annealing.
In one or more of the foregoing and following embodiments, the
annealing operation is laser annealing. In one or more of the
foregoing and following embodiments, a thickness of the middle
layer after the annealing operation is in a range from 15 nm to 90
nm. In one or more of the foregoing and following embodiments, the
bottom layer is made of an organic material. In one or more of the
foregoing and following embodiments, a thickness of the bottom
layer is in a range from 50 nm to 200 nm. In one or more of the
foregoing and following embodiments, the middle layer contains
silicon in an amount of 80 wt % or less. In one or more of the
foregoing and following embodiments, the middle layer is formed by
spin-coating a silicon containing solution. In one or more of the
foregoing and following embodiments, the silicon containing
solution includes a silicon particle and a solvent. In one or more
of the foregoing and following embodiments, a size of the silicon
particle is in a range from 1 nm to 20 nm. In one or more of the
foregoing and following embodiments, the silicon particle includes
a silicon core surrounded by a plurality of ligands. In one or more
of the foregoing and following embodiments, a diameter of the
silicon core is in a range from 2 nm to 10 nm. In one or more of
the foregoing and following embodiments, each of the plurality of
ligands is an organic ligand. In one or more of the foregoing and
following embodiments, the organic ligand has a chemical structure
R-Lp, which includes at least a first spacer group R and a polar
group Lp, the first spacer group R include one or more of hydrogen,
aromatic carbon ring, or straight or cyclic alkyl, alkoxyl,
fluoroalkyl, fluoroalkoxyl, alkene, alkyne, hydroxyl, ketone,
aldehyde, carbonate, carboxylic acid, ester, ether, amide, amine,
imine, imide, azide, nitrate, nitrile, nitrite or thiol spacer
group with the chain carbon 1.about.12, and the polar group Lp
includes one or more of --Cl, --Br, --I, --NO.sub.2, --SO.sub.3--,
--H--, --CN, --NCO, --OCN, --CO.sub.2--, --OH, --OR*, --OC(O)CR*,
--SR, --SO.sub.2N(R*).sub.2, --SO.sub.2R*, SOR, --OC(O)R*,
--C(O)OR*; --C(O)R*; --Si(OR*).sub.3; --Si(R*).sub.3; epoxyl
groups, where R* is H, an unbranched or branched, cyclic or
noncyclic saturated or unsaturated alkyl or alkenyl or alkynyl
groups.
[0099] In accordance with another aspect of the present disclosure,
in a pattern formation method, a Si-containing layer is formed over
an underlying layer. A resist pattern is formed over the
Si-containing layer. The Si-containing layer is patterned by using
the resist pattern as an etching mask. The underlying layer is
patterned by using the patterned Si-containing layer. The
Si-containing layer contains silicon in an amount of 50 wt % or
more or 70 wt % or less, and is none of an amorphous silicon layer,
a polysilicon layer, a silicon oxide based layer or a silicon
nitride based layer.
[0100] In accordance with another aspect of the present disclosure,
a silicon containing solution for manufacturing a semiconductor
device is provided. The silicon containing solution includes
silicon particles or silicon clusters and a solvent. The silicon
particles or the silicon clusters include silicon in an amount of
50 wt % or more or 80 wt % or less, and each of the silicon
particles or the silicon clusters includes a silicon core
surrounded by a plurality of organic ligands.
[0101] The foregoing outlines features of several embodiments or
examples so that those skilled in the art may better understand the
aspects of the present disclosure. Those skilled in the art should
appreciate that they may readily use the present disclosure as a
basis for designing or modifying other processes and structures for
carrying out the same purposes and/or achieving the same advantages
of the embodiments or examples introduced herein. Those skilled in
the art should also realize that such equivalent constructions do
not depart from the spirit and scope of the present disclosure, and
that they may make various changes, substitutions, and alterations
herein without departing from the spirit and scope of the present
disclosure.
* * * * *