U.S. patent application number 13/085698 was filed with the patent office on 2012-10-18 for footing reduction using etch-selective layer.
This patent application is currently assigned to ASM JAPAN K.K.. Invention is credited to Ryu Nakano.
Application Number | 20120264305 13/085698 |
Document ID | / |
Family ID | 47006700 |
Filed Date | 2012-10-18 |
United States Patent
Application |
20120264305 |
Kind Code |
A1 |
Nakano; Ryu |
October 18, 2012 |
Footing Reduction Using Etch-Selective Layer
Abstract
A method of forming side spacers upwardly extending from a
substrate, includes: providing a template constituted by a
photoresist formed on and in contact with an etch-selective layer
laminated on a substrate; anisotropically etching the template in a
thickness direction with an oxygen-containing plasma to remove a
footing of the photoresist and an exposed portion of the underlying
layer; depositing a spacer film on the template by atomic layer
deposition (ALD); and forming side spacers using the spacer film by
etching. The etch-selective layer has a substantially lower etch
rate than that of the photoresist.
Inventors: |
Nakano; Ryu;
(Sagamihara-shi, JP) |
Assignee: |
ASM JAPAN K.K.
Tokyo
JP
|
Family ID: |
47006700 |
Appl. No.: |
13/085698 |
Filed: |
April 13, 2011 |
Current U.S.
Class: |
438/694 ;
257/E21.249 |
Current CPC
Class: |
H01L 21/31138 20130101;
H01L 21/0337 20130101; H01L 21/0276 20130101; H01L 21/0273
20130101; H01L 21/31116 20130101 |
Class at
Publication: |
438/694 ;
257/E21.249 |
International
Class: |
H01L 21/311 20060101
H01L021/311 |
Claims
1. A method of forming side spacers upwardly extending from a
substrate, comprising: providing a template constituted by a
photoresist formed on and in contact with an etch-selective layer
laminated on a substrate, said photoresist having footing at a base
of the photoresist, said etch-selective layer having a
substantially lower etch rate than that of the photoresist;
anisotropically etching the template in a thickness direction with
an oxygen-containing plasma to remove the footing of the
photoresist and an exposed portion of the underlying layer;
depositing a spacer film on the template by atomic layer deposition
(ALD); and forming side spacers using the spacer film by
etching.
2. The method according to claim 1, wherein the side spacers are
for spacer-defined double patterning (SDDP).
3. The method according to claim 1, wherein the etch-selective
layer has a substantially higher etch rate than that of the side
spacers.
4. The method according to claim 1, wherein the etch-selective
layer is constituted by an organic bottom antireflective coating
(BARC) formed from a carbon/silicon-containing compound having a
ratio of (number of C, H, and O atoms in total)/(number of C
atoms-number of O atoms) which is no more than 5.
5. The method according to claim 1, wherein the etch-selective
layer is constituted by an organic bottom antireflective coating
(BARC) having an etch selectivity substantially equivalent to that
of a SiN film.
6. The method according to claim 1, wherein the etch-selective
layer is constituted by an inorganic silicon- or carbon-containing
layer as an antireflective coating (ARC) and a nitrogen-free oxide
layer laminated on the inorganic silicon- or carbon-containing
layer.
7. The method according to claim 1, further comprising etching the
photoresist of the template to trim the photoresist prior to the
anisotropical etching, wherein the etch-selective layer has a
substantial resistance to the trimming, and substantially no
footing of the photoresist remains.
8. The method according to claim 1, wherein the anisotropical
etching and the deposition of the spacer film are conducted
continuously in the same reactor.
9. The method according to claim 1, wherein the spacer film is
constituted by SiO.sub.2 or TiO.
10. The method according to claim 1, wherein an underlying layer
formed underneath the etch-selective layer is constituted by
amorphous carbon.
11. The method according to claim 1, wherein the etch-selective
layer is constituted by a Si-rich organic bottom antireflective
coating (BARC), and the anisotropical etching comprises trimming
the photoresist and removing the footing by an oxygen-containing
plasma, and then etching the Si-rich BARC by a fluorine-containing
oxygen plasma.
Description
BACKGROUND
[0001] 1. Field of the Invention
[0002] The present invention relates to semiconductor integrated
circuit manufacturing and, more particularly to a method of forming
side spacers, particularly on space-defined double patterning
(SDDP).
[0003] 2. Description of the Related Art
[0004] Photolithography technology has recently faced difficulty of
forming patterns having pitches smaller than the submicron level.
Various approaches have been studied, and one of the promising
methods is space-defined double patterning (SDDP) which makes it
possible to create narrow pitches beyond limitations of
conventional lithography such as light source wavelength and high
index immersion fluid. Generally, SDDP needs one conformal spacer
film and hardmask template wherein the conformal spacer film is
deposited on the template normally having convex patterns. A
silicon oxide layer is commonly used as a conformal spacer, and a
hardmask template is typically constituted by photoresist (PR)
prepared by a spin-on or CVD process.
[0005] As discussed below, the present inventors have recognized
several problems in SDDP and developed solutions thereto, which
solutions can also be applicable to general patterning processes.
Thus, the present invention relates to improvement on general
patterning processes using a hardmask, and particularly on
SDDP.
[0006] Any discussion of problems and solutions involved in the
related art has been included in this disclosure solely for the
purposes of providing a context for the present invention, and it
should not be taken as an admission that any or all of the
discussion were known at the time the invention was made.
[0007] In SDDP process flow, a photoresist pattern 12 is formed on
a substrate 11 as shown in FIG. 1(a). When etching a photoresist
layer to form the photoresist pattern, each formed photoresist
protrusion 12 has a widened footing portion at its bottom, and
thus, the distance between the formed photoresist protrusions at
their bottoms (W') is shorter than that their side walls (W). When
depositing a spacer layer 13 such as a SiO layer by plasma enhanced
atomic layer deposition (PE-ALD) over the photoresist pattern as
shown in FIG. 1(b), the spacer layer 13 deposits along the surface
of the photoresist pattern having the widened footing portions.
When the spacer layer is etched by, e.g., reactive ion etching
(RIE) to remove the top and bottom to form side spacers 14 as shown
in FIG. 1(c), the widened footings of the photoresist pattern are
transferred to the side spacers 14. As a result, the thickness of
the side spacer at the bottom appears to be widened (F), which is
significantly greater than the thickness of the side spacer itself,
thereby causing unexpected critical dimension (CD) changes or the
like.
[0008] In order to achieve patterning smaller than the resolution
limit by, e.g., SDDP, many photoresist trimming techniques such as
trimming by plasma have been reported. However, it is still
difficult to control the transferred footing shape. For example, by
using an underlying layer having an increased etch rate, while
trimming a photoresist layer, a mask pattern is formed in the
underlying layer (e.g., JP 2004-310019). However, by using a
combination of an underlying layer and a photoresist layer, even if
the footing of the etched photoresist can be smaller while trimming
the etched photoresist, a footing shape is transferred to and
formed in the underlying layer. Thus, the footing problem is not
solved. FIG. 2 shows this problem. When a photoresist layer which
is formed on an underlying layer 21 formed on a substrate 24 is
etched, a widened footing is formed in the etched photoresist 22 as
shown in FIG. 2(a). While trimming the etched photoresist 22
isotropically (FIG. 2(b)), the widened footing of the etched
photoresist is smaller. However, the footing of the etched
photoresist is transferred to the underlying layer as shown in FIG.
2(c).
SUMMARY
[0009] In some embodiments of the present invention, by conducting
plasma irradiation prior to formation of a spacer layer to
anisotropically etch a template constituted by a photoresist formed
on and in contact with an etch-selective layer laminated on a
substrate, said etch-selective layer has a substantially lower etch
rate than that of the photoresist, thereby reducing a widened
footing of the photoresist.
[0010] Some embodiments of the present invention provide a method
of forming side spacers upwardly extending from a substrate,
comprising: (i) providing a template constituted by a photoresist
formed on and in contact with an etch-selective layer laminated on
a substrate, said photoresist having footing at a base of the
photoresist, said etch-selective layer having a substantially lower
etch rate than that of the photoresist; (ii) anisotropically
etching the template in a thickness direction with an
oxygen-containing plasma to remove the footing of the photoresist
and an exposed portion of the underlying layer; (iii) depositing a
spacer film on the template by atomic layer deposition (ALD); and
(iv) forming side spacers using the spacer film by etching.
[0011] In some embodiments, the side spacers are for spacer-defined
double patterning (SDDP). In some embodiments, the etch-selective
layer has a substantially higher etch rate than that of the side
spacers. In some embodiments, the etch-selective layer is
constituted by an organic bottom antireflective coating (BARC)
formed from a carbon-containing (or carbon- and silicon-containing)
compound having a ratio of (number of C, H, and O atoms in
total)/(number of C atoms-number of O atoms) which is no more than
5. In some embodiments, the etch-selective layer is constituted by
an organic bottom antireflective coating (BARC) having an etch
selectivity substantially equivalent to that of a SiN film. In some
embodiments, the etch-selective layer is constituted by an
inorganic silicon- or carbon-containing layer as an antireflective
coating (ARC) and a nitrogen-free oxide layer laminated on the
inorganic silicon- or carbon-containing layer. In some embodiments,
the spacer film is constituted by SiO.sub.2, TiO, or any suitable
metal oxide materials (e.g., a co-assigned U.S. Provisional
Application No. 61/427,661, the disclosure of which is herein
incorporated by reference in its entirety). In some embodiments, an
underlying layer formed underneath the etch-selective layer is
constituted by amorphous carbon.
[0012] In some embodiments, any of the disclosed methods further
comprise etching the photoresist of the template to trim the
photoresist (e.g., by isotropical etching or any suitable etching)
prior to the anisotropical etching, wherein the etch-selective
layer has a substantial resistance to the isotropic trimming, and
substantially no footing of the photoresist remains. Particularly,
when the inorganic ARC is used as the etch-selective layer,
substantially no footing can remain. In some embodiments, the
anisotropical etching and the deposition of the spacer film are
conducted continuously in the same reactor.
[0013] For purposes of summarizing aspects of the invention and the
advantages achieved over the related art, certain objects and
advantages of the invention are described in this disclosure. Of
course, it is to be understood that not necessarily all such
objects or advantages may be achieved in accordance with any
particular embodiment of the invention. Thus, for example, those
skilled in the art will recognize that the invention may be
embodied or carried out in a manner that achieves or optimizes one
advantage or group of advantages as taught herein without
necessarily achieving other objects or advantages as may be taught
or suggested herein.
[0014] Further aspects, features and advantages of this invention
will become apparent from the detailed description which
follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] These and other features of this invention will now be
described with reference to the drawings of preferred embodiments
which are intended to illustrate and not to limit the invention.
The drawings are oversimplified for illustrative purpose and are
not necessarily to scale.
[0016] FIG. 1 is a schematic representation illustrating a part of
the SDDP sequence of (a) photoresist (PR) patterning, (b) SiO
deposition by PE-ALD, and (c) reactive ion etch (RIE).
[0017] FIG. 2 is a schematic representation illustrating a part of
the SDDP sequence of (a) photoresist (PR) patterning, (b) the
beginning of isotropic PR trimming, and (c) the end of isotropic PR
trimming.
[0018] FIG. 3 is a schematic representation illustrating a part of
the SDDP sequence of (a) photoresist (PR) patterning, (b) isotropic
PR trimming, (c) anisotropic etching (removal of the footing), (d)
etching of the etch-selective layer, (e) spacer layer deposition,
(f) etching of top and bottom of the etch-selective layer, (g)
removal of the PR, and (h) removal of the remaining etch-selective
layer and the top of the side spacers, according to an embodiment
of the present invention.
[0019] FIG. 4 is a schematic representation illustrating a part of
the SDDP sequence of (a) photoresist (PR) patterning, (b) isotropic
PR trimming, (c) anisotropic etching (removal of the footing and
the N-free layer), (d) etching of the etch-selective layer, (e)
spacer layer deposition, (f) etching of top and bottom of the
etch-selective layer, (g) removal of the PR, and (h) removal of the
remaining N-free layer and etch-selective layer and the top of the
side spacers, according to an embodiment of the present
invention.
DETAILED DESCRIPTION
[0020] In this disclosure, "gas" may include vaporized solids
and/or liquids and may be constituted by a mixture of gases. In
this disclosure, the reactant gas, the additive/carrier gas, and
the precursor may be different from each other or mutually
exclusive in terms of gas types, i.e., there is no overlap of gases
among these categories. In some embodiments, "film" refers to a
layer continuously extending in a direction perpendicular to a
thickness direction substantially without pinholes to cover an
entire target or concerned surface, or simply a layer covering a
target or concerned surface. In some embodiments, "layer" refers to
a structure having a certain thickness formed on a surface or a
synonym of film. In this disclosure, any defined meanings do not
necessarily exclude ordinary and customary meanings in some
embodiments. In the disclosure, "substantially lower",
"substantially higher", "substantially different", etc. refer to a
difference of at least 10%, 50%, 100%, 200%, 300%, or any ranges
thereof, for example. Also, in the disclosure, "substantially the
same", "substantially equivalent", "substantially uniform", etc.
refer to a difference of less than 20%, less than 10%, less than
5%, less than 1%, or any ranges thereof, for example. The numerical
numbers applied in examples may be modified by a range of at least
.+-.50% in other conditions, and further, in this disclosure, any
ranges indicated may include or exclude the endpoints. In the
present disclosure where conditions and/or structures are not
specified, the skilled artisan in the art can readily provide such
conditions and/or structures, in view of the present disclosure, as
a matter of routine experimentation.
[0021] In the disclosure, the "footing" or "widened footing"
generally refers to an outwardly extended portion at the bottom of
a protrusion relative to the side wall of the protrusion, said
extended portion being typically inclined or sloped. The size of
the footing may be defined as a difference between the width of the
protrusion at about 50% of the height and the width at the bottom.
In some embodiments, the "removal of the footing" does not
necessarily refer to removal of the entire footing, but refers to
removal of a substantial portion of the footing or substantially
diminishing the size of the footing.
[0022] In the disclosure, the "etch rate" refers to an actual etch
rate of a material in process or an etch rate evaluated beforehand
which is a dry etch rate (NF.sub.3 at 100.degree. C.) or a wet etch
rate (DHF at 1:100), depending on the actual process.
[0023] In the present disclosure where conditions and/or structures
are not specified, the skilled artisan in the art can readily
provide such conditions and/or structures, in view of the present
disclosure, as a matter of routine experimentation.
[0024] In some embodiments, in order to solve at least one or all
of the problems discussed above in patterning processes, an
etch-selective layer is formed underneath a PR pattern. The
etch-selective layer has a substantially lower etch rate than that
of the PR, but has a substantially higher etch rate than that of a
side spacer. In some embodiments, the etch-selective layer is
constituted by an organic BARC which has an etch selectivity
substantially equivalent to that of a SiN film. In some
embodiments, the BARC is formed from a carbon-containing (or
carbon- and silicon-containing) compound having a ratio of (number
of C, H, and O atoms in total)/(number of C atoms-number of O
atoms) which is no more than 5. The ratio is called "Ohnishi
parameter" (J. Electrochem Soc 143, 130 (1983) H. Gokan, S. Esho
and Y. Ohnishi, the disclosure of which is herein incorporated by
reference in its entirety). In general, the higher the ratio, the
higher the concentration of carbon becomes. When the concentration
of carbon is high, the etch rate becomes low. For example,
hexamethyldisiloxane (HMDSO) has a ratio of 5, hexamethyldisilazane
(HMDS) has a ratio of 4.2.
[0025] In some embodiments, the etch-selective layer is constituted
by an inorganic silicon- or carbon-containing layer and a
nitrogen-free oxide layer laminated on the inorganic silicon- or
carbon-containing layer. The nitrogen-free oxide layer is used in
order to inhibit the occurrence of resist poisoning, and this layer
can contribute to suppression of formation of a widened footing (by
inhibiting migration of N from the etch-selective layer to the
photoresist), but a thinner layer is better (e.g., about 1-3 nm) as
long as it is capable of inhibiting contact between the PR and the
inorganic silicon- or carbon-containing layer.
[0026] In some embodiments, the etch rate refers to chemical
resistance (low dry etch rate, NF.sub.3 at 100.degree. C.) or a wet
etch rate (DHF at 1:100).
[0027] FIG. 3 is a schematic representation illustrating a part of
the SDDP sequence using a BARC layer as the etch-selective layer,
which includes (a) photoresist (PR) patterning, (b) PR trimming
(e.g., isotropic trimming), (c) etching (e.g., anisotropic etching)
(removal of the footing), (d) etching of the etch-selective layer,
(e) spacer layer deposition, (f) etching of top and bottom of the
etch-selective layer, (g) removal of the PR, and (h) removal of the
remaining etch-selective layer and the top of the side spacers,
according to an embodiment of the present invention, which is not
intended to limit the invention. In some embodiments, step (b) can
be omitted, and in step (c), both PR trimming and footing removal
can be accomplished by any suitable etching.
[0028] In some embodiments, the sequences of forming a final
pattern using a BARC layer as the etch-selective layer are as
follows:
[0029] 1) A BARC layer 31 is formed on a substrate 34. The BARC
layer has high etch selectivity relative to a photoresist (PR).
[0030] 2) A photoresist film material is then applied on the BARC
layer, and prebaked, thereby forming a photoresist film. A pattern
circuit area of the photoresist film is then exposed to
irradiation, and then developed with a developing liquid, thereby
forming a photoresist pattern 32 in the photoresist film (FIG. 3
(a)).
[0031] 3) The photoresist has a widened footing as a result of the
patterning. Thus, the photoresist is subjected to isotropic
trimming using a plasma generated in an environment where a gas
containing oxygen is introduced, thereby forming a trimmed
photoresist 32a (FIG. 3(b)). Because the etching speed of the BARC
layer is lower than that of the photoresist, the footing of the
photoresist is effectively reduced. This trimming can be conducted
continuously from the formation of side spacers in the same
reactor. The subsequent steps 4) to 7) can also be conducted
continuously in the same reactor.
[0032] 4) The trimming may not sufficiently remove the footing of
the photoresist, although a reduction of the footing is
significant. Also, in some embodiments, trimming is not performed.
Thus, the template (including the substrate, BARC layer, and
photoresist) is subjected to anisotropic etching, thereby removing
the remaining footing and forming a photoresist 32b without footing
(FIG. 3(c)). The anisotropic etching continues to remove the BARC
layer, thereby forming the photoresist 32b and etched BARC layer
31a underneath the photoresist (FIG. 3(d)). Because the BARC layer
has higher resistance to etching than the photoresist, when the
BARC layer is removed, the photoresist is diminished to a certain
degree (the height of the photoresist is lowered due to the
anisotropic etching). Considering the above, an appropriate etch
selectivity of the BARC layer is selected.
[0033] 5) Next, an ALD film 33 is formed as a side spacer film on
the template (FIG. 3(e)). Since the ALD film is deposited on the
photoresist, the deposition temperature may be, for example, about
150.degree. C. or lower or about 100.degree. C. or lower, depending
on the heat resistance of the photoresist and BARC.
[0034] 6) The top and bottom portions of the side spacer film 33
are then removed, thereby forming provisional side spacers 33a
enclosing the photoresist 32b and the BARC layer 31a underneath the
photoresist as a core material (FIG. 3(f)).
[0035] 7) After the top of the side spacer film, the photoresist
32b is irradiated with an O.sub.2-containing plasma (FIG. 3(g)),
and the BARC layer 31a is irradiated with the O.sub.2-containing
plasma (FIG. 3(h)), thereby obtaining a final pattern with side
spacers 33b.
[0036] In the above, in some embodiments, the photoresist is
arranged at a pitch of about 80 nm (.+-.50%). In some embodiments,
the side of the photoresist prior to the trimming (FIG. 3(a)) has a
height of about 60 nm (.+-.50%), a width of about 26 nm to about 47
nm (.+-.50%), and a footing of about 11.1 nm (.+-.50%). In some
embodiments, the side of the photoresist after the trimming (FIG.
3(c)) has a height of about 47 nm (.+-.50%), a width of about 14 nm
to about 17 nm (.+-.50%), and a footing of about 0 nm.
[0037] In some embodiments, as the organic BARC, a resist used for
dry ArF or wet ArF can be used, which can be selected from the
group consisting of alicyclic acrylic resin, cycloolefin resin,
cyclolefin-maleic anhydride resin, and methacrylate resin. In some
embodiments, a BARC having a low Ohnishi parameter (high in carbon
concentration) can be used. In some embodiments, a BARC having high
silicon concentration ("a Si-rich BARC", e.g., at least 5, 10, or
20 atomic %) can be used. In some embodiments, the etch selectivity
of a BARC relative to the photoresist (footing) is adjusted by
changing the silicon content of the BARC so that the footing can
selectively be etched readily by adjusting the oxygen concentration
of an etchant (a Si-rich BARC has effective or substantial
resistance to oxygen plasma). As described below, the Si-rich BARC
can be etched by fluorine-containing oxygen plasma, whereas the
photoresist has effective or substantial resistance to the
fluorine-containing oxygen plasma so that the height of the
photoresist can effectively or substantially be maintained. In some
embodiments, the BARC can be applied by spin coating or further
baking after spin coating to vaporize a resist solvent. In some
embodiments, the thickness of the BARC is about 10 nm to about 50
nm. If the thickness is lower than the range, it will be difficult
to form a layer. On the other hand, if the thickness is greater
than the range, when removing the BARC, side spacers may be
significantly diminished.
[0038] In some embodiments, the trimming and the footing removal
etching can be conducted under conditions as follows:
TABLE-US-00001 Gas containing oxygen O.sub.2, N.sub.2O, and/or
CO.sub.2 Flow rate (sccm) of Oxygen- About 100 to about 2,000
containing gas Inert gas Ar, He Flow rate (sccm) of Inert gas About
500 to about 1,000 Plasma Temperature (.degree. C.) About 50 to
about 150, depending on conditions the thermal resistance of RR and
BARC Pressure (Pa) About 15 to about 800 RF frequency About 13.56
(MHz) RF power (W) About 30 to about 300
[0039] When using a gas containing more oxygen (e.g., more than 50%
of the gas in volume), the etch rate of the BARC becomes low,
whereas the etch rate of the photoresist becomes high. That is, the
higher the oxygen content of the etch gas, the lower the etch rate
of the BARC becomes.
[0040] In some embodiments, the removal of the BARC can be
conducted under conditions as follows or the conditions disclosed
in JP 10-261620, for example (the disclosure of which is herein
incorporated by reference in its entirety):
TABLE-US-00002 Gas for O.sub.2-containing O.sub.2, CF.sub.4 +
O.sub.2, CF.sub.3I + O.sub.2 plasma Flow rate (sccm) of About 1,000
to about 2,000 (CF.sub.4: about 10 O2-containing gas to about 100)
Plasma Temperature About 50 to about 150, depending on the
conditions (.degree. C.) thermal resistance of RR and BARC Pressure
(Pa) About 10 to about 2000 RF frequency About 2.45 GHz (about 400
to 1,200 W) + and power about 13.56 MHz (about 30 to 100 W)
[0041] When using a gas containing more oxygen (e.g., more than 50%
of the gas in volume), the etch rate of the BARC containing Si
becomes low, whereas when using a gas containing lower oxygen
concentration, etching effect by florin becomes more significant,
thereby increasing etch rate of the BARC (e.g., JP 2010-205967, the
disclosure of which is herein incorporated by reference in its
entirety).
[0042] In some embodiments, the ALD film is selected from the group
consisting of SiO, SiN, SiC, SiCN, and TiO. Any suitable ALD
methods can be used. In some embodiments, the methods disclosed in
a co-assigned application, U.S. patent application Ser. No.
12/901,323, can be used (the disclosure of which is herein
incorporated by reference in its entirety). For example, as a
process gas, a combination of BDEAS (bis(diethylamino)silane),
O.sub.2 (500 sccm), He (200 sccm), and Ar (2500 sccm) can be used.
In some embodiments, the pressure is about 200 Pa (.+-.50%), and RF
frequency (about 13.56 MHz.+-.50%), power (about 50 W.+-.50%), and
duration (about 0.4 seconds.+-.50%) may be used. After stabilizing
the pressure and gas flows in the reactor, the precursor is
introduced into the reactor for a certain time period to cause the
precursor to adsorb on the surface of a substrate, followed by
purging the remaining precursor with another gas. RF plasma is then
applied to the substrate, thereby oxidizing the adsorbed precursor.
The above steps constitute one cycle, and by repeating the cycle,
an ALD film such as a SiO film having a desired thickness can be
formed on the substrate.
[0043] In some embodiments, a pulse control valve can realize the
pulsing of the precursor and/or the inert/additive gas. Further, RF
power can be pulsed. In the above, the pulsing of the RF power can
be accomplished by adjusting a matching box (not shown). The RF
power requires a minimum time period for discharging, which is
typically as short as 8 msec. Thus, by adjusting the matching box,
the duration of the RF power can easily be controlled at about 0.1
sec, for example. In some embodiments, the average thickness
deposited per cycle may be about 0.05 nm/cycle to about 0.2
nm/cycle. The pulse supply of the precursor can be continued until
a desired thickness of film is obtained. If the desired thickness
of film is about 20 nm to about 100 nm, about 100 cycles to about
2,000 cycles (e.g., about 200 to about 1,000 cycles) may be
conducted.
[0044] In some embodiments, the removal of the top and bottom of
the ALD film can be conducted under conditions shown below:
TABLE-US-00003 Etching gas CHF.sub.3, CF.sub.4, C.sub.2F.sub.6 Flow
rate (sccm) of etching About 10 to about 100 gas Additive gas Ar,
O.sub.2 Flow rate (sccm) of additive About 10 to about 100 gas
Plasma Temperature About 50 to about 150, depending on the
conditions (.degree. C.) thermal resistance of RR and BARC Pressure
(Pa) Less than about 1 RF frequency About 13.56 (MHz) RF power (W)
About 50 to about 300
[0045] In some embodiments, the removal of the enclosed photoresist
and BARC through the opened top can be conducted under conditions
shown below.
TABLE-US-00004 Gas for O.sub.2-containing O.sub.2, CF.sub.4 +
O.sub.2 plasma Flow rate (sccm) of About 1,000 to about 2,000
(CF.sub.4: about 10 O.sub.2-containing gas to about 100) Plasma
Temperature About 50 to about 150, depending on the conditions
(.degree. C.) thermal resistance of RR and BARC Pressure (Pa) About
100 to about 200 RF frequency About 2.45 GHz (about 400 to 1,200 W)
+ and power about 13.56 MHz (about 30 to 100 W)
[0046] In some embodiments, in order to remove the enclosed
photoresist through the opened top, a gas containing a high
concentration (more than 50% in volume) of oxygen can be used.
After the completion of the removal of the enclosed photoresist, in
order to remove the BARC containing Si, a gas containing a low
concentration (less than 50% in volume) of oxygen can be used,
wherein the plasma can be intermittently or continuously applied.
If it takes a long time to remove the BARC including Si, the side
spacers may be diminished. Thus, considering the above, the oxygen
concentration (oxygen flow rate) should be appropriately
selected.
[0047] FIG. 4 is a schematic representation illustrating a part of
the SDDP sequence using a SiN layer as the etch-selective layer,
which includes (a) photoresist (PR) patterning, (b) isotropic PR
trimming, (c) anisotropic etching (removal of the footing and the
N-free layer), (d) etching of the etch-selective layer, (e) spacer
layer deposition, (f) etching of top and bottom of the
etch-selective layer, (g) removal of the PR, and (h) removal of the
remaining N-free layer and etch-selective layer and the top of the
side spacers, according to an embodiment of the present
invention.
[0048] In some embodiments, the sequences of forming a final
pattern using a SiN layer as the etch-selective layer are as
follows:
[0049] 1) A SiN film 41 is formed on a substrate 44. The SiN film
has high etch selectivity relative to a photoresist (PR). The
reason for using the SiN film instead of e.g., a SiON film is that
it is easier to set substantially different etch selectivity of the
SiN film, not only from that of a photoresist but also from that of
a SiO film constituting side spacers.
[0050] 2) Next, a super thin SiO film 45 (N-free film) is formed on
the SiN film. Alternatively, by oxidation of the surface of the SiN
film by e.g., O.sub.2 or N.sub.2O plasma treatment or other
oxidation methods, the surface of the SiN film can become N-free.
By using the N-free film, promotion of formation of a widened
footing can be suppressed. If a photoresist is in contact directly
with the SiN film, footing may be promoted due to the influence of
base group including nitrogen during lithography after formation of
a photoresist film. However, if the N-free film is thick, when
removing the N-free film in a subsequent step of removing the
photoresist and the SiN film after removing the top of a side
spacer film, the side spacers may also be diminished (i.e.,
lowering the height of the side spacers). Thus, it is preferable to
make the film thin (e.g., about 1-3 nm).
[0051] 3) The SiN film 45 and the N-free film 41 also serve as an
antireflective film (inorganic ARC).
[0052] 4) Next, a photoresist film material is then applied on the
N-free film and the SiN film, and prebaked, thereby forming a
photoresist film. A pattern circuit area of the photoresist film is
then exposed to irradiation, and then developed with a developing
liquid, thereby forming a photoresist pattern 42 in the photoresist
film (FIG. 4 (a)).
[0053] 5) The photoresist has a widened footing as a result of the
patterning. Thus, the photoresist is subjected to isotropic
trimming using a plasma generated in an environment where a gas
containing oxygen is introduced, thereby forming a trimmed
photoresist 42a (FIG. 4(b)). Because the etching speed of the SiN
film is lower than that of the photoresist, the footing of the
photoresist is effectively reduced (although FIG. 4(b) shows that
the N-free film is maintained, through the trimming, most portions
of the N-free film may be removed as the footing is reduced). This
trimming can be conducted continuously from the formation of side
spacers in the same reactor. The subsequent steps 6) to 10) can
also be conducted continuously in the same reactor.
[0054] 6) The trimming may not sufficiently remove the footing of
the photoresist, although a reduction of the footing is
significant. Also, in some embodiments, trimming is not performed.
Thus, the template (including the substrate, SiN film, and
photoresist) is subjected to anisotropic etching, thereby removing
the remaining footing and forming a photoresist 42b and the etched
N-free film 45a underneath the photoresist without footing (FIG.
4(c)). The anisotropic etching continues to remove the SiN film,
thereby forming the photoresist 42b, etched N-free film 45a, and
etched SiN film 41a underneath the photoresist (FIG. 4(d)). Because
the SiN film has higher resistance to etching than the photoresist,
when the SiN film is removed, the photoresist is diminished to a
certain degree (the height of the photoresist is lowered due to the
anisotropic etching). Considering the above, an appropriate etch
selectivity of the SiN film is selected.
[0055] 7) Next, an ALD film 43 is formed as a side spacer film on
the template (FIG. 4(e)). Since the ALD film is deposited on the
photoresist, the deposition temperature may be about 100.degree. C.
or lower.
[0056] 8) The top and bottom portions of the side spacer film 43
are then removed, thereby forming provisional side spacers 43a
enclosing the photoresist 42b, the N-free film 45a, and the SiN
film 41a underneath the photoresist as a core material (FIG.
4(f)).
[0057] 9) After the top of the side spacer film is removed, the
photoresist 42b is irradiated with an O.sub.2-containing plasma
(FIG. 4(g)).
[0058] 10) After the photoresist 42b is removed, in order to remove
the N-free film 45a and the SiN film 41a, they are irradiated with
a plasma generated in an environment with a gas containing florin
(FIG. 4(h)), thereby obtaining a final pattern with side spacers
43b.
[0059] In some embodiments, the substrate on which the
etch-selective layer is formed can be made of poly-silicon or
amorphous carbon or other carbon materials. When amorphous carbon
is used as the substrate without the etch-selective layer disclosed
herein, the amorphous carbon is etched while removing an underlying
layer, and as a result, a footing is transferred to the amorphous
carbon. In some embodiments, the substrate made of amorphous carbon
is used without formation of footing.
[0060] In some embodiments, the process conditions for the sequence
using the inorganic ARC as the etch-selective layer can be similar
to or the same as those for the sequence using the organic BARC as
the etch-selective layer as described earlier, unless stated
otherwise.
[0061] In some embodiments, the inorganic ARC can be formed by CVD
or ALD. In some embodiments, the thickness of the inorganic ARC is
about 5 nm to about 10 nm. In some embodiments, the inorganic ARC
may be selected from the group consisting of SiN, SiC, SiCN, and
TiO.
[0062] In some embodiments, the N-free film can be formed by
TEOS-Based CVD or ALD-SiO. In some embodiments, the thickness of
the SiO film may be about 1 nm to about 3 nm. The thinner the
better, as long as the film can prevent the photoresist and the SiN
film from contacting each other. In some embodiments, the N-free
film can be formed by an O.sub.2 plasma (e.g., using O.sub.2 gas at
a flow rate of 1,000 sccm and an RF power (13.56 MHz) of about 100
to about 500 W at a temperature of about 50-150.degree. C. under a
pressure of about 150-800 Pa for a duration of about 10 to about
180 seconds). The temperature depends on the thermal resistance of
the photoresist and BARC. In some embodiments, the depth of
oxidation by the O.sub.2 plasma is about 3 nm. In some embodiments,
the N-free film can be formed by a N.sub.2O plasma under conditions
corresponding to the O.sub.2 plasma. In some embodiments, the depth
of oxidation by the N.sub.2O plasma is about 3 nm.
[0063] In some embodiments, the trimming and the footing removal
etching can be conducted under conditions corresponding to those
used for the sequence for the organic BARC.
[0064] In some embodiments, the removal of the N-free film and the
SiN film can be conducted under conditions shown below.
TABLE-US-00005 Etching gas CHF.sub.3, CF.sub.4, C.sub.2F.sub.6 (low
flow of oxygen) Flow rate (sccm) of etching gas About 10 to about
100 Additive gas Ar, O.sub.2 Flow rate (sccm) of additive gas About
10 to about 100 Plasma Temperature About 50 to about 150, depending
on conditions (.degree. C.) the thermal resistance of RR and BARC
Pressure (Pa) Less than about 1 RF frequency About 13.56 (MHz) RF
power (W) About 30 to about 300
[0065] In some embodiments, in order to remove the inorganic films
(N-free film (SiO) and SiN), a gas containing a low concentration
of oxygen is used.
[0066] In some embodiments, the ALD film can be formed under
conditions corresponding to those used for the sequence for the
organic BARC.
[0067] In some embodiments, the removal of the top and bottom of
the ALD film can be conducted under conditions corresponding to
those used for the sequence for the organic BARC.
[0068] In some embodiments, the removal of the enclosed
photoresist, N-free film, and SiN film through the opened top can
be conducted under conditions corresponding to those used for the
sequence for the organic BARC.
[0069] In some embodiments, in order to remove the enclosed
photoresist through the opened top, a gas containing a high
concentration (more than 50% in volume) of oxygen can be used.
After the completion of the removal of the enclosed photoresist, in
order to remove the N-free film and SiN film, a gas containing a
low concentration (less than 50% in volume) of oxygen can be used,
wherein the plasma can be intermittently or continuously applied.
If it takes a long time to remove the N-free film and SiN film, the
side spacers may be diminished. Thus, considering the above, the
oxygen concentration (oxygen flow rate) should be appropriately
selected.
[0070] A remote plasma unit can be connected to the apparatus,
through which an etching gas or a process gas can be supplied to
the interior of the apparatus through a showerhead.
[0071] It will be understood by those of skill in the art that
numerous and various modifications can be made without departing
from the spirit of the present invention. Therefore, it should be
clearly understood that the forms of the present invention are
illustrative only and are not intended to limit the scope of the
present invention.
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