U.S. patent application number 11/580399 was filed with the patent office on 2007-02-08 for forming a dielectric layer using a hydrocarbon-containing precursor.
Invention is credited to Michael D. Goodner, Grant M. Kloster, Bob E. Leet, Michael L. McSwiney, Robert P. Meagley, Andrew W. Ott.
Application Number | 20070032675 11/580399 |
Document ID | / |
Family ID | 32908064 |
Filed Date | 2007-02-08 |
United States Patent
Application |
20070032675 |
Kind Code |
A1 |
Meagley; Robert P. ; et
al. |
February 8, 2007 |
Forming a dielectric layer using a hydrocarbon-containing
precursor
Abstract
In one embodiment, the present invention includes introducing a
precursor containing hydrocarbon substituents and optionally a
second conventional or hydrocarbon-containing precursor into a
vapor deposition apparatus; and forming a dielectric layer having
the hydrocarbon substituents on a substrate within the vapor
deposition apparatus from the precursor(s). In certain embodiments,
at least a portion of the hydrocarbon substituents may be later
removed from the dielectric layer to reduce density thereof.
Inventors: |
Meagley; Robert P.; (Aloha,
OR) ; Goodner; Michael D.; (Hillsboro, OR) ;
Ott; Andrew W.; (Hillsboro, OR) ; Kloster; Grant
M.; (Lake Oswego, OR) ; McSwiney; Michael L.;
(Hillsboro, OR) ; Leet; Bob E.; (Scottsdale,
AZ) |
Correspondence
Address: |
TROP PRUNER & HU, PC
1616 S. VOSS ROAD, SUITE 750
HOUSTON
TX
77057-2631
US
|
Family ID: |
32908064 |
Appl. No.: |
11/580399 |
Filed: |
October 13, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10377061 |
Feb 28, 2003 |
7138158 |
|
|
11580399 |
Oct 13, 2006 |
|
|
|
Current U.S.
Class: |
556/482 ;
106/287.1; 106/287.16; 257/E21.261; 257/E21.277; 556/400 |
Current CPC
Class: |
H01L 21/02274 20130101;
C23C 16/401 20130101; H01L 21/3122 20130101; H01L 21/31633
20130101; H01L 21/02216 20130101; H01L 21/02126 20130101 |
Class at
Publication: |
556/482 ;
106/287.16; 106/287.1; 556/400 |
International
Class: |
C04B 41/50 20060101
C04B041/50; C07F 7/02 20060101 C07F007/02 |
Claims
1. A precursor comprising: silicon; a first functional group
comprising an organic porogen, the first functional group attached
to the silicon; and a sacrificial functional group attached to the
silicon.
2. The precursor of claim 1, further comprising a first alkoxy
group attached to the silicon and a second alkoxy group attached to
the silicon.
3. The precursor of claim 1, wherein the sacrificial functional
group fragments preferentially.
4. The precursor of claim 1, wherein the first functional group
comprises a group stabilized against beta-hydride elimination.
5. The precursor of claim 1, wherein the first functional group
comprises a polydentate ligand.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application
Ser. No. 10/377,061, filed on Feb. 28, 2003.
BACKGROUND
[0002] The present invention relates to forming layers on a
substrate and more particularly to forming a dielectric layer using
a hydrocarbon-containing material.
[0003] Semiconductor devices typically include metal layers that
are insulated from each other by dielectric layers. It is desirable
that these dielectric layers which are made of an insulative
material have a relatively low dielectric constant. While such
dielectric layers may be made of various materials, silicon dioxide
is one material used, however it has a higher dielectric constant
than is desired for forming advanced semiconductor devices. One
material used to provide a low dielectric constant (K.sub.eff) is a
carbon doped oxide (CDO). Typically, CDO films are formed using a
vapor deposition process. It is desirable however, to obtain a
dielectric layer having a lower K.sub.eff than possible using
conventional vapor deposition processing and precursor
materials.
[0004] Certain materials used as dielectric films may be instead
formed using a spin-on process. While such spin-on materials may
have a relatively low K.sub.eff, they typically have poor
mechanical strength and may suffer from structural integrity
problems during subsequent processing. Thus there is a need for a
dielectric layer that has reliable mechanical strength for
subsequent processing and a relatively low dielectric constant upon
device completion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIGS. 1A-1B are chemical structures of substituted
precursors in accordance with various embodiments of the present
invention.
[0006] FIGS. 2A-2C are chemical structures of substituted
precursors in accordance with various embodiments of the present
invention.
[0007] FIGS. 3A-3E are chemical structures of substituted
precursors in accordance with various embodiments of the present
invention.
[0008] FIG. 4 is an example plasma enhanced chemical vapor
deposition reaction in accordance with one embodiment of the
present invention.
[0009] FIGS. 5A-5B are chemical structures of substituted
precursors in accordance with several embodiments of the present
invention.
[0010] FIG. 6 is an example plasma enhanced chemical vapor
deposition in accordance with a second embodiment of the present
invention.
DETAILED DESCRIPTION
[0011] In one embodiment of the present invention, a dielectric
layer may be deposited using a hydrocarbon substituted
silicon-based precursor (a "substituted precursor"). In various
embodiments, the hydrocarbon substituents may vary in chain length,
branching, sterics, C/H ratio, heteroatoms and other chemical
attributes to control resulting material composition and
engineering properties (e.g., activation energy (E.sub.a), carbon
to silicon (C/Si) ratio, rate of degradation, and K.sub.eff) . In
some embodiments, large hydrocarbon substituents may act as
porogenic functional groups.
[0012] In other embodiments, a percentage of a substituted
precursor may be co-deposited with conventional silicon oxide and
CDO precursor(s) (hereafter "conventional precursors"), which
include, but are not limited to tetraethylorthosilicate (TEOS),
TOMCATS, dimethyldimethoxysilane (DMDMOS), and OMCTS. The
percentage of substituted precursor to conventional precursor may
vary from a minimal amount (e.g., less than 5%) to 100%. This
percentage may vary based upon the morphology, mechanical strength,
C/Si ratio, and/or the porogenic characteristics desired of the
dielectric film. In certain embodiments, the percentage of
substituted precursor to conventional precursor may be between
approximately 10% to approximately 50%.
[0013] After deposition of the dielectric layer, various subsequent
processing may be performed. For example, metal interconnects may
be formed in or on the dielectric layer via a dual damascene or
other process. After the desired subsequent processing has been
completed, the hydrocarbon functionality of the substituted
precursors may be removed (hereafter referred to as
"post-treatment") to form a dielectric layer with greater porosity
and a lower dielectric constant. While the dielectric constant
obtained may vary in different embodiments, in certain embodiments,
the dielectric constant may be reduced to below 3.0 and even 2.5.
More so, in embodiments in which the substituted precursor includes
a large moiety, the dielectric constant may be reduced to
approximately 2.0.
[0014] In different embodiments, a dielectric layer may be
deposited using various techniques, including for example physical
vapor deposition (PVD), chemical vapor deposition, (CVD), or plasma
enhanced chemical vapor deposition (PECVD). One example deposition
may be thermal deposition of a substituted precursor with a
conventional molecular precursor such as TEOS, TMOS, and the like.
Similarly, deposition may be accomplished via plasma assisted
deposition of a substituted precursor with a molecular precursor
such as TEOS, DMDMOS, and the like. Alternately, the reaction of a
substituted precursor and a silane-based precursor with an oxygen
source (such as oxygen or water), or a mixture of any of the above
techniques may be used to deposit the dielectric layer (e.g., an
interlayer dielectric (ILD)).
[0015] Deposition of the dielectric layer may be accomplished using
a conventional reaction chamber operating at conventional
temperatures and pressures. In certain embodiments, the thickness
of the deposited dielectric layer may be between approximately 100
Angstroms and approximately 10,000 Angstroms.
[0016] In certain embodiments, the substituted precursor may be
engineered to take up additional space in the CDO lattice and
modulate its engineering properties (including K.sub.eff,
decomposition temperature, decomposition speed, E.sub.a, mechanical
strength, porosity, pore structure, film uniformity, modulus,
hardness, adhesion, cohesive strength, and the like).
[0017] Design of a substituted precursor may follow one of several
design motifs in accordance with various embodiments of the present
invention. In one embodiment, depicted in FIG. 1A, the substituted
precursor may have the general formula
[R.sub.2].sub.4-xSi[R.sub.1].sub.x, where x equals one, two, or
three; R.sub.1 may be a functional group that forms Si--O bonds
during deposition (i.e., a silanating/alkoxy silanating functional
group), for example, H, a halogen, OCH.sub.3, OCH.sub.2CH.sub.3, or
an alkoxy; and R.sub.2 may provide porogen functionality via a
bulky carbon-based functional group, for example, norbornyl,
neopentyl, adamantyl, cyclopentadienyl, methyl adamantyl, an
alicyclic, a heterocyclic, a branched alkyl, a straight chain
alkyl, or an aromatic. In the case of x=1 (a single silanating
group), more than one precursor may be used to build the film to
promote bonding between precursor molecules during the deposition
process.
[0018] In another embodiment, depicted in FIG. 1B, the substituted
precursor may have the general formula
[R.sub.2X].sub.4-xSi[R.sub.1].sub.x, where X is a heteroatom, such
as O, N, or S, for example; and x, R.sub.1 and R.sub.2 may be as
above.
[0019] In still another embodiment, the substituted precursor may
have the general formula [R.sub.2].sub.xSi[R.sub.1].sub.y, where
R.sub.1, R.sub.2 and x are as above and y is one or two, depending
on the value of x.
[0020] Referring now to FIGS. 2A-2C, shown are example substituted
precursors for use in forming dielectric layers in accordance with
various embodiments of the present invention. As shown in FIG. 2A,
in one embodiment a substituted precursor may be norbornyl
trimethoxysilane. As shown in FIG. 2B, in a second embodiment a
substituted precursor may be adamantyl trimethoxysilane. As shown
in FIG. 2C, in a third embodiment a substituted precursor may be
dicyclopentadienyl trimethoxysilane. In other embodiments,
substituted precursors may include trietoxynorbornylsilane,
tethered cage, substituted cage
(2-methyl-2-(triethoxysilyl)norbornane), aryl functionality (benzyl
and phenyl), straight chain, and branched chain, and fluorocarbon
substitutions. More so, derivatives or analogs of these compounds
may also be used as substituted precursors in certain
embodiments.
[0021] While the silicon content of the precursors of FIGS. 2A-2C
is shown as single silicon atoms, it is to be understood that in
other embodiments dimeric and oligomeric species, such as
disilanes, diazides, silsesquioxanes and others, may be used.
Hydrocarbon substituents may have many possible substitution
patterns in such multinuclear systems.
[0022] Heteroatom substituents may serve several functions,
including direction of plasma activation and energy transfer during
deposition, promotion of reactivity at specific locations, as well
as modulation of decomposition rate and mechanism, and the thermal
and mechanical properties of the deposited film. Examples of
heteroatoms and functionality include halogen, nitrogen, nitro
group, diazo group, and azo group, for example.
[0023] In certain embodiments, films may be deposited using
multiple substituted precursors having differing activation
energies for degradation and differing amounts of hydrocarbon bulk
available for loss. Referring now to FIGS. 3A-3E, shown are example
substituted precursors for use in forming dielectric layers in
accordance with other embodiments of the present invention. As
shown in FIG. 3A, in one embodiment a substituted precursor may be
tertbutoxy trimethoxysilane. As shown in FIG. 3B, in a second
embodiment a substituted precursor may be isoproxy
trimethoxysilane. As shown in FIG. 3C, in a third embodiment a
substituted precursor may be alpha methyl norbornyl
oxytrimethoxysilane. As shown in FIG. 3D in a fourth embodiment a
substituted precursor may be norbornyl oxytrimethoxysilane. As
shown in FIG. 3E, in a fifth embodiment a substituted precursor may
be adamantyl methoxy trimethoxysilane. As shown in FIGS. 3A-3E, the
hydrocarbons are bound to the silicon through a linker moiety
(e.g., oxygen). In other embodiments, other derivatives or analogs
may be bound to the silicon.
[0024] In certain embodiments in which post-treatment of a single
precursor is performed, the precursor may have multiple different
hydrocarbon functionalities. In one embodiment, two of these sites
may be silanating functional groups to form the silicon-oxygen
backbone of the dielectric layer, while a third site may be an
organic functional group that is desired to be incorporated into
the dielectric layer, and a fourth site may be a sacrificial
functional group. Such a precursor is depicted in FIG. 4.
[0025] For example, in one embodiment two alkoxy groups may be
attached to form the silicon-oxygen backbone. In this example, a
third site may be a functional group that attaches to the silicon
molecule at one or two points (denoted by R in FIG. 4). For
example, a ring structure, such as a tetra-substituted carbon in
the beta position or another structure stabilized against
beta-hydride elimination may be used. As an example, FIG. 5A
depicts a norbornyl-functionalized trimethoxysilane, and FIG. 5B
depicts a .beta.,.beta.-dimethylnorbornyl trimethoxysilane, which
is stabilized against beta-hydride elimination. This third site may
be a sterically large molecule. In other embodiments, this third
site may be an electron-accepting functional group, for example, a
phenyl group, such as a benzene ring, or an amide group having a
conjugated double bond or an alternating double bond single bond
structure. Alternately the third site may be a polydentate ligand
or other functional group which is multiply bonded to the silicon
atom. Examples of such ligands include, but are not limited to,
2,4-pentanedioate (acetyl acetonate; acac),
2,2,6,6-tetramethyl-3,5-heptanedionate (thd), dipivaloylmethane
(dpm), and bipyridine (bpy).
[0026] In various embodiments, a fourth site attached to the
silicon molecule may be, for example, an alkoxy, an alkyl, a
sacrificial functional group or the same functional group chosen
for the third site (denoted as X in FIG. 4).
[0027] In one embodiment, the third and fourth sites may be
functional groups having different reaction pathways. For example,
one functional group may be very reactive and be the primary
reaction pathway for monomer activation and subsequent film
deposition, in accordance with the scheme depicted in FIG. 4. The
second functional group may be large and unreactive so that it may
be incorporated into the film and may be selected to avoid common
plasma reaction pathways, such as beta hydride elimination or
hydrolysis, in certain embodiments. In certain embodiments,
sacrificial components that decompose preferentially may include,
but are not limited to, halogens, olefins, functional groups highly
susceptible to beta-hydride elimination such as ethyl or ethoxy
groups, or other functional groups (e.g., a precursor with two
different organic functional ethoxy groups, either of which may be
susceptible to post-treatment if incorporated into the film).
[0028] In an embodiment in which an Si-based organic precursor is
reacted with an oxidizing agent, reactions may be modulated by
steric hindrance of surface reactions or by electronic effects of
substituents groups. In such an embodiment, Si--H or Si--R (where R
is a small functional group) may be susceptible to attack by water
(i.e., hydrolysis) to create a new hydroxyl group, which can act as
an active site for film growth. Alternately, a much larger
functional group that can block access to reactive sites will not
react and will be incorporated into the film. Thus, surface
reactions of the film may be prevented during film growth, enabling
incorporation of organic porogens which may be later removed from
the film. In addition to the organic precursors described above,
hydroxyl-substituted functional groups may also be used (such
groups may be chemically bound to the film at more than one
site).
[0029] As discussed above, in one embodiment the precursor may be
stabilized during deposition by adding a sacrificial functional
group that will fragment preferentially during decomposition,
leaving the rest of the molecule (including the organic porogen)
intact. Such a precursor may have the sacrificial functional group
attached directly to the silicon (shown as X in FIG. 4) or attached
to the organic portion (also shown as X in FIG. 6).
[0030] Referring now to FIG. 4, shown is an example PECVD reaction
in accordance with one embodiment of the present invention. As
shown in FIG. 4, a silicon molecule has four sites attached
thereto, namely two alkoxy groups, a third site which is a
functional group (R) desired to be incorporated into the dielectric
film, and a fourth site which is a sacrificial functional group
(X). In one embodiment, X may be a functional group which is
especially labile under plasma deposition conditions, such as a
halogen, an olefin (e.g., a vinyl group), or a moiety susceptible
to beta-hydride elimination (e.g., an ethyl group). As shown in
FIG. 4, the sacrificial functional group (shown as X* after the
reaction) is not incorporated into the dielectric film.
[0031] Referring now to FIG. 6, shown is an example PECVD reaction
in accordance with a second embodiment of the present invention. As
shown in FIG. 6, a silicon molecule has four sites attached
thereto. In this embodiment, in addition to the two alkoxy groups,
a methyl group and an organic moiety (e.g., the benzene ring shown
in FIG. 6) are attached directly to the silicon molecule. In this
embodiment, the sacrificial functional group (X) is attached to the
organic moiety, rather than the silicon molecule itself. As
discussed above with regard to FIG. 4, X represents a functional
group which is especially labile under plasma deposition
conditions. As shown in FIG. 6, the sacrificial functional group
(shown as X* after the reaction) is not incorporated into the
dielectric film. While FIG. 6 shows a sacrificial group attached to
an aromatic functionality which is attached directly to the
silicon, other aromatic groups or non-aromatic groups may be used
and thus incorporated into the film during deposition.
[0032] In one embodiment, reaction conditions may be chosen so that
the reaction/decomposition of one functional group is much faster
than the other so that organic functional groups may be included in
the film. These groups may be removed during later post-treatment
to reduce the dielectric constant of the film.
[0033] In one embodiment, the dielectric layer may be used as a
substrate for desired subsequent processing. For example, a dual
damascene process may be performed to form metal interconnects in
the dielectric layer.
[0034] Certain embodiments of the present invention may provide
hydrocarbon bulk for loss, and subsequent removal of the
hydrocarbon bulk may increase the porosity of the dielectric layer.
When the porosity of the dielectric layer increases, the K.sub.eff
decreases. The stoichiometry of the original film (and thus the
ratio of precursors) depends upon the desired final K.sub.eff.
[0035] In one embodiment, after the metal stack (i.e., metal
interconnect) is complete, the dielectric layer may be subjected to
an additional process (the aforementioned "post-treatment") to
remove the hydrocarbon substitutions in the matrix (and the
accompanying bulk). However, it is to be understood that in other
embodiments, hydrocarbon removal may occur at other points in the
process flow, such as after chemical mechanical planarization, if a
particular integration scheme dictates.
[0036] In one embodiment, thermal decomposition may be employed to
remove the substituted precursor. In certain embodiments, the
thermal removal may occur at temperatures between approximately
200.degree. Celsius (C.) and approximately 500.degree. C. The
duration of such thermal removal may also vary in different
embodiments, and may range from approximately one minute to
approximately two hours, in certain embodiments.
[0037] All or substantially all of the substituted precursor may be
removed to provide for increased porosity in one embodiment.
However, in other embodiments, particularly where the substituted
precursor includes a large cage, for example, a methyl-based
precursor, a greater portion of the substituted precursor (i.e.,
the methyl group) may remain in the dielectric layer after the
removal process.
[0038] The removal process may be aided by a photo-acid generator
or other catalysts in certain embodiments. For example, an acid or
other catalyst may be co-deposited with the precursors which may
later aid in removal of the substituted precursor. Such acids may
include Lewis and Bronsted acids, for example.
[0039] In other embodiments, the removal process may include a
plasma etch or ashing process. Such etching or ashing may be
performed using conventional parameters and materials.
[0040] While the above embodiments relate to substituted
precursors, it is to be understood that in certain embodiments,
hydrocarbon substituted structures may be in a polymer or oligomer
form and may be co-deposited (along with conventional polymers or
oligomers) on a substrate via a spin-on technique.
[0041] While the present invention has been described with respect
to a limited number of embodiments, those skilled in the art will
appreciate numerous modifications and variations therefrom. It is
intended that the appended claims cover all such modifications and
variations as fall within the true spirit and scope of this present
invention.
* * * * *