U.S. patent application number 14/249272 was filed with the patent office on 2014-10-09 for methods and apparatus for dielectric deposition.
This patent application is currently assigned to Novellus Systems, Inc.. The applicant listed for this patent is Novellus Systems, Inc.. Invention is credited to Kaihan Ashtiani, Nerissa Draeger, John Drewery, Lakshminarayana Nittala, Naohiro Shoda, Bart van Schravendijk, Michael Wood.
Application Number | 20140302689 14/249272 |
Document ID | / |
Family ID | 44146182 |
Filed Date | 2014-10-09 |
United States Patent
Application |
20140302689 |
Kind Code |
A1 |
Ashtiani; Kaihan ; et
al. |
October 9, 2014 |
METHODS AND APPARATUS FOR DIELECTRIC DEPOSITION
Abstract
Methods for depositing flowable dielectric films are provided.
In some embodiments, the methods involve introducing a
silicon-containing precursor to a deposition chamber wherein the
precursor is characterized by having a partial pressure:vapor
pressure ratio between 0.01 and 1. In some embodiments, the methods
involve depositing a high density plasma dielectric film on a
flowable dielectric film. The high density plasma dielectric film
may fill a gap on a substrate. Also provided are apparatuses for
performing the methods.
Inventors: |
Ashtiani; Kaihan;
(Cupertino, CA) ; Wood; Michael; (San Jose,
CA) ; Drewery; John; (Santa Clara, CA) ;
Shoda; Naohiro; (Los Gatos, CA) ; van Schravendijk;
Bart; (Cupertino, CA) ; Nittala; Lakshminarayana;
(Sunnyvale, CA) ; Draeger; Nerissa; (Fremont,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Novellus Systems, Inc. |
Fremont |
CA |
US |
|
|
Assignee: |
Novellus Systems, Inc.
Fremont
CA
|
Family ID: |
44146182 |
Appl. No.: |
14/249272 |
Filed: |
April 9, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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12964110 |
Dec 9, 2010 |
8728958 |
|
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14249272 |
|
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61285091 |
Dec 9, 2009 |
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Current U.S.
Class: |
438/786 ;
118/697; 438/788; 438/792 |
Current CPC
Class: |
H01L 21/76224 20130101;
H01L 21/02274 20130101; H01L 21/02208 20130101; H01L 21/02164
20130101; H01L 21/0214 20130101; H01L 21/0217 20130101 |
Class at
Publication: |
438/786 ;
438/788; 438/792; 118/697 |
International
Class: |
H01L 21/02 20060101
H01L021/02 |
Claims
1. An apparatus comprising: a flowable dielectric deposition
chamber configured to deposit flowable dielectric film; and a
controller, said controller comprising instructions for introducing
into the flowable dielectric deposition chamber a process gas
comprising a silicon-containing precursor, wherein the
silicon-containing precursor is characterized by having a partial
pressure (Pp):vapor pressure (Pvp) ratio of 0.01-1.
2. The apparatus of claim 1, further comprising a high density
plasma chemical vapor deposition (HDP-CVD) deposition chamber
configured to deposit HDP dielectric film.
3. The apparatus of claim 2, wherein the controller further
comprises instructions for transferring a substrate from the
flowable dielectric deposition chamber to the HDP-CVD chamber after
introducing the process gas to the flowable dielectric deposition
chamber.
4. The apparatus of claim 3, wherein the controller further
comprises instructions to deposit HDP dielectric film after
transferring the substrate.
5. The apparatus of claim 1, wherein the flowable dielectric
deposition chamber comprises a plasma generator.
6. The apparatus of claim 6, wherein the controller further
comprises instructions to, after introducing the process gas to the
flowable dielectric deposition chamber, generate a high-density
plasma in the plasma generator and deposit HDP dielectric film.
7. The apparatus of claim 1, wherein the process gas further
comprises an oxidant, wherein the wherein the oxidant is
characterized by the following partial pressure (Pp):vapor pressure
(Pvp) ratio: 0.25-2.
8. The apparatus of claim 1, wherein the process gas further
comprises a solvent, wherein the wherein the solvent is
characterized by having a partial pressure (Pp):vapor pressure
(Pvp) ratio of 0.1-1.
9. A method, comprising: introducing a process gas comprising a
silicon-containing precursor and an oxidant to a deposition,
wherein the process gas is characterized as having an
oxidant:precursor partial pressure ratio of about 5 to 15 to
thereby deposit a flowable dielectric film on a substrate in the
process chamber.
10. The method of claim 9, wherein the process gas further
comprises a solvent.
11. The method of claim 9, further comprising a depositing a high
density plasma chemical vapor deposition (HDP-CVD) dielectric film
via a high density plasma chemical vapor deposition reaction on the
flowable dielectric film.
12. A method of depositing a dielectric film on a substrate, the
method comprising: introducing a process gas comprising a
silicon-containing precursor to thereby deposit a flowable
dielectric film on the substrate, wherein the silicon-containing
precursor is characterized by having a partial pressure (Pp):vapor
pressure (Pvp) ratio of 0.01-1.
13. The method of claim 12, wherein the process gas further
comprises an oxidant, wherein the wherein the oxidant is
characterized by the following partial pressure (Pp):vapor pressure
(Pvp) ratio 0.25-2.
14. The method of claim 12, wherein the process gas further
comprises a solvent, wherein the wherein the solvent is
characterized by the following partial pressure (Pp):vapor pressure
(Pvp) ratio 0.1-1.
15. The method of claim 12, further comprising depositing a high
density plasma (HDP) dielectric film on the flowable dielectric
film.
16. The method of claim 12, wherein the flowable dielectric film is
a silicon oxide film, a silicon nitride film or a silicon
oxynitride film.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of and claims priority to
U.S. application Ser. No. 12/964,110, filed Dec. 9, 2010, which
claims the benefit of priority to U.S. Provisional Patent
Application No. 61/285,091, filed Dec. 9, 2009, all of which are
incorporated herein by reference in their entireties and for all
purposes.
BACKGROUND OF THE INVENTION
[0002] It is often necessary in semiconductor processing to fill
high aspect ratio gaps with insulating material. This is the case
for shallow trench isolation (STI), inter-metal dielectric (IMD)
layers, inter-layer dielectric (ILD) layers, pre-metal dielectric
(PMD) layers, passivation layers, etc. As device geometries shrink
and thermal budgets are reduced, void-free filling of narrow width,
high aspect ratio (AR) features (e.g., AR>6:1) becomes
increasingly difficult due to limitations of existing deposition
processes.
SUMMARY OF THE INVENTION
[0003] Methods for depositing flowable dielectric films are
provided. In some embodiments, the methods involve introducing a
silicon-containing precursor to a deposition chamber wherein the
precursor is characterized by having a partial pressure:vapor
pressure ratio between 0.01 and 1. In some embodiments, the methods
involve depositing a high density plasma dielectric film on a
flowable dielectric film. The high density plasma dielectric film
may fill a gap on a substrate. Also provided are apparatuses for
performing the methods.
[0004] The detailed description below will further discuss the
benefits and features of this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1A includes schematic cross-sectional depictions of
unfilled gaps in a shallow trench isolation (STI) integration
process.
[0006] FIGS. 1B and 1C are schematic cross-sectional depiction of
gaps filled by a method according to certain embodiments.
[0007] FIG. 2A is a process flow diagram illustrating operations in
a method of filling trenches or other gaps with dielectric material
according to certain embodiments.
[0008] FIG. 2B includes schematic cross-sectional depictions of
operations in FIG. 2A.
[0009] FIG. 3A is a process flow diagram illustrating operations in
a method of filling trenches or other gaps with dielectric material
according to certain embodiments.
[0010] FIG. 3B includes schematic cross-sectional depictions of
operations in FIG. 3A.
[0011] FIG. 4A is a process flow diagram illustrating operations in
a method of filling trenches or other gaps with dielectric material
according to certain embodiments.
[0012] FIG. 4B includes schematic cross-sectional depictions of
operations in FIG. 4A.
[0013] FIG. 5A is a process flow diagram illustrating operations in
a method of filling trenches or other gaps with dielectric material
according to certain embodiments.
[0014] FIG. 5B includes schematic cross-sectional depictions of
operations in FIG. 5A.
[0015] FIG. 6A includes a schematic cross-sectional depiction of
incoming aspect ratio (AR) and AR after flowable oxide deposition
in features of various sizes. FIG. 6A also includes a plot of
aspect ratio for various sized features before and after flowable
deposition.
[0016] FIG. 6B is another plot of aspect ratio for various sized
features before and after flowable deposition. Images of gaps
filled with flowable oxide and an HDP oxide cap are shown on the
plot.
[0017] FIG. 7 is a process flow diagram illustrating operations in
a method of depositing flowable dielectric material in gaps
according to certain embodiments.
[0018] FIGS. 8A-8D are schematic depictions of reaction mechanisms
in an example of a method of filling a gap with dielectric material
according to certain embodiments.
[0019] FIG. 9A is a graph qualitatively illustrating the tunability
of feature fill selectivity.
[0020] FIG. 9B is a plot illustrating the dependence of fill height
for a particular feature size on solvent partial pressure.
[0021] FIG. 10 is a process flow diagram illustrating operations in
a method of depositing flowable dielectric material in gaps
according to certain embodiments.
[0022] FIG. 11 is a process flow diagram illustrating operations in
a method of depositing flowable oxide in a gap in a silicon or SOI
substrate according to certain embodiments.
[0023] FIG. 12 is a process flow diagram illustrating operations in
method of filling a gap with dielectric material according to
certain embodiments.
[0024] FIG. 13 is a top view diagram illustrating a multi-station
apparatus suitable for practicing selected embodiments.
[0025] FIG. 14 is simplified illustration of a HDP-CVD module
suitable for practicing various embodiments.
[0026] FIG. 15 is a simplified illustration of a direct plasma
deposition/cure module suitable for practicing various
embodiments.
[0027] FIG. 16 is a simplified illustration of a remote plasma
deposition/cure module suitable for practicing various
embodiments.
DETAILED DESCRIPTION OF THE INVENTION
Introduction
[0028] The present invention pertains to methods of filling gaps on
a substrate. In certain embodiments, the methods pertain to filling
high aspect (AR) ratio (typically at least 6:1, for example 7:1 or
higher), narrow width (e.g., sub-50 nm) gaps. In certain
embodiments, the methods pertain filling both low AR gaps (e.g.,
wide trenches). Also in certain embodiments, gaps of varying AR may
be on the substrate, with the embodiments directed at filling low
and high AR gaps.
[0029] According to various embodiments, the methods involve
depositing both flowable oxide films and high density plasma
chemical vapor deposition oxide (HDP oxide) films in a gap.
According to various embodiments, the flowable oxide films may be
used as a sacrificial layer and/or as a material for bottom up gap
fill. In certain embodiments, the top surface of the filled gap is
an HDP oxide film. The resulting filled gap may be filled only with
HDP oxide film or a combination of HDP oxide and flowable oxide
films. The methods provide improved top hat reduction and avoid
clipping of the structures defining the gaps.
[0030] As used herein, the term "HDP oxide film" refers to doped or
undoped silicon oxide films deposited using high density plasma
chemical vapor deposition processes. Generally, a high density
plasma is any plasma having electron density of at least about
5.times.10.sup.10 electrons per cubic centimeter, and more typical
1.times.10.sup.11 electrons per cubic centimeter. HDP CVD reactions
may also be characterized in certain embodiments, by relatively low
reactor pressures, in the range of 100 mTorr or lower.
[0031] While the below description refers chiefly to HDP oxide cap
films, other types of dielectric films may be used including TEOS
oxide deposited by plasma enhanced chemical vapor deposition
(PECVD), sub-atmospheric CVD (SACVD) or dielectric deposited by any
other method.
[0032] As used herein, the term "flowable oxide film" is a flowable
doped or undoped silicon oxide film having flow characteristics
that provide consistent fill of a gap. The flowable oxide film may
also be described as a soft jelly-like film, a gel having liquid
flow characteristics, a liquid film, or a flowable film. Unlike
HDP-CVD reactions, forming a flowable film may involve reacting a
silicon-containing precursor and an oxidant to form a condensed
flowable film on the substrate. Formation of the film may be aided
by a catalyst, e.g., as described in U.S. patent application Ser.
No. 11/925,514, filed Oct. 26, 2007, incorporated by reference
herein. The flowable oxide deposition methods described herein are
not limited to a particular reaction mechanism, e.g., the reaction
mechanism may involve an adsorption reaction, a hydrolysis
reaction, a condensation reaction, a polymerization reaction, a
vapor-phase reaction producing a vapor-phase product that
condenses, condensation of one or more of the reactants prior to
reaction, or a combination of these. The substrate is exposed to
the process gases for a period sufficient to deposit a flowable
film to fill at some of the gaps. The deposition process typically
forms soft jelly-like film with good flow characteristics,
providing consistent fill. In certain embodiments, the flowable
film is an organo-silicon film, e.g., an amorphous organo-silicon
film.
[0033] As deposited HDP oxide films are densified solids and not
flowable, whereas as-deposited flowable oxide films are not fully
densified. The term "flowable oxide film" may be used herein to
refer to flowable oxide films that have undergone a densification
process that wholly or partially densifies the film and/or a
conversion process that wholly or partially chemically converts the
film as well as as-deposited flowable oxide films. Details of
HDP-CVD and flowable oxide deposition processes are described
further below.
[0034] While the description below refers chiefly to flowable
silicon oxide films, the integration schemes described herein may
also be used with other types of flowable dielectric films. For
example, the film as-deposited may be primarily silicon nitride,
with Si--N and N--H bonds, or silicon oxynitride. In certain
embodiments, such films may be converted by a cure process to a SiO
or SiON network.
[0035] In certain embodiments, shallow trench isolation (STI)
integration methods are provided. FIG. 1A depicts cross-sectional
schematic representations of dense (at 101) and isolated (at 102)
gaps to be filled in an STI process. At 101, gaps 104a-104d are
trenches formed in a silicon or silicon-on-insulator (SOI)
substrate 103. Pad oxide layer 105 and silicon nitride layer 106
are also depicted. The sidewalls of the trench may also be coated
with an oxide layer or a liner layer (not shown), for example a
SiON or SiN layer. At 102, an isolated gap 104 formed in a silicon
or SOI substrate 103 is depicted. Although not shown, the sidewalls
of gap 104 may also be defined by oxide, nitride and other layers.
While the gaps depicted schematically in FIG. 1A have a generally
square profile, the sidewalls of the gap may be slanted, e.g., as
depicted schematically in FIG. 6, below.
[0036] A gap typically is defined by a bottom surface and
sidewalls. The term sidewall or sidewalls may be used
interchangeably to refer to the sidewall or sidewalls of a gap of
any shape, including a round hole, a long narrow trench, etc. The
sidewall and bottom surfaces that define the gap may be one or
multiple materials. Examples of gap sidewall and bottom materials
include nitrides, oxides, carbides, oxynitrides, oxycarbides,
silicides, as well as bare silicon or other semiconductor material.
Particular examples include SiN, SiO.sub.2, SiC, SiON, NiSi, and
any other silicon-containing material. In certain embodiments,
prior to flowable dielectric deposition, the gap is provided with a
liner, barrier or other type of conformal layer formed in the gap,
such that all or a portion of the bottom and/or sidewalls of the
gap is the conformal layer.
[0037] A gap may also be characterized by the structures it lies
between. In certain embodiments, such as in the examples depicted
in FIG. 1A, the structures are or include areas of a silicon
substrate between gaps etched into the substrate. The structures
(also referred to herein as raised features or features) may also
be, for example, hardmasks, metal vias or trench lines, transistor
gates or other features. Adjacent structures define a gap
there-between. The structures may include one or more liner layers
that form the sidewalls of the gap.
[0038] In gaps that are filled solely with HDP oxide, in addition
to fill of HDP oxide at the bottom of the gaps, HDP oxide is
deposited on top of the structures (top hats) and overhangs and
cusps at the entry region of the gap to be filled. The overhang
formations result from sputtering and redeposition processes. The
directional aspect of the deposition process produces some high
momentum charged species that sputter away material from within the
gap. The sputtered material tends to redeposit on the sidewalls of
high AR structures. If allowed to grow, the cusps deposited on the
sidewalls of the feature can prematurely close-off the gap. To
remove these cusps and top hat formations, an etch back process is
performed. The etching is accomplished by exposure to a
fluorine-containing compound, e.g., a plasma containing fluorine
species. These species normally originate from a
fluorine-containing process gas component such as SiF.sub.4,
SiH.sub.2F.sub.2, Si.sub.2F.sub.6, C.sub.2F.sub.6, NF.sub.3,
CF.sub.4, and the like. Other etch processes may also be employed
such as a wet etch in HF.
[0039] The etch is limited by clipping of the structure by the
etchants, typically at top corner of structure or sidewall of gap,
as shown. Clipping refers to damage due to the exposure of the
structure to etchants and may be the result of either physical or
chemical etch processes. Clipping causes problems in subsequent
process steps, such as lack of CMP polish stop due to SiN erosion,
and problems in electrical performance, such as clipping (erosion)
into a Si sidewall in trenches. For example, an NF3 etch of an HDP
oxide deposited in a high AR gap next to a wide gap (such as a
trench) can result in sidewall clipping of the high AR feature by
lateral chemical etch by NF3, due to thin sidewall coverage. For
advanced structure, the deposition amount per cycle becomes
thinner, resulting in a disappearing NF3 etch process window.
[0040] FIG. 1B is a representation of gaps 104 filled according to
certain embodiments. In the depicted embodiment, each gap 104 is
filled with dielectric material, a flowable dielectric material 110
and HDP oxide material 112. According to various embodiments, the
flowable dielectric material 110 fills the gap to a level beneath
that of silicon nitride layer 106. According to various
embodiments, the flowable dielectric material 110 is at least 50 nm
from the bottom of the silicon nitride layer 106. A wide trench 114
filled with HDP oxide 112 is also depicted in FIG. 1B. A small
amount of flowable dielectric 110a is present on the depicted
sidewall of trench 114; as with the flowable dielectric material in
narrow gaps 104, it is at least 50 nm or so below the silicon
nitride layer of that sidewall.
[0041] In certain embodiments, there is substantially no flowable
oxide deposition on the sidewall in narrow gaps above the level of
the flowable oxide deposition; that is to say that there is
substantially no conformal component to the bottom up flowable
oxide deposition. FIG. 1C depicts a cross-section a gap partially
filled with flowable oxide 110, with the remainder of the gap
filled with HDP oxide 112. A capillary condensation reaction
mechanism used in certain embodiments to deposit the flowable oxide
and described further below results in bottom up flow with a
concave meniscus, as shown. Above the meniscus, deposition on the
sidewall is no more than about 1 monolayer, or less than about 4
Angstroms, per flowable oxide deposition cycle; with total
deposition (depending on the number of cycles) on the sidewalls
less than twenty Angstroms or less than ten Angstroms for example.
This results in substantially all HDP oxide in the gap above the
flowable oxide level (e.g., at least 50 nm below a SiN layer). This
beneficial as a substantial amount of flowable dielectric sidewall
deposition (e.g., 100 Angstroms or more) may result in unwanted
etching at the sidewall during later processes in which the HDP
oxide is etched.
[0042] According to various embodiments, the methods of the
invention provide improved gap fill by using a flowable oxide film
as a sacrificial film during HDP-CVD gap fill and/or using a
flowable oxide film for bottom up gap fill in conjunction with HDP
oxide, as shown in FIG. 1B. According to various embodiments, an
unfilled gap is provided, with HDP oxide and flowable oxide
deposition processes used to deposit HDP oxide and flowable oxide
in the gap. According to various embodiments, the HDP oxide may be
deposited first, followed by the flowable oxide or vice-versa. In
certain embodiments, the final deposition operation is an HDP-CVD
operation such that top surface of the filled gap is HDP oxide. One
or more etch operations may be performed after various deposition
operations to etch back HDP oxide and/or flowable oxide. The etch
operations may be non-selective (etching both HDP oxide and
flowable oxide material) or selective (etching primarily or solely
flowable oxide or HDP oxide while leaving the other substantially
un-etched). FIG. 1B provides an example of filled gaps according to
one process scheme. Various embodiments are set forth below as
examples of process schemes.
[0043] FIG. 2A is a process flow diagram illustrating an embodiment
in which flowable oxide film is used as a sacrificial material to
reduce top hat formation while protecting feature sidewalls from
the deleterious effects of chemical etchants. The process begins by
providing a substrate having raised features and unfilled gaps
between the raised features (201). Unfilled generally refers to
unfilled with insulation material that is to be deposited to fill
the gap; as indicated above, various liner or other layers may be
present in the gap. The substrate is provided to an HDP-CVD
reactor, additional details of which are described below. One or
more HDP-CVD deposition operations may then be performed to
partially fill the gap with HDP oxide dielectric material (203).
Further details of HDP-CVD deposition processes and parameters are
given below. If multiple deposition operations are to be performed,
in certain embodiments, they may be interspersed with one or more
intervening etch operations and/or an etch operation may be
performed after the one or more HDP-CVD deposition operations, e.g.
to remove cusp material. In certain embodiments, however, no etch
operations are performed prior to the flowable oxide deposition.
After HDP-CVD deposition to partially fill the gap, HDP oxide is in
the bottom of the gap, on the sidewalls and on top of the raised
features (top hats). The sidewall deposition is typically
characterized by a narrowing of the gap from a bottom-up
perspective, with the most deposition occurring at the entry to the
gap. This can be seen in the cross-sectional representations of a
partially filled gap after HDP-CVD deposition in FIG. 2B, which
depicts features and gaps at various stages of a process as
described in this example. At 220, top hats 221 and cusps 223
formed by deposited HDP oxide 112 are depicted. Returning to FIG.
2A, the next operation involves depositing flowable oxide film to
overfill the gap (205). That is, enough flowable oxide film is
deposited to fill the gap as well as cover the features. In certain
embodiments, the HDP oxide top hats are also covered by the
flowable oxide film. This is depicted in FIG. 2B as 230, with
flowable oxide film 110 filling the gaps and covering HDP oxide top
hats 221. Details of the flowable oxide deposition are described
further below. According to various embodiments, the flowable oxide
deposition may occur in the HDP-CVD deposition chamber or in a
separate deposition chamber. In certain embodiments, it may occur
in a different station of a multistation chamber. Also in certain
embodiments, different process modules are attached on one
mainframe. Thus, depending on the embodiment, transitioning between
HDP-CVD deposition and flowable oxide deposition may or may not
involve transferring the substrate to a different chamber or
process module. Note also that if an etch operation is performed
between these operations, it may involve transfer to and from a
separate etch chamber. Once the flowable oxide is deposited, an
optional cure operation may be performed (207). As described below,
in the cure process, the film may be densified and/or chemically
converted to a desired dielectric composition. In certain
embodiments, the densification and conversion are performed in
separate operations; or multiple operations may be performed, each
densifying and/or curing the film. Still in other embodiments, the
as-deposited film may be chemically converted without densification
or vice versa. In certain embodiments, cure of the flowable film
may be used to tune etch characteristics of the flowable film. In
the next operation, a non-selective removal of HDP oxide and
flowable oxide is performed; depending on the removal chemistry and
process used and the characteristics of the flowable oxide and HDP
oxide, performing a cure process may be useful to harmonize the
etch rates of these films. As discussed further below, various cure
processes may be performed. These processes may densify the film
and may completely solidify it in certain cases. In certain
embodiments, only a top portion that is to be etched the succeeding
operation is cured. In this manner different etch characteristics
can be imparted to the top portion of the flowable oxide film,
which is to be non-selectively removed, and the bottom portion of
the film, which is to be selectively removed. A partially cured
film is depicted at 240 in FIG. 2B in which a portion 110b of the
flowable oxide film 110 that is above the gap is cured. Portion
110b may be densified and/or chemically converted to a silicon
oxide (or other desired dielectric). In certain embodiments,
portion 110c remaining in the gap is lower density than portion
110b, but is still chemically converted to a SiO network. In other
embodiments, portion 110c is compositionally different than portion
110c. In certain embodiments, no cure operation is performed, with
the etch chemistry or conditions suitably to remove the desired
film(s). As indicated, a non-selective removal of HDP oxide and
flowable oxide is performed (209). The etch stops above the raised
features and the gap openings, but removes at least a portion of
the top hat deposition, in certain embodiments, most of the top hat
deposition. This is depicted at 250 in FIG. 2B, which shows only a
thin layer of HDP oxide 112 above the features and the gap opening.
The remaining flowable oxide film may then be optionally cured,
e.g., to modify its etch characteristics (211). The remaining
flowable oxide is then selectively removed, that is it is removed
without removing a significant amount of the HDP oxide (213). This
is depicted at 260 in FIG. 2B, with only HDP oxide 112 remaining.
This may be done using the same or a different removal process as
performed in operation 209, for example a wet etch rather than a
plasma etch may be used. Operations 203-213 may then be repeated to
further partially fill the gap with HDP oxide, overfill the gap
with a sacrificial layer of a flowable oxide film, remove HDP oxide
and flowable oxide from above the features and gap, and selectively
remove the flowable oxide from the gap (215). If these operations
are not repeated, or after one or more such repetitions, one or
more additional HDP-CVD depositions are performed to complete fill
of the gap with HDP oxide (217). In certain embodiments wherein
multiple depositions are performed, intervening etch operations may
be performed. Alternatively, the gap fill may be completed without
additional etch operations. The resulting gap is filled with HDP
oxide, with substantially no flowable oxide. In other embodiments,
a small amount of flowable oxide film may remain, filling e.g.,
less than ten percent by volume of the gap. As shown in FIG. 2B at
270, a small amount of top hat HDP oxide deposition may be present,
however, because of the previous one or more etch operations 209,
the top hats are significantly smaller than they otherwise would
be. Moreover, the features are protected during these etch
operations. In certain embodiments, the only etch operations
performed are those depicted in operations 209 and 213. After
completing gap fill, the top of the gap and features may be
planarized, e.g., in a chemical-mechanical planarization (CMP)
process (219).
[0044] FIG. 3A is a process flow diagram showing certain operations
in a method of gap fill in which flowable oxide increases bottom up
fill, with the flowable oxide encapsulated by the HDP oxide, so
that the flowable oxide does not touch the sidewalls and bottoms of
gaps, and is not exposed on surface. The process begins by
providing a substrate having raised features and unfilled gaps
between the raised features to an HDP-CVD reactor (301). One or
more HDP-CVD deposition operations may then be performed to
partially fill the gap with HDP oxide dielectric material (303). As
with the process described above with reference to FIG. 2A, if
multiple deposition operations are to be performed, in certain
embodiments, they may be interspersed with one or more intervening
etch operations and/or an etch operation may be performed after the
one or more HDP-CVD deposition operations, e.g. to remove cusp
material. In certain embodiments, however, no etch operations are
performed prior to the flowable oxide deposition. The next
operation involves depositing flowable oxide film to further fill
the gap (305). After the deposition of flowable oxide film, the gap
is still only partially filled in certain embodiments, that is, the
flowable oxide is deposited to a point below the top surface of the
adjacent features. This is depicted in FIG. 3B, which depicts
features and gaps at various stages of a process as described in
FIG. 3A. As with all examples described herein, the flowable oxide
deposition may occur in the HDP-CVD deposition chamber or in a
separate deposition chamber according to various embodiments. The
flowable oxide film is then optionally cured (307). As described
above and detailed further below, the cure process may convert all
or part of the film to a Si--O network. The film may be wholly or
partially solidified by a cure process. In certain embodiments, the
film is uncured prior to the subsequent HDP oxide deposition. One
or more additional HDP-CVD depositions are performed to complete
fill of the gap with HDP oxide (309). In certain cases, the HDP-CVD
process may densify the flowable oxide film and may wholly or
partially solidify it. The resulting gap is filled with HDP oxide
and flowable oxide. In certain embodiments, the HDP oxide
encapsulates the flowable oxide such that the flowable oxide does
not contact the sidewalls and bottoms of gaps, and is not exposed
on surface of the filled gap. In alternate embodiments, the HDP
oxide partially encapsulates the flowable oxide, for example,
contacting the sidewalls of the gap only. After completing gap
fill, the top of the gap and features may be planarized, e.g., in a
chemical-mechanical planarization (CMP) process (319).
[0045] FIG. 3B depicts cross-sectional schematics of deposition in
narrow trenches, as well as in a wide trench, as described in FIG.
3A. At 320, narrow gaps 104 are depicted partially filled with HDP
oxide 112, including top hat 221 and cusp 223 deposition as well as
bottom-up fill. At 330, flowable oxide deposition 110 to a level
below the top surface of the adjacent features is depicted. At 340,
subsequent HDP deposition 112 is depicted. At 350, FIG. 3B also
shows deposition in a wide trench 114. In certain embodiments in
which high AR gaps are filled next to such a trench 114 by the
method shown in FIG. 3A, the thickness of flowable oxide deposited
in the trench during operation 305 is very small and may be
negligible. Accordingly, as depicted in FIG. 3B, the trench is
substantially filled completely with HDP oxide, with no significant
amount of flowable oxide deposited therein.
[0046] FIG. 4A is a process flow diagram illustrating another
embodiment in which flowable oxide film increases bottom up fill.
The process begins by providing a substrate having raised features
and unfilled gaps between the raised features to a HDP-CVD reactor
(401). One or more HDP-CVD deposition operations are then performed
to partially fill the gap with HDP oxide dielectric material (403)
as in the methods described in FIGS. 2A and 3A. The next operation
involves depositing flowable oxide film to overfill the gap (405),
also as described above with respect to FIG. 2A. Once the flowable
oxide is deposited, an optional cure operation may be performed
(407), which may be used to tune etch characteristics of the
deposited flowable oxide. In certain embodiments, the flowable
oxide film is left uncured to exploit the differences in etch
properties of the as-deposited HDP oxide and as-deposited flowable
oxide films. A portion of the flowable oxide film is then
selectively removed, with the etchback stopping at a point below
the gap opening, leaving the gap partially filled with HDP oxide
and flowable oxide (409). In certain embodiments, a non-selective
etch of the HDP oxide and flowable oxide is performed prior to the
selective removal, with the non-selective etchback stopping above
the raised features and the gap openings, removing at least a
portion of the top hat HDP oxide deposition. After the selective
removal, all or part of the remaining flowable oxide film is
optionally cured (411). As with the other embodiments, multiple
cycles of all or part of the described operations may be performed
in certain embodiments. One or more additional HDP-CVD depositions
are performed to complete fill of the gap with HDP oxide (413). In
certain embodiments wherein multiple depositions are performed,
intervening etch operations may be performed. The resulting gap is
filled with HDP oxide and flowable oxide. After completing gap
fill, the top of the gap and features may be planarized, e.g., in a
chemical-mechanical planarization (CMP) process (415).
[0047] FIG. 4B which depicts features and gaps at various stages of
a process as described in FIG. 4A. At 420, narrow gaps 104 are
depicted partially filled with HDP oxide 112, including top hat 221
and cusp 223 deposition as well as bottom-up fill. At 430, flowable
material 110 overfills the gaps with the etched back flowable film
depicted at 440. Complete fill of the narrow gaps with a
combination of HDP oxide 112 flowable oxide 110 is depicted at 450.
Deposition in a wide gap is depicted at 460.
[0048] In certain embodiments, this process scheme provides a more
uniform flowable oxide height across gaps than the process scheme
described in FIGS. 3A and 3B. Also, in comparison to that process
scheme, the total HDP thickness deposited in this scheme is less in
certain embodiments. As a result, the CMP process is easier. As
shown in FIG. 4B, the flowable oxide deposition is thicker in
smaller gaps and thinner in wider gaps. Note that because at least
the high AR gaps are overfilled, the amount of flowable oxide
deposited in the wide gaps is greater than that depicted in FIG.
3B. In certain embodiments, the HDP oxide encapsulates the flowable
oxide such that the flowable oxide does not contact the sidewalls
and bottoms of gaps, and is not exposed on surface of the filled
gap. In alternate embodiments, the HDP oxide partially encapsulates
the flowable oxide, for example, contacting the sidewalls of the
gap only.
[0049] FIG. 5A is a process flow diagram illustrating an embodiment
in which flowable oxide film is used for bottom up fill with HDP
oxide used as a cap layer to complete fill. The process begins by
providing a substrate having raised features and unfilled gaps
between the raised features to a reactor (501). Unlike the other
examples, HDP oxide is not initially used to partially fill the
unfilled gap. Rather, one or more flowable oxide depositions are
performed to partially fill the gap with flowable oxide dielectric
material (503). If multiple deposition operations are to be
performed, in certain embodiments, they may be interspersed with
one or more intervening cure operations. As with all examples
described herein, the flowable oxide deposition may occur in a
HDP-CVD deposition chamber or in a separate deposition chamber
according to various embodiments. The flowable oxide film is then
optionally cured (505). The film may be wholly or partially
solidified by a cure process. In certain embodiments, the film is
uncured prior to the subsequent HDP oxide deposition. One or more
additional HDP-CVD depositions are performed to complete fill of
the gap with HDP oxide (507). In certain cases, the HDP-CVD process
may densify the flowable oxide film and may wholly or partially
solidify it. The resulting gap is filled with HDP oxide and
flowable oxide, with only the HDP oxide exposed at the surface.
After completing gap fill, the top of the gap and features may be
planarized, e.g., in a chemical-mechanical planarization (CMP)
process (509). FIG. 5B depicts features and gaps at various stages
of a process as described in this example. At 520, flowable oxide
deposition 110 is depicted in gaps 104. At 530, HDP oxide
deposition 112 to cap the flowable oxide deposition is depicted.
And, at 540, HDP deposition 112 in a wide gap is depicted. As with
the process depicted in FIG. 3B, because there is no overfill
operation of flowable oxide, the flowable oxide thickness in a wide
gap (trench) is much smaller and may be negligible in certain
embodiments.
[0050] In certain embodiments, flowable dielectric material is
deposited in an incoming unfilled gap to reduce the aspect ratio of
the gap for subsequent fill with HDP oxide. FIG. 6A schematically
depicts a cross-section of gaps of various aspect ratios partially
filled with flowable oxide 110. The aspect ratio is defined as the
depth of the trench or other gap divided by the width of its
opening. As depicted qualitatively in FIG. 6A, the aspect ratio
decreases after bottom-up fill with flowable oxide. Also in FIG. 6A
is a plot illustrating aspect ratios prior to and after partial
fill by flowable oxide for various critical dimensions. Critical
dimension refers to the narrowest dimension of the gap opening. Gap
aspect ratios as high as 14:1 were reduced to about 4:1. HDP
deposition improves dramatically as aspect ratios are reduced.
According to various embodiments, the methods described herein may
be used to fill gaps having aspect ratios as high as 60:1, e.g.,
about 30:1, about 20:1 or about 10:1. Critical dimensions may be as
low as 10 nm, 15 nm or 22 nm. In certain embodiments, flowable
oxide is deposited to height such that the aspect ratio of the
partially filled feature is about 6:1 or lower prior to HDP
deposition. FIG. 6B is another plot providing aspect ratios before
and after HDP (white square pre-flowable, and black diamonds, post
flowable.) In certain embodiments, gaps of different incoming AR
are partially filled with a deposition process, with the height of
flowable oxide greatest for the narrowest features.
HDP-CVD Processes
[0051] As described above, the gap fill methods according to the
embodiments described herein include one or more operations in
which the gap is partially filled with a dielectric (HDP oxide)
deposited by high density plasma (HDP) chemical vapor deposition
(CVD) process. Generally, a high density plasma is any plasma
having electron density of at least about 5.times.10.sup.10
electrons per cubic centimeter. Typically, though not necessarily,
high density plasma reactors operate at relatively low pressures,
in the range of 100 mTorr or lower. The HDP CVD deposition results
in beneficial filling of the gap from the bottom up.
[0052] Any suitable deposition chemistry may be used. In general,
an HDP CVD process gas will include a precursor for the deposition
layer. If the dielectric is a silicon-containing dielectric, then
the process gas will include a silicon-bearing compound such as
silane. The process gas will also generally include a carrier gas.
The carrier gas may be an inert gas, such as He and/or other noble
gases. Or the carrier gas may be or include elemental or molecular
hydrogen. Oxygen to form the silicon oxide or other dielectric
material may be provided by the silicon-containing precursor itself
or from another process gas such as elemental oxygen (O.sub.2),
nitric oxide (NO), and/or nitrous oxide (N.sub.2O).
[0053] The deposition process gas will have a particular
composition represented by flow rates of the constituent gases in
units of standard cubic centimeter per minute (sccm). The process
gas will include a precursor for the deposition layer. If the
dielectric is a silicon-containing dielectric, then the process gas
will include a silicon-bearing compound such as SiH.sub.4,
SiF.sub.4, Si.sub.2H.sub.6, TEOS (tetraethyl orthosilicate), TMCTS
(tetramethyl-cyclotetrasiloxane), OMCTS
(octamethyl-cyclotetrasiloxane), methyl-silane, dimethyl-silane,
3MS (trimethylsilane), 4MS (tetramethylsilane), TMDSO
(tetramethyl-disiloxane), TMDDSO
(tetramethyl-diethoxyl-disiloxane), DMDMS
(dimethyl-dimethoxyl-silane) and mixtures thereof. During
deposition, the process decomposes the silicon-containing reactant
to form a silicon-containing gas and plasma phase species, which
can react on the surface of the substrate.
[0054] The process gas will also generally include a carrier gas.
The carrier gas may be an inert gas, such as He and/or other noble
gases, e.g., Ar. Or the carrier gas may be or include elemental or
molecular hydrogen.
[0055] Example flow rate ranges for process gases of the present
invention are listed below.
TABLE-US-00001 Gas Flow Rate (sccm) SiH.sub.4 10-300 O.sub.2
20-1000 He 0-500 H.sub.2 0-5000 Ar 0-500
[0056] Generally, other oxygen and silicon-containing compounds can
be substituted for those listed in this table. Depending upon the
atom counts in the precursor gases, the flow rate ranges may have
to be changed. While there are no precise rules for modifying flow
rates as a function of molecular structure, generally the flow rate
of the silicon-containing precursor may be reduced by a factor
corresponding to the number of silicon atoms in the molecule.
HDP-CVD process gases may contain noble gases (e.g., argon, helium,
or xenon) either as the sole carrier gas, or in a mixture with
hydrogen.
[0057] For doped dielectrics (particularly silicon dioxide based
dielectrics), the process gas may include a dopant precursor such
as a boron-containing gas, a phosphorus-containing gas, a
carbon-containing gas, or a mixture thereof. In a specific
embodiment, the gas includes one or more boron-containing reactants
and one or more phosphorus-containing reactants and the dielectric
film includes a phosphorus- and boron-doped silicon oxide glass
(BPSG). Examples of suitable boron and phosphorus precursor gases
include the following: B.sub.2H.sub.6 and PH.sub.3.
[0058] If the dielectric is to contain an oxyfluoride (e.g.,
silicon oxyfluoride), then the process gas preferably includes a
fluorine-containing reactant such as silicon hexafluoride
(SiF.sub.4). If the dielectric is to contain an oxynitride (e.g.,
silicon oxynitride), then the process gas preferably includes a
nitrogen-containing reactant such as N.sub.2, NH.sub.3, NF.sub.3,
NO, N.sub.2O, and mixtures thereof.
[0059] The method applies as well to the deposition (biased or
unbiased) of carbon-doped silicon oxide from process gas mixtures
including organosilanes (e.g., TEOS (tetraethyl orthosilicate),
TMCTS (tetramethyl-cyclotetrasiloxane), OMCTS
(octamethyl-cyclotetrasiloxane), methyl-silane, dimethyl-silane,
3MS (trimethylsilane), 4MS (tetramethylsilane), TMDSO
(tetramethyl-disiloxane), TMDDSO
(tetramethyl-diethoxyl-disiloxane), DMDMS
(dimethyl-dimethoxyl-silane) and mixtures thereof).
[0060] Reactor pressure is held at a value necessary to sustain the
high-density plasma. In certain embodiments the process vessel is
maintained at a pressure of at most about 100 mTorr. In some cases,
the process chamber pressure is maintained below 1 mTorr. For many
applications, however, the pressure is maintained between about 1
and 100 mTorr; most preferably between about 1 and 30 mTorr.
[0061] The temperature within the process vessel should be
maintained sufficiently high to ensure that the dielectric
deposition reaction proceeds efficiently. Hence, the temperature
preferably resides at values between about 30 and 1000.degree. C.
This temperature will vary depending upon the types of precursors
employed in the reaction. Further, the temperature may be limited
by process constraints, such as thermal budget limitations that
preclude temperatures above 700-750.degree. C. Such constraints
become increasingly common with advanced technologies and
corresponding smaller feature sizes. For such applications, the
process temperature may be maintained between about 30 and
750.degree. C.
[0062] As indicated, to control the substrate temperature, the
reactor may supply a heat transfer gas between a surface of the
substrate and a surface of the substrate holder on which the
substrate is supported during film deposition. The heat transfer
gas may include at least one of helium and argon. The back-side
helium pressure is set by the temperature requirements of the
process (a typical range being between 0-15 Torr).
[0063] For some applications, it may be desirable to preheat the
wafer to a pre-specified relatively low temperature and then
gradually raise the temperature. This allows for isothermal
operation. The goal is to start the deposition and then maintain
the wafer temperature within a narrow range during the entire
deposition process.
[0064] The low frequency power applied to the upper electrode (for
generating the plasma) typically varies from 1 kW to 20 kW, and the
high frequency power (for biasing the wafer) typically reaches at
least about 0.2 W/cm.sup.2 (preferably varying from about 0.5 kW to
10 kW) depending on the substrate size (e.g., 200 or 300 mm
diameter) and the requirements of the specific process being
used.
[0065] As indicated above, the bias applied to the substrate is
typically a radio frequency bias. Applying radio frequency bias to
the substrate involves supporting the substrate on a substrate
holder having an electrode supplying a radio frequency bias to the
substrate. For many embodiments, the radio frequency bias applied
to the substrate is at the frequency range of between about 100 kHz
and 27 MHz. The frequency range applied to the upper,
plasma-generating electrode is typically between about 300 kHz and
27 MHz.
[0066] The deposition conditions may be selected to optimize
deposition topography. The deposition topography can be optimized
by manipulating the S/D ratio of the deposition process. S/D ratio
refers to the sputter/deposition ratio. It is obtained by measuring
the deposition rate for a given dielectric deposition process and
then measuring the sputter rate for that same process performed
without the silicon-containing precursor (e.g., silane). The S/D
ratio is given by the following expression: [0067] S/D=sputter
rate/(sputter rate+deposition rate).
[0068] The conditions may be set so that the isotropic etch is
selective for the HDP CVD deposited dielectric (e.g., SiO.sub.2)
relative to the feature material, e.g., a silicon nitride barrier
layer lining the gap.
[0069] An HDP deposition operation may include only a single
deposition, or a single deposition-etch operation, or may include a
multiple deposition-etch cycles. For example, multiple
SiH.sub.4/O.sub.2 deposition operations may include intervening
NF.sub.3 plasma etch operations.
[0070] While the above provides a description of example HDP-CVD
processes and conditions, the methods described herein are not
limited to these particular HDP-CVD processes but may be applied
with other HDP-CVD processes.
Flowable Oxide Deposition Processes
[0071] As described above, the gap fill methods according to the
embodiments described herein include one or more operations in
which the gap is partially filled or overfilled with a dielectric
flowable oxide film. In many embodiments, the flowable dielectric
film is a flowable silicon and oxygen-containing film, though the
integration schemes described herein can also be implemented with
other flowable dielectric films. According to various embodiments,
the flowable film is formed by a spin-on glass technique. In
alternate embodiments, the flowable film is formed by introducing
vapor phase reactants to a deposition chamber at conditions such
that a flowable film is formed on the substrate to fill the
gap.
[0072] After the substrate is provided to the reaction chamber,
process gases are introduced. For forming silicon oxides, the
process gas reactants generally include a silicon-containing
compound and an oxidant, and may also include a catalyst, a solvent
and other additives. The gases may also include one or more dopant
precursors, e.g., a fluorine, phosphorous and/or boron-containing
gas. Sometimes, though not necessarily, an inert carrier gas is
present. In certain embodiments, the gases are introduced using a
liquid injection system. In certain embodiments, the
silicon-containing compound and the oxidant are introduced via
separate inlets or are combined just prior to introduction into the
reactor in a mixing bowl and/or showerhead. The catalyst and/or
optional dopant may be incorporated into one of the reactants,
pre-mixed with one of the reactants or introduced as a separate
reactant. The substrate is then exposed to the process gases at an
operation. Conditions in the reactor are such that the
silicon-containing compound and the oxidant react to form a
condensed flowable film on the substrate. Formation of the film may
be aided by presence of a catalyst. The method is not limited to a
particular reaction mechanism, e.g., the reaction mechanism may
involve a condensation reaction, a vapor-phase reaction producing a
vapor-phase product that condenses, condensation of one or more of
the reactants prior to reaction, or a combination of these. The
substrate is exposed to the process gases for a period sufficient
to deposit a flowable film to fill at least some of the gap or
overfill the gap as desired.
[0073] In certain embodiments, the overall deposition process may
be described in context of two steps: hydrolysis and condensation.
The first step involves hydrolysis of silicon-containing precursors
by the oxidant. For example, alkoxy groups (--OR) of the silicon
containing precursor may be replaced with hydroxyl groups (--OH).
In the condensation step, Si--O--Si linkages may be formed when
--OH groups are removed from Si. It should be noted that while
these reaction steps provide a useful framework for describing
various aspects of the invention, the methods described herein are
not necessarily limited to a particular reaction mechanism.
[0074] FIG. 7 provides certain operations in a method of filling a
gap with a flowable oxide material according to certain
embodiments. The process typically begins prior to any oxide
material being deposited in the gap, with the gap defined by
sidewall and bottom surfaces. The sidewall and bottom surfaces may
be silicon nitride, silicon oxide, silicon oxynitride, or other
silicon-containing materials.
[0075] At 701, a substrate including a gap is provided. Then an
optional pretreatment operation is performed (Block 703). According
to various embodiments, a pretreatment operation involves exposure
to a plasma containing oxygen, nitrogen, helium or some combination
of these. The plasma may be downstream or in-situ, generated by a
remote plasma generator, such as an Astron.RTM. remote plasma
source, an inductively-coupled plasma generator or a
capacitively-coupled plasma generator. Examples of pre-treatment
gases include O.sub.2, O.sub.3, H.sub.2O, NO, NO.sub.2, N.sub.2O,
H.sub.2, N.sub.2, He, Ar, and combinations thereof, either alone or
in combination with other compounds. Examples of chemistries
include O.sub.2, O.sub.2/N.sub.2, O.sub.2/He, O.sub.2/Ar,
O.sub.2/H.sub.2. The particular process conditions may vary
depending on the implementation. In alternate embodiments, the
pretreatment operation involves exposing the substrate to O.sub.2,
O.sub.2/N.sub.2, O.sub.2/He, O.sub.2/Ar or other pretreatment
chemistries, in a non-plasma environment. In these embodiments, the
substrate may be exposed to the pretreatment chemistry in the
presence energy from another energy source, including a thermal
energy source, a ultra-violet source, a microwave source, etc. In
certain embodiments, other pretreatment operations described above,
a substrate is pretreated with exposure to a catalyst. The
pre-treatment operation, if performed, may occur in the deposition
chamber or may occur in another chamber prior to transfer of the
substrate to the deposition chamber. Once in the deposition
chamber, and after the optional pre-treatment operation, process
gases are introduced.
Deposition Chemistries
[0076] For forming silicon oxides, the process gas reactants
generally include a silicon-containing compound and an oxidant, and
may also include a catalyst, a solvent and other additives. The
gases may also include one or more dopant precursors, e.g., a
fluorine, phosphorous and/or boron-containing gas. Sometimes,
though not necessarily, an inert carrier gas is present. In certain
embodiments, the gases are introduced using a liquid injection
system. In certain embodiments, the silicon-containing compound and
the oxidant are introduced via separate inlets or are combined just
prior to introduction into the reactor in a mixing bowl and/or
showerhead. The catalyst and/or optional dopant may be incorporated
into one of the reactants, pre-mixed with one of the reactants or
introduced as a separate reactant. The substrate is then exposed to
the process gases to deposit a flowable film in the gap at an
operation 705. Conditions in the reactor are such that the
silicon-containing compound and the oxidant react to form a
condensed flowable film on the substrate. Formation of the film may
be aided by presence of a catalyst. The method is not limited to a
particular reaction mechanism, e.g., the reaction mechanism may
involve a condensation reaction, a vapor-phase reaction producing a
vapor-phase product that condenses, condensation of one or more of
the reactants prior to reaction, or a combination of these. The
substrate is exposed to the process gases for a period sufficient
to deposit a flowable film to fill at least some of the gap or
overfill the gap as desired.
[0077] In certain embodiments, the silicon-containing precursor is
an alkoxysilane. Alkoxysilanes that may be used include, but are
not limited to, the following:
H.sub.x--Si--(OR).sub.y where x=0-3, x+y=4 and R is a substituted
or unsubstituted alkyl group; R'.sub.x--Si--(OR).sub.y where x=0-3,
x+y=4, R is a substituted or unsubstituted alkyl group and R' is a
substituted or unsubstituted alkyl, alkoxy or alkoxyalkane group;
and H.sub.x(RO).sub.y--Si--Si--(OR).sub.yH.sub.x where x=0-2,
x+y=0-2 and R is a substituted or unsubstituted alkyl group.
[0078] Examples of silicon containing precursors include, but are
not limited to, alkoxysilanes, e.g.,
tetraoxymethylcyclotetrasiloxane (TOMCTS),
octamethylcyclotetrasiloxane (OMCTS), tetraethoxysilane (TEOS),
triethoxysilane (TES), trimethoxysilane (TriMOS),
methyltriethoxyorthosilicate (MTEOS), tetramethylorthosilicate
(TMOS), methyltrimethoxysilane (MTMOS), dimethyldimethoxysilane
(DMDMOS), diethoxysilane (DES), dimethoxysilane (DMOS),
triphenylethoxysilane,
1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane,
tri-t-butoxylsilanol, hexamethoxydisilane (HMODS),
hexaethoxydisilane (HEODS), tetraisocyanatesilane (TICS), and
bis-tert-butylamino silane (BTBAS). Further examples of silicon
containing precursors include silane (SiH.sub.4) and alkylsilanes,
e.g., methylsilane, and ethylsilane.
[0079] In certain embodiments, carbon-doped precursors are used,
either in addition to another precursor (e.g., as a dopant) or
alone. Carbon-doped precursors include at least one Si--C bond.
Carbon-doped precursors that may be used include, but are not
limited to the, following:
R'.sub.x--Si--R.sub.y where x=0-3, x+y=4, R is a substituted or
unsubstituted alkyl group and R' is a substituted or unsubstituted
alkyl, alkoxy or alkoxyalkane group; and SiH.sub.xR'.sub.y--R.sub.z
where x=1-3, y=0-2, x+y+z=4, R is a substituted or unsubstituted
alkyl group and R' is a substituted or unsubstituted alkyl, alkoxy
or alkoxyalkane group.
[0080] Examples of carbon-doped precursors include
(CH.sub.3Si(OCH.sub.2).sub.3, trimethylsilane (3MS),
tetramethylsilane (4MS), diethoxymethylsilane (DEMS),
dimethyldimethoxysilane (DMDMOS), methyl-triethoxysilane (MTES),
methyl-trimethoxysilane, methyl-diethoxysilane and
methyl-dimethoxysilane. Additional carbon-doped precursors are
described above. In certain embodiments, the film is doped with
extra silicon.
[0081] Examples of suitable oxidants include, but are not limited
to, ozone (O.sub.3), peroxides including hydrogen peroxide
(H.sub.2O.sub.2), oxygen (O.sub.2), water (H.sub.2O), alcohols such
as methanol, ethanol, and isopropanol, nitric oxide (NO), nitrous
dioxide (NO.sub.2) nitrous oxide (N.sub.2O), carbon monoxide (CO)
and carbon dioxide (CO.sub.2). In certain embodiments, a remote
plasma generator may supply activated oxidant species.
[0082] One or more dopant precursors, catalysts, inhibitors,
buffers, solvents and other compounds may be introduced. In certain
embodiments, a proton donor catalyst is employed. Examples of
proton donor catalysts include 1) acids including nitric,
hydrofluoric, phosphoric, sulphuric, hydrochloric and bromic acids;
2) carboxylic acid derivatives including R--COOH and R--C(.dbd.O)X
where R is substituted or unsubstituted alkyl, aryl, acetyl or
phenol and X is a halide, as well as R--COOC--R carboxylic
anhydrides; 3) Si.sub.xX.sub.yH.sub.z where x=1-2, y=1-3, z=1-3 and
X is a halide; 4) R.sub.xSi--X.sub.y where x=1-3 and y=1-3; R is
alkyl, aloxy, aloxyalkane, aryl, acetyl or phenol; and X is a
halide; and 5) ammonia and derivatives including ammonium
hydroxide, hydrazine, hydroxylamine, and R--NH.sub.2 where R is
substituted or unsubstituted alkyl, aryl, acetyl, or phenol.
[0083] In addition to the examples of catalysts given above,
halogen-containing compounds which may be used include halogenated
organic molecule such as dichlorosilane (SiCl.sub.2H.sub.2),
trichlorosilane (SiCl.sub.3H), methylchlorosilane
(SiCH.sub.3ClH.sub.2), chlorotriethoxysilane, and
chlorotrimethoxysilane. Acids which may be used may be mineral
acids such as hydrochloric acid (HCl), sulphuric acid
(H.sub.2SO.sub.4), and phosphoric acid (H.sub.3PO.sub.4); organic
acids such as formic acid (HCOOH), acetic acid (CH3COOH), and
trifluoroacetic acid (CF.sub.3COOH). Bases which may be used
include ammonia (NH3) or ammonium hydroxide (NH.sub.4OH), phosphine
(PH.sub.3); and other nitrogen- or phosphorus-containing organic
compounds. Additional examples of catalysts are
chloro-diethoxysilane, methanesulfonic acid (CH.sub.3SO.sub.3H),
trifluoromethanesulfonic acid ("triflic", CF.sub.3SO.sub.3H),
chloro-dimethoxysilane, pyridine, acetyl chloride, chloroacetic
acid (CH.sub.2ClCO.sub.2H), dichloroacetic acid
(CHCl.sub.2CO.sub.2H), trichloroacetic acid (CCL.sub.2CO.sub.2H),
oxalic acid (HO.sub.2CCO.sub.2H) and benzoic acid
(C.sub.6H.sub.5CO.sub.2H).
[0084] According to various embodiments, catalysts and other
reactants may be introduced simultaneously or in particular
sequences. For example, in some embodiments, a acidic compound may
be introduced into the reactor to catalyze the hydrolysis reaction
at the beginning of the deposition process, then a basic compound
may be introduced near the end of the hydrolysis step to inhibit
the hydrolysis reaction and the catalyze the condensation reaction.
Acids or bases may be introduced by normal delivery or by rapid
delivery or "puffing" to catalyze or inhibit hydrolysis or
condensation reaction quickly during the deposition process.
Adjusting and altering the pH by puffing may occur at any time
during the deposition process, and difference process timing and
sequence may result in different films with properties desirable
for different applications. Some examples of catalysts are given
above. Examples of other catalysts include hydrochloric acid (HCl),
hydrofluoric acid (HF), acetic acid, trifluoroacetic acid, formic
acid, dichlorosilane, trichlorosilane, methyltrichlorosilane,
ethyltrichlorosilane, trimethoxychlorosilane, and
triethoxychlorosilane. Methods of rapid delivery that may be
employed are described in U.S. application Ser. No. 12/566,085,
incorporated by reference herein. In certain embodiments, a
multistage flowable oxide deposition is performed, in which the
presence, identity or amount of catalyst is varied according to if
a gap is being filled, or a planar or overburden layer is
deposited. For example, features are selectively filled by an
uncatalyzed process, and an overburden or blanket layer is
deposited using a catalyst.
[0085] Solvents may be non-polar or polar and protic or aprotic.
The solvent may be matched to the choice of dielectric precursor to
improve the miscibility in the oxidant. Non-polar solvents include
alkanes and alkenes; polar aprotic solvents include acetones and
acetates; and polar protic solvents include alcohols and carboxylic
compounds.
[0086] Examples of solvents that may be introduced include
alcohols, e.g., isopropyl alcohol, ethanol and methanol, or other
compounds, such as ethers, carbonyls, nitriles, miscible with the
reactants. Solvents are optional and in certain embodiments may be
introduced separately or with the oxidant or another process gas.
Examples of solvents include, but not limited to, methanol,
ethanol, isopropanol, acetone, diethylether, acetonitrile,
dimethylformamide, and dimethyl sulfoxide, tetrahydrofuran (THF),
dichloromethane, hexane, benzene, toluene, isoheptane and
diethylether. The solvent may be introduced prior to the other
reactants in certain embodiments, either by puffing or normal
delivery. In some embodiments, the solvent may be introduced by
puffing it into the reactor to promote hydrolysis, especially in
cases where the precursor and the oxidant have low miscibility.
[0087] Sometimes, though not necessarily, an inert carrier gas is
present. For example, nitrogen, helium, and/or argon, may be
introduced into the chamber with one of the compounds described
above.
[0088] As indicated above, any of the reactants (silicon-containing
precursor, oxidant, solvent, catalyst, etc.) either alone or in
combination with one or more other reactants, may be introduced
prior to the remaining reactants. Also in certain embodiments, one
or more reactants may continue to flow into the reaction chamber
after the remaining reactant flows have been shut off.
[0089] In certain embodiments, reactions conditions are such that
the silicon-containing compound and oxidant, undergo a condensation
reaction, condensing on the substrate surface to form a flowable
film. In certain embodiments, the reaction takes place in dark or
non-plasma conditions. In other embodiments, the reaction takes
place in the presence of a plasma. Methods of depositing a flowable
film for gap fill via a plasma-enhanced chemical vapor deposition
(PECVD) reaction are described in U.S. patent application Ser. No.
12/334,726, incorporated by reference herein.
[0090] Chamber pressure may be between about 1-200 Torr, in certain
embodiments, it is between 10 and 75 Torr. In a particular
embodiment, chamber pressure is about 10 Torr.
[0091] Partial pressures of the process gas components may be
characterized in terms of component vapor pressure and range as
follows, with Pp the partial pressure of the reactant and Pvp the
vapor pressure of the reactant at the reaction temperature:
Precursor partial pressure ratio (Pp/Pvp)=0.01-1, e.g., 0.01-0.5
Oxidant partial pressure ratio (Pp/Pvp)=0.25-2, e.g., 0.5-1 Solvent
partial pressure ratio (Pp/Pvp)=0-1, e.g., 0.1-1
[0092] In certain embodiments, the process gas is characterized by
having a precursor partial pressure ratio is 0.01 and 0.5, an
oxidant partial ratio between 0.5 and 1, and a solvent (if present)
partial pressure ratio between 0.1 and 1. In the same or other
embodiments, the process gas is characterized by the following:
Oxidant:Precursor partial pressure ratio
(Pp.sub.oxidant/Pp.sub.precursor)=1-30, e.g., 5-15 Solvent:Oxidant
partial pressure ratio (Pp.sub.solvent/Pp.sub.oxidant)=0-10, e.g.,
0.1-5
[0093] In certain embodiments, the process gas is characterized by
an oxidant:precursor partial pressure ratio of between about 5 and
15 and a solvent:oxidant partial pressure ratio of between about
0.1 and 5; as well as further characterized by the ratios described
above.
[0094] Substrate temperature is between about -20.degree. C. and
100.degree. C. in certain embodiments. In certain embodiments,
temperature is between about -20.degree. C. and 30.degree. C.,
e.g., between -10.degree. C. and 10.degree. C. Pressure and
temperature may be varied to adjust deposition time; high pressure
and low temperature are generally favorable for quick deposition.
High temperature and low pressure will result in slower deposition
time. Thus, increasing temperature may require increased pressure.
In one embodiment, the temperature is about 5.degree. C. and the
pressure about 10 Torr. Exposure time depends on reaction
conditions as well as the desired film thickness. Deposition rates
are from about 100 angstroms/min to 1 micrometer/min according to
various embodiments. In certain embodiments, deposition time is
0.1-180 seconds, e.g., 1-90 seconds. In certain embodiments,
deposition time is less than nucleation delay for the same
deposition process on a blanket film.
[0095] The substrate is exposed to the reactants under these
conditions for a period long enough to deposit a flowable film in
the gap. In the depicted embodiment, the entire desired thickness
of film is deposited in operation 705, as it is a single cycle
deposition. In other embodiments which employ multiple deposition
operations, only a portion of the desired film thickness is
deposited in a particular cycle. In certain embodiments, the
substrate is continuously exposed to the reactants during operation
705, though in other embodiments, one or more of the reactants may
be pulsed or otherwise intermittently introduced. Also as noted
above, in certain embodiments, one or more of the reactants
including a dielectric precursor, oxidant, catalyst or solvent, may
be introduced prior to introduction of the remaining reactants
and/or continue flowing into the reactor after the remaining
reactant flows are shut off.
[0096] Exposure time depends on reaction conditions as well as the
desired film thickness. Deposition rates are typically from about
100 angstroms/min to 1 micrometer/min. In certain embodiments, the
deposition may be a plasma-enhanced chemical vapor deposition
(PECVD) reaction that uses a capacitively-coupled plasma source.
PECVD reactions have lower plasma densities than HDP plasmas, e.g.,
10.sup.8 electrons/cm.sup.3 and up to 10.sup.10
electrons/cm.sup.3.
Post-Deposition Treatments
[0097] After deposition, the as-deposited film is treated according
to various embodiments (Block 707). According to various
embodiments, one or more treatment operations are performed to do
one or more of the following: introduction of a dopant, chemical
conversion of the as-deposited film, and densification. In certain
embodiments, a single treatment may do or more of these. A
post-deposition treatment may be performed in situ, i.e., in the
deposition chamber, or in another chamber. Densification operations
may be plasma-based, purely thermal, or by exposure to radiation
such as ultra-violet, infra-read or microwave radiation.
[0098] Post-deposition treating of the flowable oxide film, if
performed, may be done in situ or ex situ of the deposition
chamber. The post-deposition densification treatment operation may
involve one or more operations, any or all of which may also result
in chemically converting the as-deposited film. In other
embodiments, any or all of the densification operations may densify
without conversion. In certain embodiments, one conversion
operation may be separately performed, or not performed at all. If
separately performed, a conversion operation may be performed
before or after a densification operation. In one example, a film
is converted and partially densified by exposure to a reactive
plasma followed by further densification by thermal anneal in an
inert environment.
[0099] According to various embodiments, the film may be densified
by purely thermal anneal, exposure to a plasma, exposure to
ultraviolet or microwave radiation or exposure to another energy
source. Thermal anneal temperatures may be 300 C or greater
(depending on thermal budget). The treatment may be performed in an
inert environment (Ar, He, etc.) or in a potentially reactive
environment. Oxidizing environments (using O.sub.2, N.sub.2O,
O.sub.3, H.sub.2O, H.sub.2O.sub.2, NO, NO.sub.2, CO, CO.sub.2 etc.)
may be used, though in certain situation nitrogen-containing
compounds will be avoided to prevent incorporation of nitrogen in
the film. In other embodiments, nitridizing environments (using
N.sub.2, N.sub.2O, NH.sub.3, NO, NO.sub.2 etc.) are used. In some
embodiments, a mix of oxidizing and nitridizing environments are
used. Carbon-containing chemistries may be used to incorporate some
amount of carbon into the deposited film. According to various
embodiments, the composition of the densified film depends on the
as-deposited film composition and the treatment chemistry. For
example, in certain embodiments, an Si(OH)x as-deposited gel is
converted to a SiO network using an oxidizing plasma cure. In other
embodiments, a Si(OH)x as-deposited gel is converted to a SiON
network.
[0100] In certain embodiments, the film is treated by exposure to a
plasma, either remote or direct (inductive or capacitive). This may
result in a top-down conversion of the flowable film to a densified
solid film. The plasma may be inert or reactive. Helium and argon
plasma are examples of inert plasmas; oxygen and steam plasmas are
examples of oxidizing plasmas (used for example, to remove carbon
as desired). Hydrogen plasmas may also be used. Temperatures during
plasma exposure are typically about 200.degree. C. or higher. In
certain embodiments, an oxygen or oxygen-containing plasma is used
to remove carbon.
[0101] Temperatures may range from 0-600.degree. C., with the upper
end of the temperature range determined by the thermal budget at
the particular processing stage. For example, in certain
embodiments, the entire process shown in FIG. 3 is carried out at
temperatures less than about 400.degree. C. This temperature regime
is compatible with NiSi contacts. In certain embodiments, the
temperatures range from about 200.degree. C.-550.degree. C.
Pressures may be from 0.1-10 Torr, with high oxidant pressures used
for removing carbon.
[0102] Other annealing processes, including rapid thermal
processing (RTP) may also be used to solidify and shrink the film.
If using an ex situ process, higher temperatures and other sources
of energy may be employed. Ex situ treatments include high
temperature anneals (700-1000.degree. C.) in an environment such as
N.sub.2, O.sub.2, H.sub.2O and He. In certain embodiments, an ex
situ treatment involves exposing the film to ultra-violet
radiation, e.g., in a ultraviolet thermal processing (UVTP)
process. For example, temperatures of 400.degree. C. or above in
conjunction with UV exposure may be used to cure the film. Other
flash curing processes, including RTP, may be used for the ex situ
treatment as well.
[0103] In certain embodiments, a film is densified and converted by
the same process operations. Converting a film involves using a
reactive chemistry. According to various embodiments, the
composition of the film depends on the as-deposited film
composition and the cure chemistry. For example, in certain
embodiments, an Si(OH)x as-deposited gel is converted to a SiO
network using an oxidizing plasma cure. In other embodiments, a
Si(OH)x as-deposited gel is converted to a SiON network by exposure
to an oxidizing and nitridizing plasma.
[0104] In other embodiments, the flowable dielectric film may be a
silicon and nitrogen-containing film, such as silicon nitride or
silicon oxynitride. It may be deposited by introducing vapor phase
reactants to a deposition chamber at conditions such that they
react to form a flowable film. The vapor phase reactants may
include species created by a plasma. Such a plasma may be generated
remotely or in the deposition chamber. The nitrogen incorporated in
the film may come from one or more sources, such as a silicon and
nitrogen-containing precursor (for example, trisilylamine (TSA) or
disilylamine (DSA)), a nitrogen precursor (for example, ammonia
(NH3) or hydrazine (N2H4)), or a nitrogen-containing gas fed into a
plasma (N2, NH3, NO, NO2, N2O). After deposition, the flowable
dielectric film may be treated to do one of more of the following:
chemical conversion of the as-deposited film, densification. The
chemical conversion may include removing some or all of the
nitrogen component, converting a Si(ON)x film to a primarily SiO
network. It may also include removal of one or more of --H, --OH,
--CH and --NH species from the film. The post-deposition treatment
may include exposure to thermal, plasma, UV, IR or microwave
energy.
Reaction Mechanism
[0105] As indicated above, the flowable dielectric deposition may
involve various reaction mechanisms depending on the specific
implementation. Examples of reaction mechanisms in a method of
depositing a flowable oxide film according to certain embodiments
are described below. It should be noted that while these reaction
steps provide a useful framework for describing various aspects of
the invention, the methods described herein are not necessarily
limited to a particular reaction mechanism.
[0106] The overall deposition process may be described in context
of two steps: hydrolysis and condensation. The first step involves
hydrolysis of silicon-containing precursors by the oxidant. For
example, alkoxy groups (--OR) of the silicon containing precursor
may be replaced with hydroxyl groups (--OH). The --OH groups and
the residual alkoxy groups participate in condensation reactions
that lead to the release of water and alcohol molecules and the
formation of Si--O--Si linkages. In this mechanism, the
as-deposited film does not have appreciable carbon content even
though the alkoxysilane precursor contains carbon. In certain
embodiments, reactant partial pressure is controlled to facilitate
bottom up fill. Liquid condensation occurs below saturation
pressure in narrow gaps; the reactant partial pressure controls the
capillary condensation. In certain embodiments, reactant partial
pressure is set slightly below the saturation pressure. In a
hydrolyzing medium, the silicon-containing precursor forms a
fluid-like film on the wafer surface that preferentially deposits
in trenches due to capillary condensation and surface tension
forces, resulting in a bottom-up fill process.
[0107] FIGS. 8A-8D provides a simplified schematic diagram of
deposition and anneal reaction mechanisms according to one
embodiment. It should be noted that the methods described herein
are not limited to the particular reactants, products and reaction
mechanisms depicted, but may be used with other reactants and
reaction mechanisms that produce flowable dielectric films. It will
also be understood that deposition and annealing may involve
multiple different concurrent or sequential reaction
mechanisms.
[0108] FIG. 8A depicts reactant condensation, hydrolysis and
initiation of the flowable film on a wafer 801, held at a reduced
temperature such as -5.degree. C. The reactants include a
dielectric precursor 802, an oxidant 804, an optional catalyst 803
and an optional solvent 805. The dielectric precursor absorbs 802
on the surface. A liquid phase reaction between precursor and
oxidant results in hydrolysis of precursor, forming silanols
Si(OH)x (806) attached to the wafer surface initiating the growth
of the film. In certain embodiments, the presence of the solvent
improves miscibility and surface wettability.
[0109] FIG. 8B depicts polymerization of the product (see Si(OH)x
chain 808) as well as condensation of the silanols to form
crosslinked Si--O chains. The result of the condensation reaction
is a gel 809. At this stage, the organic groups may be
substantially eliminated from the gel 809, with alcohol and water
released as byproducts, though as depicted Si--H groups 811 remain
in the gel as do hydroxyl groups. In some cases, a minute but
detectable amount of carbon groups remains in the gel. The overall
carbon content may be less than 1% (atomic). In some embodiments,
essentially no carbon groups remain, such that Si--C groups are
undetectable by FTIR. FIG. 8C depicts a reaction mechanism during
an anneal, in this case in the presence of an activated oxygen
species O* (810), e.g. oxygen radicals, ions, etc. In certain
embodiments, the anneal has two effects: 1) oxidation of the gel,
to convert SiOH and SiH to SiO and the gel to a SiO network 813;
and 2) film densification or shrinkage. The oxygen oxidizes Si--H
bonds and facilitates formation of a SiOx network with
substantially no Si--H groups. The substrate temperature may be
raised, e.g., to 375.degree. C. to facilitate film shrinkage and
oxidization. In other embodiments, the oxidation and shrinkage
operations are carried out separately. In some embodiments,
oxidation may occur at a first temperature (e.g., 300.degree. C.)
with further densification occurring at a higher temperature (e.g.,
375.degree. C.). FIG. 8D shows a schematic depiction of a densified
SiO film 814.
Fill Height Selectivity
[0110] Flowable oxide fill height is a function of critical
dimension. That is, deposition into wide features results in little
to no fill height with height increasing as the feature dimension
narrows. It has been found that in certain embodiments, the slope
of the fill height vs. critical dimension curve is tunable by
tuning reactant partial pressures. FIG. 9A presents qualitative
examples in which curve 902 is obtained by lowering the solvent
partial pressure and curve 903 is obtained by raising the solvent
partial pressure. In this manner, the fill selectivity across
features of various critical dimensions can be tuned for a
particular deposition, for example, to increase fill height in
narrow features and decrease it in wide features.
[0111] FIG. 9B is a graph showing two data series: the data points
represented by a square are from a process having a higher solvent
(ethanol) partial pressure; the data points represented by a
diamond using the same process but with lower solvent (ethanol)
partial pressure. As can be seen lower solvent partial pressure
changes the slope of the curve such that fill selectivity of
narrower features is increased. Without being bound by a particular
theory, it is believed that the tunability of fill height
selectivity is a feature of depositions involving capillary
condensation mechanisms. The amount of solvent, for example, has a
large effect on the surface tension of the fill already in the
feature, and hence the capillary condensation mechanism. Ranges of
reactant partial pressure ratios are provided above. Capillary
condensation mechanisms according to certain embodiments are
described above and in U.S. Pat. No. 7,074,690, incorporated by
reference above.
Process Sequences
[0112] FIGS. 10-12 provide examples of process sequences according
to various embodiments. First, in FIG. 10, a process begins by
pre-treating a wafer, e.g., to make it hydrophilic or otherwise
treated for deposition. (Block 1001). Examples of pre-treatments
are described above. In some embodiments, this operation may not be
performed, that is the wafer may be provided directly to a flowable
oxide deposition module for deposition. As indicated in FIG. 10, if
the pre-treatment is performed outside the flowable oxide
deposition module, the wafer is then transferred to the flowable
oxide deposition module (1003). This typically occurs under inert
atmosphere or vacuum to preserve the effects of the pre-treatment.
One or more gaps are then partially filled with a flowable oxide
film. (Block 1005). According to various embodiments, this may
involve a single deposition, or multiple deposition cycles. If an
in situ post-deposition treatment is to be performed, it is done in
the deposition module (Block 1007). After the in situ
post-deposition treatment is performed, or directly after
deposition if no in situ treatment is performed, the wafer is
transferred to a separate cure module and treated if a separate
treatment is to be performed (Block 1009). For example, in certain
embodiments, the wafer is transferred to a remote cure module for
exposure to a remotely generated oxidizing plasma. The wafer is
then transferred to an HDP deposition module for HDP deposition.
(Block 1011). HDP oxide is then deposited. (Block 1013). Although
not indicated, exposure to a direct inductively couple oxidizing
plasma or other treatment may occur in the HDP module prior to
deposition of HDP oxide in some embodiments. In some embodiments,
the flowable film is oxidized during HDP oxide deposition.
[0113] Various modifications may be made in the process shown in
FIG. 10. For example, in certain embodiments, pre-treatment and/or
flowable oxide deposition may take place in the HDP deposition
module, eliminating certain transfer operations. It should be noted
that prior to operation 1001, the gaps on the wafer may be unfilled
(e.g., as depicted in FIG. 1A) or may be partially filled from one
or more preceding flowable oxide or HDP depositions as described
above.
[0114] Once in the HDP chamber, the wafer may be subjected to a
pre-heat operation. According to various embodiments, the pre-heat
may be accompanied by exposure to an oxidant to oxidize the
flowable film prior to HDP oxide deposition. In other embodiments,
the pre-heat is performed in an oxidant-free environment. The
latter may be done, e.g., after treatment in a remote plasma cure
module.
[0115] FIG. 11 is a process sequence according to certain
embodiments in which the flowable dielectric material is deposited
in a gap formed in a silicon or SOI surface. An example is gap fill
in an STI integration process. The process described in FIG. 11 may
be used in conjunction with that described in FIG. 10, for example.
First, a silicon or SOI wafer including a gap formed in the silicon
or SOI is provided. (Block 1101). Flowable dielectric material is
then deposited in the gap. (Block 1103). Various pre-treatments as
described above may be performed prior to deposition. The flowable
dielectric material is then selectively oxidized, i.e., it is
oxidized without oxidizing the underlying silicon. (Block
1105).
[0116] Selectively oxidizing the flowable dielectric material may
involve exposure to a remotely generated oxidizing plasma, exposure
to ultraviolet radiation in the presence of steam or another
oxidant, or exposure to an oxidant in a thermal anneal, e.g., a
steam anneal. As described above, these may be performed in the
deposition chamber or in another chamber. In certain embodiments, a
direct (non-remote) inductively-coupled or capacitively-coupled
oxidizing plasma is used to selectively oxidize the flowable
dielectric material. In such instances, selective oxidation may
involve not applying a bias to the substrate and/or performing the
oxidation at relatively low temperatures. In one example, the
plasma is applied at the deposition temperature in situ in the
chamber. Lowering plasma density may also improve selectivity. Also
in certain embodiments, pre-heat in an HDP chamber is done in a
non-oxidant environment to prevent oxidation of the underlying
layer.
[0117] As mentioned above, in certain embodiments deposition of the
flowable dielectric film involves multiple deposition-cure cycles.
FIG. 12 illustrates a process sequence involving such an operation.
First, a substrate including a gap is provided. (Block 1201). Then,
an amount of flowable oxide film is deposited in the gap. (Block
1203). In certain embodiments, the amount of flowable oxide
deposited in operation 1203 is less than the total desired amount
of flowable oxide desired in the gap. The deposited flowable
dielectric material is then treated to wholly or partially solidify
the material deposited in the previous operation. (Block 1205).
Here, the treatment that is performed does not appreciably shrink
the film, but dries or solidifies it such that it provides
structural reinforcement to the sidewalls of the gap.
Solidification or drying without substantial shrinkage may be
accomplished in certain embodiments by an in-situ inert or reactive
plasma at the deposition temperature or non-plasma exposure to an
oxidant. While there may be some amount of cross-linking and
densification, this operation is distinct from a full densification
and cross-linking. In certain embodiments, the treatment also
functions as a pre-treatment for a subsequent deposition operation.
In one example, the film is exposed to a nitrogen and
oxygen-containing plasma at the deposition temperature. In other
embodiments, the solidification operation may be succeeded by a
pre-treatment operation prior to additional flowable oxide
deposition. For example, this may involve exposure to an inert
plasma followed by exposure to an oxidizing pre-treatment plasma.
The flowable oxide deposition and treatment operations are repeated
until the desired amount of flowable oxide is deposited. In the
depicted embodiment, this is enough only to partially fill the gap,
though in other embodiments, it may be to fully fill the gap. In
the depicted embodiment, gap fill is then completed with HDP oxide
deposition. (Block 1207). Densification or other treatments may be
performed prior to the HDP oxide deposition.
Apparatus
[0118] The methods of the present invention may be performed on a
wide-range of apparatuses. The deposition operations may be
implemented on any chamber equipped for deposition of dielectric
film, including HDP-CVD reactors, PECVD reactors, sub-atmospheric
CVD reactor, any chamber equipped for CVD reactions, and chambers
used for PDL (pulsed deposition layers), with the treatment
operations performed using these or other chambers.
[0119] Generally, an apparatus will include one or more chambers or
"reactors" (sometimes including multiple stations) that house one
or more wafers and are suitable for wafer processing. Each chamber
may house one or more wafers for processing. The one or more
chambers maintain the wafer in a defined position or positions
(with or without motion within that position, e.g. rotation,
vibration, or other agitation). While in process, each wafer is
held in place by a pedestal, wafer chuck and/or other wafer holding
apparatus. For certain operations in which the wafer is to be
heated, the apparatus may include a heater such as a heating
plate.
[0120] FIG. 13 depicts example tool configuration 1300 in which the
tool includes two high density plasma chemical vapor deposition
(HDP-CVD) modules 1310, flowable gap fill module 1320, WTS (Wafer
Transfer System) 1340, loadlocks 1350, in some embodiments
including a wafer cooling station, and vacuum transfer module 1335.
HDP-CVD modules 1310 may, for example, be Novellus SPEED MAX
modules. Flowable gap fill module 1320 may, for example, be a
Novellus Flowable Oxide module.
[0121] FIG. 14 is a simplified illustration of various components
of a HDP-CVD apparatus that may be used for deposition of HDP oxide
and pre- and/or post-deposition treatment or cures according to
various embodiments. Also in certain embodiments, it may be used
for flowable oxide deposition. As shown, a reactor 1401 includes a
process chamber 1403 which encloses other components of the reactor
and serves to contain the plasma. In one example, the process
chamber walls are made from aluminum, aluminum oxide, and/or other
suitable material. The embodiment shown in FIG. 14 has two plasma
sources: top RF coil 1405 and side RF coil 1407. Top RF coil 1405
is a medium frequency or MFRF coil and side RF coil 1407 is a low
frequency or LFRF coil. In the embodiment shown in FIG. 14, MFRF
frequency may be from 430-470 kHz and LFRF frequency from 340-370
kHz. However, apparatuses having single sources and/or non-RF
plasma sources may be used.
[0122] Within the reactor, a wafer pedestal 1409 supports a
substrate 1411. A heat transfer subsystem including a line 1413 for
supplying heat transfer fluid controls the temperature of substrate
1411. The wafer chuck and heat transfer fluid system can facilitate
maintaining the appropriate wafer temperatures.
[0123] A high frequency RF of HFRF source 1415 serves to
electrically bias substrate 1411 and draw charged precursor species
onto the substrate for the pre-treatment or cure operation.
Electrical energy from source 1415 is coupled to substrate 1411 via
an electrode or capacitive coupling, for example. Note that the
bias applied to the substrate need not be an RF bias. Other
frequencies and DC bias may be used as well.
[0124] The process gases are introduced via one or more inlets
1417. The gases may be premixed or not. The gas or gas mixtures may
be introduced from a primary gas ring 1421, which may or may not
direct the gases toward the substrate surface. Injectors may be
connected to the primary gas ring 1421 to direct at least some of
the gases or gas mixtures into the chamber and toward substrate.
The injectors, gas rings or other mechanisms for directing process
gas toward the wafer are not present in certain embodiments.
Process gases exit chamber 1403 via an outlet 1422. A vacuum pump
typically draws process gases out and maintains a suitably low
pressure within the reactor. While the HDP chamber is described in
the context of pre- and/or post-deposition treatment or cure, in
certain embodiments, it may be used as a deposition reactor for
deposition of a flowable film. For example, in a thermal
(non-plasma) deposition, such a chamber may be used without
striking a plasma.
[0125] FIG. 15 shows an example of a reactor that may be used in
accordance with certain embodiments of the invention. The reactor
shown in FIG. 15 is suitable for both the dark (non-plasma) or
plasma-enhanced deposition as well as cure, for example, by
capacitively-coupled plasma anneal. As shown, a reactor 1500
includes a process chamber 1524, which encloses other components of
the reactor and serves to contain the plasma generated by a
capacitor type system including a showerhead 1514 working in
conjunction with a grounded heater block 1520. A low-frequency RF
generator 1502 and a high-frequency RF generator 1504 are connected
to showerhead 1514. The power and frequency are sufficient to
generate a plasma from the process gas, for example 400-700 W total
energy. In the implementation of the present invention, the
generators are not used during dark deposition of the flowable
film. During the plasma anneal step, one or both generators may be
used. For example, in a typical process, the high frequency RF
component is generally between 2-60 MHz; in a preferred embodiment,
the component is 13.56 MHz.
[0126] Within the reactor, a wafer pedestal 1518 supports a
substrate 1516. The pedestal typically includes a chuck, a fork, or
lift pins to hold and transfer the substrate during and between the
deposition and/or plasma treatment reactions. The chuck may be an
electrostatic chuck, a mechanical chuck or various other types of
chuck as are available for use in the industry and/or research.
[0127] The process gases are introduced via inlet 1512. Multiple
source gas lines 1510 are connected to manifold 1508. The gases may
be premixed or not. The temperature of the mixing bowl/manifold
lines should be maintained at levels above the reaction
temperature. Temperatures at or above about 80 C at pressures at or
less than about 20 Torr usually suffice. Appropriate valving and
mass flow control mechanisms are employed to ensure that the
correct gases are delivered during the deposition and plasma
treatment phases of the process. In case the chemical precursor(s)
is delivered in the liquid form, liquid flow control mechanisms are
employed. The liquid is then vaporized and mixed with other process
gases during its transportation in a manifold heated above its
vaporization point before reaching the deposition chamber.
[0128] Process gases exit chamber 1524 via an outlet 1522. A vacuum
pump 1526 (e.g., a one or two stage mechanical dry pump and/or a
turbomolecular pump) typically draws process gases out and
maintains a suitably low pressure within the reactor by a close
loop controlled flow restriction device, such as a throttle valve
or a pendulum valve.
[0129] FIG. 16 illustrates a simplified schematic of a remote
plasma pre-treatment and/or cure module according to certain
embodiments. Apparatus 1600 has a plasma producing portion 1611 and
an exposure chamber 1601 separated by a showerhead assembly or
faceplate 1617. Inside exposure chamber 1601, a platen (or stage)
1605 provides a wafer support. Platen 1605 is fitted with a
heating/cooling element. In some embodiments, platen 1605 is also
configured for applying a bias to wafer 1603. Low pressure is
attained in exposure chamber 1601 via vacuum pump via conduit 1607.
Sources of gaseous treatment gases provide a flow of gas via inlet
1609 into plasma producing portion 1611 of the apparatus. Plasma
producing portion 1611 may surrounded by induction coils (not
shown). During operation, gas mixtures are introduced into plasma
producing portion 1611, the induction coils are energized and a
plasma is generated in plasma producing portion 1611. Showerhead
assembly 1617 may have an applied voltage and terminates the flow
of some ions and allows the flow of neutral species into exposure
chamber 1601.
Etching
[0130] As indicated, embodiments of the invention include
non-selective and selective removal (etch) operations. According to
various embodiments, non-selective etching of the HDP oxide and
flowable oxide involves exposing the dielectric layer to a plasma
containing fluorine species. These species may originate from a
fluorine-containing process gas component such as SiF.sub.4,
SiH.sub.2F.sub.2, Si.sub.2F.sub.6, C.sub.2F.sub.6, NF.sub.3,
CF.sub.4, and the like.
[0131] Selective etching of the flowable oxide material may also
involve exposing the dielectric layer to a plasma containing
fluorine species. In other embodiments, it may be accomplished via
a wet etch, e.g., a HF wet etch.
[0132] In certain embodiments, one or more of the etch operations
involve a downstream etch process, in which the substrate is not
directly exposed to a plasma. A remote plasma generator may be used
to generate the plasma. In other embodiments, a sputter etch using
a non-fluorine chemistry is used. The sputter etch chemistry may
include one or more of He, Ar, O2 or H2. In certain embodiments,
one or more of these gases are fed to a remote or in situ plasma
generator. The etch processes may be performed in the same or
different chambers as the preceding deposition process.
[0133] FIGS. 13-16 provide examples of apparatuses that may be used
to implement the pre-treatments described herein. However, one of
skill in the art will understand that various modifications may be
made from the description.
[0134] In certain embodiments, a system controller is employed to
control process parameters. The system controller typically
includes one or more memory devices and one or more processors. The
processor may include a CPU or computer, analog and/or digital
input/output connections, stepper motor controller boards, etc.
Typically there will be a user interface associated with system
controller. The user interface may include a display screen,
graphical software displays of the apparatus and/or process
conditions, and user input devices such as pointing devices,
keyboards, touch screens, microphones, etc. The system controller
may be connected to any or all of the components shown in FIG. 13
of a tool; its placement and connectivity may vary based on the
particular implementation.
[0135] In certain embodiments, the system controller controls the
pressure in the processing chambers. The system controller may also
control concentration of various process gases in the chamber by
regulating valves, liquid delivery controllers and MFCs in the
delivery system as well as flow restriction valves an the exhaust
line. The system controller executes system control software
including sets of instructions for controlling the timing, flow
rates of gases and liquids, chamber pressure, substrate
temperature, and other parameters of a particular process. Other
computer programs stored on memory devices associated with the
controller may be employed in some embodiments. In certain
embodiments, the system controller controls the transfer of a
substrate into and out of various components of the apparatuses
shown in FIG. 13.
[0136] The computer program code for controlling the processes in a
process sequence can be written in any conventional computer
readable programming language: for example, assembly language, C,
C++, Pascal, Fortran or others. Compiled object code or script is
executed by the processor to perform the tasks identified in the
program. The system software may be designed or configured in many
different ways. For example, various chamber component subroutines
or control objects may be written to control operation of the
chamber components necessary to carry out the described processes.
Examples of programs or sections of programs for this purpose
include process gas control code, pressure control code, and plasma
control code.
[0137] The controller parameters relate to process conditions such
as, for example, timing of each operation, pressure inside the
chamber, substrate temperature, process gas flow rates, RF power,
as well as others described above. These parameters are provided to
the user in the form of a recipe, and may be entered utilizing the
user interface. Signals for monitoring the process may be provided
by analog and/or digital input connections of the system
controller. The signals for controlling the process are output on
the analog and digital output connections of the apparatus.
[0138] The above-described processes and apparatuses may deposit
dielectric on any type of substrate that requires thin dielectric
layers. Often, the substrate will be a semiconductor wafer having
gaps in need of dielectric filling. The invention is not, however,
limited to such applications. It may be employed in a myriad of
other fabrication processes such as for fabricating flat panel
displays.
[0139] As indicated above, this invention may be used in integrated
circuit fabrication. The gap filling processes are performed on
partially fabricated integrated circuits employing semiconductor
substrates. In specific examples, the gap filling processes of this
invention are employed to form shallow trench isolation (STI),
inter-metal layer dielectric (ILD) layers, passivation layers, etc.
In certain embodiments, the methods described herein may be applied
to integration processes using flowable oxide deposition and any
solid dielectric deposition technique, including atomic layer
deposition (ALD) and pulsed deposition layer (PDL) techniques. The
disclosed methods and apparatuses may also be implemented in
systems including lithography and/or patterning hardware for
semiconductor fabrication. Further, the disclosed methods may be
implemented in a process with lithography and/or patterning
processes preceding or following the disclosed methods.
[0140] Although the foregoing invention has been described in some
detail for purposes of clarity of understanding, it will be
apparent that certain changes and modifications may be practiced
within the scope of the appended claims. It should be noted that
there are many alternative ways of implementing the processes,
systems and apparatus of the present invention. Accordingly, the
present embodiments are to be considered as illustrative and not
restrictive, and the invention is not to be limited to the details
given herein.
* * * * *