U.S. patent application number 14/932869 was filed with the patent office on 2016-03-03 for high growth rate process for conformal aluminum nitride.
The applicant listed for this patent is Lam Research Corporation. Invention is credited to Ananda Banerji, Adrien LaVoie, Nagraj Shankar, Shankar Swaminathan.
Application Number | 20160064211 14/932869 |
Document ID | / |
Family ID | 53798704 |
Filed Date | 2016-03-03 |
United States Patent
Application |
20160064211 |
Kind Code |
A1 |
Swaminathan; Shankar ; et
al. |
March 3, 2016 |
HIGH GROWTH RATE PROCESS FOR CONFORMAL ALUMINUM NITRIDE
Abstract
Methods of depositing conformal aluminum nitride films on
semiconductor substrates are provided. Disclosed methods involve
(a) exposing a substrate to an aluminum-containing precursor, (b)
purging the aluminum-containing precursor for a duration
insufficient to remove substantially all of the aluminum-containing
precursor in gas phase, (c) exposing the substrate to a
nitrogen-containing precursor to form aluminum nitride, (d) purging
the nitrogen-containing precursor, and (e) repeating (a) through
(d). Increased growth rate and 100% step coverage and conformality
are attained.
Inventors: |
Swaminathan; Shankar;
(Beaverton, OR) ; Banerji; Ananda; (West Linn,
OR) ; Shankar; Nagraj; (Tualatin, OR) ;
LaVoie; Adrien; (Newberg, OR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Lam Research Corporation |
Fremont |
CA |
US |
|
|
Family ID: |
53798704 |
Appl. No.: |
14/932869 |
Filed: |
November 4, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
14183287 |
Feb 18, 2014 |
9214334 |
|
|
14932869 |
|
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Current U.S.
Class: |
438/478 |
Current CPC
Class: |
C23C 16/45544 20130101;
H01L 21/02178 20130101; C23C 16/45523 20130101; H01L 21/0228
20130101; C23C 16/52 20130101; C23C 16/303 20130101; H01L 21/02274
20130101; C23C 16/458 20130101; C23C 16/045 20130101; H01L 21/76831
20130101; H01L 21/3141 20130101; H01L 21/28194 20130101; H01L
21/0254 20130101; H01L 21/76829 20130101 |
International
Class: |
H01L 21/02 20060101
H01L021/02 |
Claims
1. A method of processing a semiconductor substrate having features
in a reaction chamber, the method comprising: (a) exposing the
substrate to a metal-containing precursor for a duration sufficient
to substantially adsorb to a surface of the substrate, the
metal-containing precursor comprising a metal selected from the
group consisting of titanium, hafnium, zirconium, manganese,
tungsten, and tantalum; (b) purging the metal-containing precursor
from the reaction chamber for a duration insufficient to remove
substantially all of the metal-containing precursor from the gas
phase; (c) exposing the substrate to a nitrogen-containing
precursor for a duration sufficient to drive a thermally mediated
reaction to form a layer of metal nitride on the surface of the
substrate, wherein the layer of metal nitride is substantially
conformal to the substrate and has a thickness of about 1.5 .ANG.
or greater; (d) purging the nitrogen-containing precursor in gas
phase from the reaction chamber; and (e) repeating (a) through
(d).
2. The method of claim 1, wherein the layer of metal nitride has
step coverage of at least about 80%.
3. The method of claim 1, wherein the substrate is processed at a
process temperature between about 250.degree. C. and about
450.degree. C.
4. The method of claim 1, wherein the substrate is processed at a
pressure between about 0.01 Torr and about 10 Torr.
5. The method of claim 1, wherein the nitrogen-containing precursor
is ammonia (NH.sub.3).
6. The method of claim 1, wherein purging the metal-containing
precursor further comprises flowing nitrogen (N.sub.2) and purging
the nitrogen-containing precursor further comprises flowing
nitrogen (N.sub.2).
7. The method of claim 1, wherein the metal-containing precursor is
purged for about 2 seconds.
8. The method of claim 1, wherein the substrate is exposed to the
metal-containing precursor for about 7.5 seconds to about 30
seconds.
9. The method of claim 1, wherein the ratio of the time the
substrate is exposed to the metal-containing precursor to the time
the metal-containing precursor is purged is between about 3.75:1
and about 15:1.
10. The method of claim 1, wherein processing exhibits
substantially no pattern loading.
11. The method of claim 1, wherein the amount of metal nitride
deposited during a cycle of (a) through (d) is at least about 2
.ANG..
12. The method of claim 1, wherein the amount of metal nitride
deposited during a cycle of (a) through (d) is at least about 5
.ANG..
13. The method of claim 1, wherein the features of the substrate
have aspect ratios of at least about 2:1.
14. The method of claim 1, wherein the features of the substrate
have openings of less than about 100 nm.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of and claims priority to
U.S. patent application Ser. No. 14/183,287, filed Feb. 18, 2014,
titled "HIGH GROWTH RATE PROCESS FOR CONFORMAL ALUMINUM NITRIDE,"
which is incorporated by reference herein in its entirety and for
all purposes.
BACKGROUND
[0002] Various thin film layers for semiconductor devices may be
deposited with atomic layer deposition (ALD) processes. However,
existing ALD processes may not be suitable for depositing highly
conformal dielectric films. For example, many existing ALD
processes cannot offer a combination of high throughput (rapid
deposition) and high conformality.
SUMMARY
[0003] Provided herein are methods of depositing conformal aluminum
nitride and other materials such as other metal nitrides and metal
oxides on semiconductor substrates.
[0004] One aspect involves a method of processing a semiconductor
substrate having features in a reaction chamber. The method
includes (a) exposing the substrate to an aluminum-containing
precursor for a duration sufficient to substantially adsorb to a
surface of the substrate; (b) purging the aluminum-containing
precursor from the reaction chamber for a duration insufficient to
remove substantially all of the aluminum-containing precursor from
the gas phase; (c) exposing the substrate to a nitrogen-containing
precursor for a duration sufficient to drive a thermally mediated
reaction to form a layer of aluminum nitride on the surface of the
substrate, such that the layer of aluminum nitride is substantially
conformal to the substrate and has a thickness of about 1.5 .ANG.
or greater; (d) purging the nitrogen-containing precursor in gas
phase from the reaction chamber; and (e) repeating (a) through (d).
In some embodiments, the amount of aluminum nitride deposited
during a cycle of (a) through (d) is at least about 2 .ANG.. In
some embodiments, the amount of aluminum nitride deposited during a
cycle of (a) through (d) is at least about 5 .ANG.. In some
embodiments, the layer of aluminum-nitride has step coverage of at
least about 80%. In various embodiments, the substrate is processed
at a process temperature between about 250.degree. C. and about
450.degree. C. The substrate may be processed at a pressure between
about 0.01 Torr and about 10 Torr.
[0005] In many embodiments, the aluminum-containing precursor is
trimethylaluminum (TMA). In many embodiments, the
nitrogen-containing precursor is ammonia (NH.sub.3). In some
embodiments, nitrogen (N.sub.2) is flowed to purge the
aluminum-containing precursor and is flowed to purge the
nitrogen-containing precursor. In many embodiments, the
aluminum-containing precursor is purged for about 2 seconds. In
many embodiments, the substrate is exposed to the
aluminum-containing precursor for about 7.5 seconds to about 30
seconds. In various embodiments, the ratio of the time the
substrate is exposed to the aluminum-containing precursor to the
time the aluminum-containing precursor is purged is between about
3.75:1 and about 15:1.
[0006] In some embodiments, the features of the substrate have
aspect ratios of at least about 2:1. In some embodiments, the
features of the substrate have openings of less than about 100 nm.
In various embodiments, processing exhibits substantially no
pattern loading.
[0007] Another aspect involves an apparatus for depositing a film
on a substrate surface including a reaction chamber including a
pedestal for holding the substrate, at least one outlet for
coupling to a vacuum, one or more process gas inlets coupled to two
or more precursor sources, and a controller for controlling
operations in the apparatus. The controller includes
machine-readable instructions for (a) introducing a first precursor
into the reaction chamber for a duration sufficient to
substantially adsorb the first precursor to the surface of the
substrate; (b) purging the chamber for a duration insufficient to
remove substantially all of the first precursor from gas phase; (c)
introducing a second precursor to the reaction chamber for a
duration sufficient to form a layer on the substrate surface, such
that the layer is substantially conformal to the substrate and has
a thickness of about 1.5 .ANG. or greater; (d) purging the chamber
for a duration sufficient to remove the second precursor from gas
phase; and (e) repeating (a) through (d).
[0008] In some embodiments, the controller includes instructions
for performing (a) for a time about 3.75 to about 15 times greater
than the time for performing (b). In various embodiments, the
instructions for introducing the first precursor include drawing
the first precursor from the headspace of a reservoir of the first
precursor to the chamber. In some embodiments, the instructions for
introducing the first precursor also includes flowing a carrier gas
with the first precursor downstream from the drawing of the first
precursor from the headspace and upstream from the reaction
chamber.
[0009] These and other aspects are described further below with
reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a process flow diagram of a method of depositing
aluminum nitride in accordance with disclosed embodiments.
[0011] FIG. 2 is a timing sequence diagram of pulses in accordance
with disclosed embodiments.
[0012] FIGS. 3A and 3B are schematic illustrations of examples of a
chamber for practicing various embodiments.
[0013] FIG. 4 is a schematic illustration of an example of an
apparatus for practicing various embodiments.
[0014] FIGS. 5, 6A, 6B, and 7 are images of deposited films in
accordance with experiments of the disclosed embodiments.
DETAILED DESCRIPTION
[0015] In the following description, numerous specific details are
set forth to provide a thorough understanding of the presented
embodiments. The disclosed embodiments may be practiced without
some or all of these specific details. In other instances,
well-known process operations have not been described in detail to
not unnecessarily obscure the disclosed embodiments. While the
disclosed embodiments will be described in conjunction with the
specific embodiments, it will be understood that it is not intended
to limit the disclosed embodiments.
[0016] Manufacture of semiconductor devices typically involves
depositing one or more thin films on a non-planar structure in an
integrated fabrication process. In some aspects of the integrated
process, it may be useful to deposit thin films that conform to
substrate topography. For example, some front-end-of-the-line
processes may involve deposition of conformal films. Example
substrates may include substrates with features having aspect
ratios of at least about 2:1, or at least about 4:1, or at least
about 6:1, or at least about 10:1. Examples of conformal films for
front-end-of-line processes include hard masks, etch stops, and
encapsulation layers. Front-end-of-line structures fabricated using
such films include transistors (e.g., FinFETs) and metal-containing
memory devices.
[0017] Atomic layer deposition (ALD) processes use surface-mediated
deposition reactions to deposit films on a layer-by-layer basis. In
one example of an ALD process, a substrate surface, including a
population of surface active sites, is exposed to a gas phase
distribution of a first precursor in a dose. Some molecules of this
first precursor may form a condensed phase atop the substrate
surface, including chemisorbed species and/or physisorbed molecules
of the first precursor. The reactor is then evacuated to remove gas
phase first precursor so that only adsorbed species remain. A
second precursor may then be introduced to the reactor so that some
of these molecules adsorb to the substrate surface. The reactor may
then be evacuated again to remove unbound second precursor
molecules. Thermal energy may activate surface reactions between
the first and second precursors to form a film layer. In some
processes, the second precursor reacts immediately with the
adsorbed first precursor. In other embodiments, the second
precursor reacts only after a source of activation is applied
temporally. Additional ALD cycles may be used to build film
thickness.
[0018] Conventional ALD processes such as the one described above
form highly conformal films. Conformality of films is often
measured by the step coverage. Step coverage may be calculated by
comparing the average thickness of a deposited film on a bottom,
sidewall, or top of a feature to the average thickness of a
deposited film on a bottom, sidewall, or top of a feature. For
example, step coverage may be calculated by dividing the average
thickness of the deposited film on the sidewall by the average
thickness of the deposited film at the top of the feature and
multiplying it by 100 to obtain a percentage. Conventional ALD
processes may deposit films with near 100% step coverage.
[0019] However, although deposited films are highly conformal,
conventional ALD processes exhibit low deposition growth rate, such
as, for example, between about 0.7 .ANG. and 1.0 .ANG. per cycle
for deposition of aluminum nitride, or less than a monolayer
deposited per cycle. A lower growth rate results in lower
production efficiency and thus lower throughput.
[0020] Higher deposition growth rates are observed with chemical
vapor deposition (CVD) and physical vapor deposition (PVD).
However, in these processes, deposited films have low conformity
with step coverage between about 50% and about 70%. Thus, existing
processes fail to deposit conformal films that have both high
growth rate and high conformality.
[0021] Provided herein are methods of depositing highly conformal
thin films at a high growth rate. Methods involve a modified ALD
method that combines CVD-like reactions with ALD surface reactions.
CVD-like conditions are promoted with no significant loss of
conformality. Methods may involve low purge to dose ratios and
formation of the deposited film is driven largely on a
thermal-mediated reaction and not a plasma-activated reaction.
Deposited films may exhibit high growth rates about 4 to about 7
times greater than conventional ALD methods, which increases
throughput and decreases cost of processing substrates. Methods
also exhibit highly conformal deposited films, significantly
greater than 70%, such as about 100% step coverage.
[0022] These methods may be performed to deposit films suitable for
use as a conformal hardmask, an etch stop film, an encapsulation
film, or one or more layers of a stack such as a gate, a memory
stack (e.g., a magnetic RAM stack), or other suitable semiconductor
device structures. In some cases, the deposited film encapsulates a
gate structure including a gate electrode and/or gate dielectric.
In some embodiments, the deposited film encapsulates a magnetic
memory stack. Disclosed methods may be performed on substrates
having "features" such as via or contact holes, which may be
characterized by one or more of narrow and/or re-entrant openings,
constrictions within the feature, and high aspect ratios. One
example of a feature is a hole or via in a semiconductor substrate
or a layer on the substrate. Another example is a trench in a
substrate or layer. The substrate may be a silicon wafer, e.g., a
200-mm wafer, a 300-mm wafer, or a 450-mm wafer, including wafers
having one or more layers of material, such as dielectric,
conducting, or semi-conducting material deposited thereon. The
feature may be formed in one or more of these layers. In some
embodiments, the feature may have an aspect ratio of at least about
2:1, at least about 4:1, at least about 6:1, at least about 10:1,
or higher. The feature may also have a dimension near the opening,
e.g., an opening diameter or line width of between about 10 nm to
500 nm, for example between about 25 nm and about 300 nm. Disclosed
methods may be performed on substrates with features having an
opening less than about 150 nm. A feature via or trench may be
referred to as an unfilled feature or a feature.
[0023] A feature that may have a re-entrant profile that narrows
from the bottom, closed end, or interior of the feature to the
feature opening. In various embodiments, the feature may have an
under-layer, such as a barrier layer or adhesion layer.
Non-limiting examples of under-layers include dielectric layers and
conducting layers, e.g., silicon oxides, silicon nitrides, silicon
carbides, metal oxides, metal nitrides, metal carbides, and metal
layers. In certain embodiments, the under-layer may be titanium
nitride (TiN), titanium metal (Ti), tungsten nitride (WN), titanium
aluminide (TiAl), or a titanium oxide (TiO.sub.x). In various
embodiments, the under-layer may be a dielectric layer, such as an
oxide or nitride or oxynitride. Examples of dielectric layers
include silicon oxide, silicon nitride, silicon oxynitride, and
others.
[0024] In many embodiments, the methods disclosed may be performed
at a temperature between about 250.degree. C. and about 450.degree.
C., or about 350.degree. C. to about 400.degree. C. In general, a
higher deposition temperature results in a higher deposition rate.
In various embodiments, the methods may be performed at a pressure
of between about 0.01 Torr and about 10 Torr, or at a pressure of
between about 0.1 Torr and about 1 Torr. A higher pressure results
in a larger amount of reactant present in the deposition space,
which may thereby increase the deposition rate. The methods
described are dominantly driven by a thermal reaction process. In
the following example, flow rates are provided for a 180 L chamber.
In some cases, depending on the reactor configuration, the flow
rates may be scaled to accommodate different volumes.
[0025] FIG. 1 is a process flow diagram of a method of depositing a
thin conformal film in accordance with a certain embodiment. Note
that the following chemistry presented is an example only to
illustrate the disclosed embodiments. A substrate to be processed
may be in a deposition chamber or deposition station. In operation
101, a substrate is exposed to a first precursor--for example, an
aluminum-containing precursor such as an organo-aluminum compound.
In some embodiments, the aluminum-containing precursor is an
alkyl-aluminum compound such as trimethylaluminum (TMA), or
dimethylaluminum hydride. In some embodiments, the
aluminum-containing precursor is an aluminum acetate, alkoxide, or
aluminum halide. In many embodiments, the exposure time or duration
is sufficient to form a substantially complete saturation or
adsorption layer on the surface of the substrate. In certain
embodiments, exposure time for this dose may be between about 5
seconds and about 60 seconds, e.g., between about 7.5 seconds and
about 30 seconds. In certain embodiments, the flow rate of TMA may
range from about 10 sccm to about 350 sccm. The process of
contacting the substrate with reactant (e.g., aluminum-containing
precursor) is sometimes referred to as "dosing."
[0026] In some embodiments, operation 101 may be performed by
drawing TMA directly from the headspace of a source of TMA, which
may be a reservoir of TMA, through a line connected to the
deposition chamber where the substrate is located.
[0027] In some embodiments, operation 101 may be performed by
inletting TMA from the headspace using a carrier gas introduced
downstream of the TMA source into the chamber through the
showerhead. The carrier gas may be downstream of the TMA source and
upstream of the chamber or showerhead. In many embodiments, the
carrier gas is an inert gas. In some embodiments, the carrier gas
may be nitrogen (N.sub.2), argon (Ar), hydrogen (H.sub.2), or
helium (He). In some embodiments, the flow rate of the carrier gas
may be between about 50 sccm and about 1000 sccm. When a carrier
gas is used to expose the substrate to TMA, the overall flow rate
of TMA may be higher, such as between about 10 sccm and about 200
sccm of pure TMA vapor for a carrier gas flow between about 150
sccm and about 950 sccm. In some embodiments, the overall flow rate
of TMA may be lower.
[0028] In operation 103, the chamber or station is purged for a
duration insufficient to completely purge the aluminum-containing
precursor in the gas phase. In many embodiments, the chamber or
station is purged by flowing a purge gas, such as, for example,
nitrogen (N.sub.2). In certain embodiments, the flow rate of the
purge gas is between about 15 sccm and about 500 sccm. The purge
gas is introduced after the flow of the first precursor is stopped.
The purge time or duration of purge may be insufficient to
completely purge the aluminum-containing precursor in the gas phase
such that there is both surface adsorption from operation 101 as
well as residual aluminum-containing precursor in the gas phase in
the reaction space not on the surface of the substrate or loosely
adhered to the substrate. In many embodiments, the purge time to
dose time ratio, such as the operation 103 to operation 101 time
ratio for example, may be between about 3:1 and about 20:1, e.g.,
between about 3.75:1 and about 15:1. In some embodiments, the purge
time is less than about 5 seconds, e.g., between about 0.1 second
and about 5 seconds, or about 2 seconds. In some embodiments, the
purge in operation 103 may be accomplished by evacuating the
reaction chamber.
[0029] In operation 105, the substrate is exposed to a second
precursor, or as an example, a nitrogen-containing precursor, for a
duration sufficient to form a layer of, e.g., aluminum nitride by a
thermal reaction on the surface of the substrate. In certain
embodiments, the nitrogen-containing precursor is ammonia
(NH.sub.3). In many embodiments, the substrate is exposed to the
nitrogen-containing precursor for a time between about 1 second and
about 60 seconds, or about 2.5 seconds, or about 30 seconds. In
various embodiments, the resulting aluminum nitride layer has a
thickness about 1.5 .ANG. or greater, typically greater than 3
.ANG./cycle. In some embodiments, the flow rate of the
nitrogen-containing precursor may be between about 0.1 slm and
about 20 slm (e.g., between about 1 slm and about 10 slm). In some
embodiments, a carrier gas may be used during the exposure to the
nitrogen-containing precursor. An example of a suitable carrier gas
is nitrogen (N.sub.2), and if nitrogen is used as a carrier gas and
co-flowed with the nitrogen-containing precursor, the nitrogen may
be flowed at a flow rate between about 500 sccm and 10 slm.
[0030] In operation 105, the primary reaction is an ALD reaction on
the surface such that surface-diffusion dominated kinetics occur to
create a conformal aluminum nitride layer. Without being bound by a
particular theory, at the same time, reactions in the gas phase, or
gas-phase nucleation, occurs due to a CVD-like reaction that occurs
between the residual aluminum-containing precursor remaining in gas
phase after the purge in operation 103 and the nitrogen-containing
precursor entering the reaction space. This may contribute to the
increased growth rate in the thin, conformal film. The strong
contribution of surface-diffusion dominated kinetics (associated
with ALD) ensures preservation of conformality.
[0031] In operation 107, the nitrogen-containing precursor is
purged. In many embodiments, purging includes flowing a purge gas,
such as, for example, nitrogen (N.sub.2). In some embodiments, the
purge gas is flowed between about 5 seconds to about 10 seconds, or
about 6 seconds at a flow rate between about 0 sccm and about
10,000 sccm. This purge may be sufficient to remove substantially
all of the remaining nitrogen-containing precursor in gas phase
from the reaction space, or station, or chamber.
[0032] In operation 109, workflow determines if the film has been
deposited to an adequate thickness, and if so, then the method of
depositing the film is complete. If the film has not yet been
deposited to an adequate thickness, operations 101 through 107 are
repeated until the film has been deposited to an adequate
thickness.
[0033] The concept of a "cycle" is relevant to the discussion of
various embodiments herein. Generally a cycle is the minimum set of
operations required to perform a surface deposition reaction one
time. The result of one cycle is production of at least a partial
film layer on a substrate surface. Typically, a cycle will include
only those steps necessary to deliver and adsorb each reactant to
the substrate surface, and then react those adsorbed reactants to
form the partial layer of film. Of course, the cycle may include
certain ancillary steps such as sweeping one of the reactants or
byproducts and/or treating the partial film as deposited.
Generally, a cycle contains only one instance of a unique sequence
of operations. As an example, a cycle may include the following
operations: (i) delivery/adsorption of reactant A, (ii) sweep a
portion of A out of the reaction chamber, (iii) delivery/adsorption
of reactant B under conditions sufficient to drive a reaction of A
and B to form the partial film layer on the surface, and (iv) sweep
B out of the reaction chamber.
[0034] Two deposition cycles of performing the method shown in FIG.
1 are depicted in the timing sequence 200 in FIG. 2. In this
sequence, a deposition cycle as shown in 210A and 210B includes
exposure of a first precursor, a purge, exposure of a second
precursor, and another purge. As shown, phases of exposure and
purges occur from left to right in the timing scheme, and whether a
gas is flowed or not is depicted by the lines on the sequence.
[0035] As an example, nitrogen (N.sub.2) is flowed during the purge
phase 240A and 280A in the deposition cycle 210A, which corresponds
with performing operation 103 and 107 in FIG. 1, respectively.
Nitrogen is also flowed during purge phase 240B and 280B in the
deposition cycle 210B, which corresponds with repeating operation
103 and 107 in FIG. 1, respectively. As an example, TMA is shown as
a gas flowed during the first precursor or TMA exposure phase 220A
in the deposition cycle 210A, which corresponds with performing
operation 101 in FIG. 1. TMA is also flowed during TMA exposure
phase 220B in the deposition cycle 210B, which corresponds with
repeating operation 101 in FIG. 1. Nitrogen or other carrier gas
may be flowed together with the TMA, as illustrated in FIG. 2. As
an example, ammonia is shown as a gas flowed during the second
precursor or ammonia exposure phase 260A in the deposition cycle
210A, which corresponds with performing operation 105 in FIG. 1.
Ammonia is also flowed during ammonia exposure phase 260B in the
deposition cycle 210B, which corresponds with repeating operation
105 in FIG. 1. It is noted here that after the first deposition
cycle 210A, the response to operation 109 in FIG. 1 is that the
film has not been deposited to an adequate thickness, and thus
operations 101 through 107 are repeated in the second deposition
cycle 210B.
[0036] For example, a "recipe" or single deposition cycle sequence
may begin with exposure of TMA at a flow rate between about 10 sccm
and 350 sccm with N.sub.2 as a carrier gas flowed between about 15
sccm and 500 sccm for between about 7.5 seconds and about 30
seconds. Next, TMA flow may be turned off and nitrogen may continue
to flow as a purge gas at a flow rate between about 0 sccm and
about 10,000 sccm for about 2 seconds. Ammonia (NH.sub.3) flow may
then be turned on for ammonia exposure at a flow rate between about
1 slm and 10 slm with nitrogen as a carrier gas flowed between
about 500 sccm and 10 slm for 30 seconds. Ammonia may then react
with adsorbed and gas phase TMA to form an aluminum nitride film.
Ammonia flow may then be turned off and nitrogen may continue to
flow as a purge gas for about 6 seconds at a flow rate between
about 0 sccm and about 10,000 sccm. This example deposition cycle
may be performed at a pressure of about 0.1 Torr at a temperature
between about 350.degree. C. and about 400.degree. C. A deposition
cycle such as the one given here as an example may be repeated
until the desired thickness of the film is deposited. For example,
the aluminum nitride film may be deposited at a deposition rate of
between about 2.5 .ANG. and about 8 .ANG. per cycle. The resulting
aluminum nitride film may have step coverage of at least about 90%
or about 100% and may depend on the number of deposition cycles
performed.
[0037] Films deposited by methods disclosed herein may result in
deposition rate or growth rate of about 1.5 .ANG. to about 10 .ANG.
per cycle, or 2 .ANG. to about 5 .ANG. per cycle. In many
embodiments, films deposited are highly conformal and exhibit step
coverage at least about 80%, or at least about 90%, or at least
about 99%, or about 100%. These levels of conformality and
deposition rate are exhibited in features having high aspect ratios
(e.g., about 1:2 or greater or about 1:6 or greater) and small size
(e.g., openings of about 100 nm or smaller or about 60 nm or
smaller). In many embodiments, the films deposited by methods
disclosed herein result in little or no pattern loading, where
pattern loading or "microloading" is defined as the tendency of a
film to deposit differently the same wafer with different aspect
ratios and different areal structure densities for the same
deposition conditions.
[0038] In some embodiments, a plasma may be used. In embodiments
where a plasma is used, the method may include (1) exposing a
substrate to a metal-containing precursor (e.g.,
aluminum-containing precursor) for a duration sufficient to adsorb
onto the surface of the substrate, (2) purging the metal-containing
precursor for a duration insufficient to remove substantially all
of the metal-containing precursor in gas phase, (3) exposing the
substrate to a nitrogen- or oxygen-containing precursor while
initiating a plasma to form a metal nitride or metal oxide film on
the substrate, (4) purging the nitrogen-containing precursor from
the gas phase, and (5) repeating (1) through (4). In certain
embodiments, the metal-containing precursor is TMA. In some
embodiments, the purging is performed by flowing a purge gas, such
as, for example, nitrogen. In certain embodiments the
nitrogen-containing precursor is ammonia. In many embodiments,
radio frequency (RF) power of the plasma may be between about 13.56
MHz and about 40 MHz. For a 300 mm wafer, the RF power may range
from about 0 kW per station to about 2.5 kW per station. In many
embodiments, the plasma has a RF power density of between about 0
Watts/cm.sup.2 and about 3.54 Watts/cm.sup.2 of substrate. Examples
of using a plasma in conformal film deposition (CFD) processes are
provided in U.S. patent application Ser. No. 13/084,399, filed Apr.
11, 2011, and U.S. patent application Ser. No. 13/224,240, filed
Sep. 1, 2011, which are incorporated herein by reference in their
entireties.
[0039] The method shown in FIG. 1 may be practiced using other
chemistries. Examples of a first precursor in operation 101 include
metal-containing compounds such as aluminum-containing precursors
such as an alkyl-aluminum compound such as trimethylaluminum (TMA),
or dimethylaluminum hydride. In some embodiments, the
aluminum-containing precursor is an aluminum acetate, alkoxide, or
aluminum halide. In general, the metal containing precursors
include organometallic compounds such as alkyl metal compounds as
well as metal halides having a high vapor pressure under deposition
conditions. Such compounds exist in a vapor state and are readily
delivered to the substrate and adsorb thereon. Some methods
described herein may be suitable for thermal ALD involving
organometallic or halide precursors and ammonia/water
(NH.sub.3/H.sub.2O) or ozone (O.sub.3) as half reactants for a
variety of metal systems. Examples of metal systems include
titanium (Ti), hafnium (Hf), zirconium (Zr), manganese (Mn),
tungsten (W), and tantalum (Ta). Examples of purge gases used in
operations 103 and 107 include nitrogen (N.sub.2), argon (Ar),
helium (He), hydrogen (H.sub.2), oxygen (O.sub.2), and others.
Examples of a second precursor in operation 105 include
nitrogen-containing precursors, such as ammonia (NH.sub.3), or
tertbutylamine (TBA). Other examples of the second precursor
include oxygen-containing precursors such as ozone (O.sub.3), water
vapor (H.sub.2O), methanol (CH.sub.4O), ethanol (C.sub.2H.sub.6O),
peroxides, and others. Examples of carrier gases that may flow with
a precursor gas include argon (Ar), helium (He), and nitrogen
(N.sub.2).
Apparatus
[0040] FIG. 3A depicts a schematic illustration of an embodiment of
an atomic layer deposition (ALD) process station 300 having a
process chamber body 302 for maintaining a low-pressure
environment. A plurality of ALD process stations 300 may be
included in a common low pressure process tool environment. For
example, FIG. 4 depicts an embodiment of a multi-station processing
tool 400. In some embodiments, one or more hardware parameters of
ALD process station 300, including those discussed in detail below,
may be adjusted programmatically by one or more computer
controllers 350.
[0041] ALD process station 300 fluidly communicates with reactant
delivery system 301a for delivering process gases to a distribution
showerhead 306. Reactant delivery system 301a includes a mixing
vessel 304 for blending and/or conditioning process gases for
delivery to showerhead 306. One or more mixing vessel inlet valves
320 may control introduction of process gases to mixing vessel
304.
[0042] FIG. 3B depicts a schematic illustration of an alternative
reactant delivery system 301b for delivering reactants to the
showerhead 306. Some reactants, such as trimethylaluminum (TMA),
may be stored in liquid form prior to vaporization at and
subsequent delivery to the process chamber body 302. In FIG. 3B,
vapor of the process liquid contained in reservoir 370 may be drawn
from the headspace 372 to a restrictor 362, which may deliver
reactants with the carrier gas to process chamber body 302. The
reservoir may include a gauge 365. In some embodiments, a carrier
gas may be upstream of the process liquid reservoir 370 such that
the carrier gas pushes the vapor of the process liquid in reservoir
370 initially drawn from the headspace 372 through conduits to the
restrictor 362 and subsequently to the chamber body 302. In many
embodiments, the carrier gas may first flow through a mass flow
controller 360 before carrying vapor from headspace 372 to the
restrictor 362. In these embodiments where a carrier gas is used to
push the vapor, the flow rate of the vapor into the chamber 302 may
be higher than in embodiments where a carrier gas is not used and
the vapor is drawn directly from the headspace 372, to the mixing
vessel 304, and to the chamber body 302.
[0043] As an example, the embodiment of FIG. 3A includes a
vaporization point 303 for vaporizing liquid reactant to be
supplied to the mixing vessel 304. In some embodiments,
vaporization point 303 may be a heated vaporizer. The saturated
reactant vapor produced from such vaporizers may condense in
downstream delivery piping. Exposure of incompatible gases to the
condensed reactant may create small particles. These small
particles may clog piping, impede valve operation, contaminate
substrates, etc. Some approaches to addressing these issues involve
purging and/or evacuating the delivery piping to remove residual
reactant. However, purging the delivery piping may increase process
station cycle time, degrading process station throughput. Thus, in
some embodiments, delivery piping downstream of vaporization point
303 may be heat traced. In some examples, mixing vessel 304 may
also be heat traced. In one non-limiting example, piping downstream
of vaporization point 303 has an increasing temperature profile
extending from approximately 100.degree. C. to approximately
150.degree. C. at mixing vessel 304.
[0044] In some embodiments, liquid precursor or liquid reactant may
be vaporized at a liquid injector. For example, a liquid injector
may inject pulses of a liquid reactant into a carrier gas stream
upstream of the mixing vessel. In one embodiment, a liquid injector
may vaporize the reactant by flashing the liquid from a higher
pressure to a lower pressure. In another example, a liquid injector
may atomize the liquid into dispersed microdroplets that are
subsequently vaporized in a heated delivery pipe. Smaller droplets
may vaporize faster than larger droplets, reducing a delay between
liquid injection and complete vaporization. Faster vaporization may
reduce a length of piping downstream from vaporization point 303.
In one scenario, a liquid injector may be mounted directly to
mixing vessel 304. In another scenario, a liquid injector may be
mounted directly to showerhead 306.
[0045] In some embodiments, a liquid flow controller (LFC) upstream
of vaporization point 303 may be provided for controlling a mass
flow of liquid for vaporization and delivery to process station
300. For example, the LFC may include a thermal mass flow meter
(MFM) located downstream of the LFC. A plunger valve of the LFC may
then be adjusted responsive to feedback control signals provided by
a proportional-integral-derivative (PID) controller in electrical
communication with the MFM. However, it may take one second or more
to stabilize liquid flow using feedback control. This may extend a
time for dosing a liquid reactant. Thus, in some embodiments, the
LFC may be dynamically switched between a feedback control mode and
a direct control mode. In some embodiments, this may be performed
by disabling a sense tube of the LFC and the PID controller.
[0046] Showerhead 306 distributes process gases toward substrate
312. In the embodiment shown in FIG. 3A, the substrate 312 is
located beneath showerhead 306 and is shown resting on a pedestal
308. Showerhead 306 may have any suitable shape, and may have any
suitable number and arrangement of ports for distributing process
gases to substrate 312.
[0047] In some embodiments, a microvolume 307 is located beneath
showerhead 306. Practicing disclosed embodiments in a microvolume
rather than in the entire volume of a process station may reduce
reactant exposure and purge times, may reduce times for altering
process conditions (e.g., pressure, temperature, etc.) may limit an
exposure of process station robotics to process gases, etc. Example
microvolume sizes include, but are not limited to, volumes between
0.1 liter and 2 liters. This also impacts productivity throughput.
In some embodiments, the disclosed embodiments are not performed in
a microvolume.
[0048] In some embodiments, pedestal 308 may be raised or lowered
to expose substrate 312 to microvolume 307 and/or to vary a volume
of microvolume 307. For example, in a substrate transfer phase,
pedestal 308 may be raised to position substrate 312 within
microvolume 307. In some embodiments, microvolume 307 may
completely enclose substrate 312 as well as a portion of pedestal
308 to create a region of high flow impedance.
[0049] Optionally, pedestal 308 may be lowered and/or raised during
portions the process to modulate process pressure, reactant
concentration, etc., within microvolume 307. In one scenario where
process chamber body 302 remains at a base pressure during the
process, lowering pedestal 308 may allow microvolume 307 to be
evacuated. Example ratios of microvolume to process chamber volume
include, but are not limited to, volume ratios between 1:500 and
1:10. It will be appreciated that, in some embodiments, pedestal
height may be adjusted programmatically by a suitable computer
controller 350.
[0050] In another scenario, adjusting a height of pedestal 308 may
allow a plasma density to be varied during plasma activation and/or
treatment cycles included in the process. At the conclusion of the
process phase, pedestal 308 may be lowered during another substrate
transfer phase to allow removal of substrate 312 from pedestal
308.
[0051] While the example microvolume variations described herein
refer to a height-adjustable pedestal, it will be appreciated that,
in some embodiments, a position of showerhead 306 may be adjusted
relative to pedestal 308 to vary a volume of microvolume 307.
Further, it will be appreciated that a vertical position of
pedestal 308 and/or showerhead 306 may be varied by any suitable
mechanism within the scope of the present disclosure. In some
embodiments, pedestal 308 may include a rotational axis for
rotating an orientation of substrate 312. It will be appreciated
that, in some embodiments, one or more of these example adjustments
may be performed programmatically by one or more suitable computer
controllers 350.
[0052] In some embodiments where plasma may be used as discussed
above, showerhead 306 and pedestal 308 electrically communicate
with a radio frequency (RF) power supply 314 and matching network
316 for powering a plasma. In some embodiments, the plasma energy
may be controlled by controlling one or more of a process station
pressure, a gas concentration, an RF source power, an RF source
frequency, and a plasma power pulse timing. For example, RF power
supply 314 and matching network 316 may be operated at any suitable
power to form a plasma having a desired composition of radical
species. Examples of suitable powers are included above. Likewise,
RF power supply 314 may provide RF power of any suitable frequency.
In some embodiments, RF power supply 314 may be configured to
control high- and low-frequency RF power sources independently of
one another. Example low-frequency RF frequencies may include, but
are not limited to, frequencies between 50 kHz and 500 kHz. Example
high-frequency RF frequencies may include, but are not limited to,
frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated
that any suitable parameters may be modulated discretely or
continuously to provide plasma energy for the surface reactions. In
one non-limiting example, the plasma power may be intermittently
pulsed to reduce ion bombardment with the substrate surface
relative to continuously powered plasmas.
[0053] In some embodiments, the plasma may be monitored in-situ by
one or more plasma monitors. In one scenario, plasma power may be
monitored by one or more voltage, current sensors (e.g., VI
probes). In another scenario, plasma density and/or process gas
concentration may be measured by one or more optical emission
spectroscopy sensors (OES). In some embodiments, one or more plasma
parameters may be programmatically adjusted based on measurements
from such in-situ plasma monitors. For example, an OES sensor may
be used in a feedback loop for providing programmatic control of
plasma power. It will be appreciated that, in some embodiments,
other monitors may be used to monitor the plasma and other process
characteristics. Such monitors may include, but are not limited to,
infrared (IR) monitors, acoustic monitors, and pressure
transducers.
[0054] In some embodiments, instructions for a controller 350 may
be provided via input/output control (IOC) sequencing instructions.
In one example, the instructions for setting conditions for a
process phase may be included in a corresponding recipe phase of a
process recipe. In some cases, process recipe phases may be
sequentially arranged, so that all instructions for a process phase
are executed concurrently with that process phase. In some
embodiments, instructions for setting one or more reactor
parameters may be included in a recipe phase. For example, a first
recipe phase may include instructions for setting a flow rate of an
inert and/or a reactant gas (e.g., the first precursor such as
TMA), instructions for setting a flow rate of a carrier gas (such
as nitrogen), and time delay instructions for the first recipe
phase. A second, subsequent recipe phase may include instructions
for modulating or stopping a flow rate of an inert and/or a
reactant gas, and instructions for modulating a flow rate of a
carrier or purge gas and time delay instructions for the second
recipe phase. A third recipe phase may include instructions for
setting a flow rate of an inert and/or reactant gas which may be
the same as or different from the gas used in the first recipe
phase (e.g., the second precursor such as ammonia), instructions
for modulating a flow rate of a carrier gas, and time delay
instructions for the third recipe phase. A fourth recipe phase may
include instructions for modulating or stopping a flow rate of an
inert and/or a reactant gas, instructions for modulating the flow
rate of a carrier or purge gas, and time delay instructions for the
fourth recipe phase. It will be appreciated that these recipe
phases may be further subdivided and/or iterated in any suitable
way within the scope of the present disclosure.
[0055] In some embodiments, pedestal 308 may be temperature
controlled via heater 310. Further, in some embodiments, pressure
control for process station 300 may be provided by butterfly valve
318. As shown in the embodiment of FIG. 3, butterfly valve 318
throttles a vacuum provided by a downstream vacuum pump (not
shown). However, in some embodiments, pressure control of process
station 300 may also be adjusted by varying a flow rate of one or
more gases introduced to the process station 300.
[0056] As described above, one or more process stations may be
included in a multi-station processing tool. FIG. 4 shows a
schematic view of an embodiment of a multi-station processing tool
400 with an inbound load lock 402 and an outbound load lock 404,
either or both of which may comprise a remote plasma source. A
robot 406, at atmospheric pressure, is configured to move wafers
from a cassette loaded through a pod 408 into inbound load lock 402
via an atmospheric port 410. A wafer is placed by the robot 406 on
a pedestal 412 in the inbound load lock 402, the atmospheric port
410 is closed, and the load lock is pumped down. Where the inbound
load lock 402 comprises a remote plasma source, the wafer may be
exposed to a remote plasma treatment in the load lock prior to
being introduced into a processing chamber 414. Further, the wafer
also may be heated in the inbound load lock 402 as well, for
example, to remove moisture and adsorbed gases. Next, a chamber
transport port 416 to processing chamber 414 is opened, and another
robot (not shown) places the wafer into the reactor on a pedestal
of a first station shown in the reactor for processing. While the
embodiment depicted in FIG. 4 includes load locks, it will be
appreciated that, in some embodiments, direct entry of a wafer into
a process station may be provided.
[0057] The depicted processing chamber 414 comprises four process
stations, numbered from 1 to 4 in the embodiment shown in FIG. 4.
Each station has a heated pedestal (shown at 418 for station 1),
and gas line inlets. It will be appreciated that in some
embodiments, each process station may have different or multiple
purposes. For example, in some embodiments, a process station may
be switchable between an ALD and plasma-enhanced ALD process mode.
Additionally or alternatively, in some embodiments, processing
chamber 414 may include one or more matched pairs of ALD and
plasma-enhanced ALD process stations. While the depicted processing
chamber 414 comprises four stations, it will be understood that a
processing chamber according to the present disclosure may have any
suitable number of stations. For example, in some embodiments, a
processing chamber may have five or more stations, while in other
embodiments a processing chamber may have three or fewer
stations.
[0058] FIG. 4 depicts an embodiment of a wafer handling system 490
for transferring wafers within processing chamber 414. In some
embodiments, wafer handling system 490 may transfer wafers between
various process stations and/or between a process station and a
load lock. It will be appreciated that any suitable wafer handling
system may be employed. Non-limiting examples include wafer
carousels and wafer handling robots. FIG. 4 also depicts an
embodiment of a system controller 450 employed to control process
conditions and hardware states of process tool 400. System
controller 450 may include one or more memory devices 456, one or
more mass storage devices 454, and one or more processors 452.
Processor 452 may include a CPU or computer, analog and/or digital
input/output connections, stepper motor controller boards, etc.
[0059] In some embodiments, system controller 450 controls all of
the activities of process tool 400. System controller 450 executes
system control software 458 stored in mass storage device 454,
loaded into memory device 456, and executed on processor 452.
Alternatively, the control logic may be hard coded in the
controller 450. Applications Specific Integrated Circuits,
Programmable Logic Devices (e.g., field-programmable gate arrays,
or FPGAs) and the like may be used for these purposes. In the
following discussion, wherever "software" or "code" is used,
functionally comparable hard coded logic may be used in its place.
System control software 458 may include instructions for
controlling the timing, mixture of gases, amount of sub-saturated
gas flow, chamber and/or station pressure, chamber and/or station
temperature, wafer temperature, target power levels, RF power
levels, substrate pedestal, chuck and/or susceptor position, and
other parameters of a particular process performed by process tool
400. System control software 458 may be configured in any suitable
way. For example, various process tool component subroutines or
control objects may be written to control operation of the process
tool components necessary to carry out various process tool
processes. System control software 458 may be coded in any suitable
computer readable programming language.
[0060] In some embodiments, system control software 458 may include
input/output control (IOC) sequencing instructions for controlling
the various parameters described above. Other computer software
and/or programs stored on mass storage device 454 and/or memory
device 456 associated with system controller 450 may be employed in
some embodiments. Examples of programs or sections of programs for
this purpose include a substrate positioning program, a process gas
control program, a pressure control program, a heater control
program, and a plasma control program.
[0061] A substrate positioning program may include program code for
process tool components that are used to load the substrate onto
pedestal 418 and to control the spacing between the substrate and
other parts of process tool 400.
[0062] A process gas control program may include code for
controlling gas composition (e.g., TMA, ammonia, and purge gases as
described herein) and flow rates and optionally for flowing gas
into one or more process stations prior to deposition in order to
stabilize the pressure in the process station. A pressure control
program may include code for controlling the pressure in the
process station by regulating, for example, a throttle valve in the
exhaust system of the process station, a gas flow into the process
station, etc.
[0063] A heater control program may include code for controlling
the current to a heating unit that is used to heat the substrate.
Alternatively, the heater control program may control delivery of a
heat transfer gas (such as helium) to the substrate.
[0064] A plasma control program may include code for setting RF
power levels applied to the process electrodes in one or more
process stations in accordance with the embodiments herein.
[0065] A pressure control program may include code for maintaining
the pressure in the reaction chamber in accordance with the
embodiments herein.
[0066] In some embodiments, there may be a user interface
associated with system controller 450. 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.
[0067] In some embodiments, parameters adjusted by system
controller 450 may relate to process conditions. Non-limiting
examples include process gas composition and flow rates,
temperature, pressure, plasma conditions (such as RF bias power
levels), etc. These parameters may be provided to the user in the
form of a recipe, which may be entered utilizing the user
interface.
[0068] Signals for monitoring the process may be provided by analog
and/or digital input connections of system controller 450 from
various process tool sensors. The signals for controlling the
process may be output on the analog and digital output connections
of process tool 400. Non-limiting examples of process tool sensors
that may be monitored include mass flow controllers, pressure
sensors (such as manometers), thermocouples, etc. Appropriately
programmed feedback and control algorithms may be used with data
from these sensors to maintain process conditions.
[0069] System controller 450 may provide program instructions for
implementing the above-described deposition processes. The program
instructions may control a variety of process parameters, such as
DC power level, RF bias power level, pressure, temperature, etc.
The instructions may control the parameters to operate in-situ
deposition of film stacks according to various embodiments
described herein.
[0070] The system controller will typically include one or more
memory devices and one or more processors configured to execute the
instructions so that the apparatus will perform a method in
accordance with the present invention. Machine-readable media
containing instructions for controlling process operations in
accordance with the present invention may be coupled to the system
controller.
[0071] An appropriate apparatus for performing the methods
disclosed herein is further discussed and described in U.S. patent
application Ser. No. 13/084,399, filed Apr. 11, 2011, and titled
"PLASMA ACTIVATED CONFORMAL FILM DEPOSITION"; and Ser. No.
13/084,305, filed Apr. 11, 2011, and titled "SILICON NITRIDE FILMS
AND METHODS," each of which is incorporated herein in its
entireties.
[0072] The apparatus/process described herein may be used in
conjunction with lithographic patterning tools or processes, for
example, for the fabrication or manufacture of semiconductor
devices, displays, LEDs, photovoltaic panels and the like.
Typically, though not necessarily, such tools/processes will be
used or conducted together in a common fabrication facility.
Lithographic patterning of a film typically includes some or all of
the following operations, each operation enabled with a number of
possible tools: (1) application of photoresist on a workpiece,
i.e., substrate, using a spin-on or spray-on tool; (2) curing of
photoresist using a hot plate or furnace or UV curing tool; (3)
exposing the photoresist to visible or UV or x-ray light with a
tool such as a wafer stepper; (4) developing the resist so as to
selectively remove resist and thereby pattern it using a tool such
as a wet bench; (5) transferring the resist pattern into an
underlying film or workpiece by using a dry or plasma-assisted
etching tool; and (6) removing the resist using a tool such as an
RF or microwave plasma resist stripper.
EXPERIMENTAL
Experiment 1
[0073] An experiment was conducted to evaluate step coverage of
features deposited using methods of the disclosed embodiments. In
this experiment, an aluminum nitride layer was deposited on a metal
dielectric substrate with features at 350.degree. C. and 0.1 Torr
using cycles of a 7.5-second exposure of trimethylaluminum (TMA), a
2-second purge, a 30-second exposure of ammonia (NH.sub.3), and a
6-second purge. The reaction was entirely thermal and no plasma was
initiated.
[0074] The results of the measurements and calculations of step
coverage are shown in Table 1 below.
TABLE-US-00001 TABLE 1 Step Coverage Step Coverage Step Coverage
Sidewall Top Bottom Sidewall/ Sidewall/ (avg, nm) (avg, nm) (avg,
nm) Top (%) Bottom (%) 20.09 19.97 19.43 100.6% 102.8%
[0075] FIG. 5 is an image of the deposited aluminum nitride film on
the substrate. The average deposition rate of aluminum nitride was
about 3.3 .ANG. per cycle and 100% conformality was achieved.
Experiment 2
[0076] An experiment was conducted to evaluate whether there was
pattern loading as a result of practicing the disclosed
embodiments. In this experiment, an aluminum nitride layer was
deposited on a metal dielectric substrate with features at
350.degree. C. and 0.1 Torr using cycles of a 7.5-second exposure
of trimethylaluminum (TMA), a 2-second purge, a 30-second exposure
of ammonia (NH.sub.3), and a 6-second purge. The reaction was
entirely thermal and no plasma was initiated. Experiments were
conducted on substrates with an aspect ratio of 2.5:1 and 6:1, and
a field or blanket substrate. The results of the measurements and
calculations of step coverage are shown in Table 2 below.
TABLE-US-00002 TABLE 2 Pattern Loading Feature Aspect Top Sidewall
Bottom Step Coverage Ratio (avg, nm) (avg, nm) (avg, nm)
(Sidewall/Top %) Field 19.14 -- -- -- 2.5:1 19.97 20.09 19.43
100.6% 6:1 18.99 19.30 19.13 102%
[0077] FIG. 5 is an image of the deposited aluminum nitride film on
the 2.5:1 aspect ratio features. FIG. 6A is an image of the
deposited aluminum nitride film on the 6:1 aspect ratio features.
FIG. 6B depicts an image of the deposited aluminum nitride film on
the field substrate. Layers deposited using disclosed embodiments
were still conformal for features with an aspect ratio of up to
about 1:6 and no pattern loading effect was observed.
Experiment 3
[0078] An experiment was conducted to evaluate film quality of
deposited films in accordance with various embodiments. In this
experiment, an aluminum nitride layer was deposited on a metal
dielectric substrate with features at 350.degree. C. and 0.1 Torr
using cycles of a 7.5-second exposure of trimethylaluminum (TMA), a
2-second purge, a 30-second exposure of ammonia (NH.sub.3), and a
6-second purge. The reaction was entirely thermal and no plasma was
initiated. FIG. 5 is an image of the deposited aluminum nitride
film before the wet etch test or dip.
[0079] The substrate was then subject to an SC2 wet etch test using
a standard clean solution at 50.degree. C. for a 25-second dip. The
composition of the SC2 standard etchant/clean solution includes
HCl, H.sub.2O.sub.2, and H.sub.2O in a 1:1:5 composition ratio. The
results of the measurements and calculations of step coverage are
shown in Table 3 below.
TABLE-US-00003 TABLE 3 Film Quality Thickness Thickness Etch Rate
(pre-dip) (post-dip) (.ANG./min) Sidewall (avg, .ANG.) 200.9 179.7
51 Top (avg, .ANG.) 199.7 177.8 53 Bottom (avg, .ANG.) 194.3 173.5
50
[0080] FIG. 7 is an image of the etched aluminum nitride film after
the wet etch test. As shown the etch was uniform throughout the
surface of the features. The calculated sidewall to top etch rate
ratio was about 0.97. The film quality was comparable to that of
conventional ALD. Even after the wet etch dip, the step coverage of
the deposited film was still about 100%, thereby indicating that
the film etches uniformly and etch rate is consistent over the
deposited film. The results also show that the quality of the film
on the sidewall is equivalent to the quality of the film in the
field regions at the top and bottom of the structure despite having
CVD-like reactions during deposition. This suggests that the film
quality generated at the surface and the gas phase are equivalent
or similar.
CONCLUSION
[0081] Although the foregoing embodiments have 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 embodiments. Accordingly, the
present embodiments are to be considered as illustrative and not
restrictive, and the embodiments are not to be limited to the
details given herein.
* * * * *