U.S. patent application number 11/035392 was filed with the patent office on 2005-08-18 for filling high aspect ratio isolation structures with polysilazane based material.
This patent application is currently assigned to INTERNATIONAL BUSINESS MACHINES CORPORATION. Invention is credited to Belyansky, Michael P., Divakaruni, Rama, Economikos, Laertis, Jammy, Rajarao, Settlemyer, Kenneth T. JR., Shafer, Padraic C..
Application Number | 20050179112 11/035392 |
Document ID | / |
Family ID | 33489117 |
Filed Date | 2005-08-18 |
United States Patent
Application |
20050179112 |
Kind Code |
A1 |
Belyansky, Michael P. ; et
al. |
August 18, 2005 |
Filling high aspect ratio isolation structures with polysilazane
based material
Abstract
Isolation trenches and capacitor trenches containing vertical
FETs (or any prior levels p-n junctions or dissimilar material
interfaces) having an aspect ratio up to 60 are filled with a
process comprising: applying a spin-on material based on silazane
and having a low molecular weight; pre-baking the applied material
in an oxygen ambient at a temperature below about 450 deg C.;
converting the stress in the material by heating at an intermediate
temperature between 450 deg C. and 800 deg C. in an H20 ambient;
and heating again at an elevated temperature in an O2 ambient,
resulting in a material that is stable up to 1000 deg C., has a
compressive stress that may be tuned by variation of the process
parameters, has an etch rate comparable to oxide dielectric formed
by HDP techniques, and is durable enough to withstand CMP
polishing.
Inventors: |
Belyansky, Michael P.;
(Bethel, CT) ; Divakaruni, Rama; (Ossining,
NY) ; Economikos, Laertis; (Wappingers Falls, NY)
; Jammy, Rajarao; (Hopewell Junction, NY) ;
Settlemyer, Kenneth T. JR.; (Poughquag, NY) ; Shafer,
Padraic C.; (Fishkill, NY) |
Correspondence
Address: |
Eric W. Petraske
68 Old Hawleyville Road
Bethel
CT
06801
US
|
Assignee: |
INTERNATIONAL BUSINESS MACHINES
CORPORATION
Armonk
NY
|
Family ID: |
33489117 |
Appl. No.: |
11/035392 |
Filed: |
January 12, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11035392 |
Jan 12, 2005 |
|
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|
10250092 |
Jun 3, 2003 |
|
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6869860 |
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Current U.S.
Class: |
257/510 ;
257/E21.548 |
Current CPC
Class: |
H01L 21/76229
20130101 |
Class at
Publication: |
257/510 |
International
Class: |
H01L 021/76 |
Claims
1. A method of forming an integrated circuit containing a set of
thermally sensitive circuit elements having a thermal budget
associated therewith and a set of isolation trenches comprising the
steps of: providing a silicon substrate; forming at least one
circuit element having a thermal budget prior to forming the
isolation structure; etching said set of trenches in said silicon
substrate; filling said set of trenches with a spin on trench
dielectric material containing silazane; heating said substrate at
a temperature of less than about 450 deg C.; converting the stress
in said trench dielectric material from tensile stress to
compressive stress by heating in an ambient containing H2O at a
temperature between about 450 deg C. and about 900 deg C.;
annealing said substrate by heating in an ambient containing O2 at
a temperature above 800 deg C.; and completing said integrated
circuit.
2. A method according to claim 1, in which the time of the stress
conversion step and the time of the anneal step are related such
that the thermal budget of the thermally sensitive component is not
exceeded.
3. A method according to claim 1, in which: said step of stress
conversion and said step of annealing are related such that the
resulting material has compressive stress in the range of 0.1 to 2
Gdynes/cm2 and has a WERR of less than about 2.
4. A method according to claim 2, in which: said step of stress
conversion and said step of annealing are related such that the
resulting material has compressive stress in the range of 0.1 to 2
Gdynes/cm2 and has a WERR of less than about 2.
5. A method according to claim 2, in which: the step of heating
said substrate in an ambient containing ) O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
6. A method according to claim 3, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
7. A method according to claim 4, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
8. A method according to claim 1, in which: the trench has an
aspect ratio of greater than 6; the trench dielectric material is
planarized by CMP after the step of annealing in an O2 ambient; and
an anneal in an ambient containing water vapor is performed after
the step of planarizing for a time sufficient to convert Si--N
bonds to Si--O bonds in trench dielectric material at the bottom of
the trench.
9. A method according to claim 8, in which the time of the stress
conversion step and the time of the anneal step are related such
that the thermal budget of the thermally sensitive component is not
exceeded.
10. A method according to claim 8, in which: said step of stress
conversion and said step of annealing are related such that the
resulting material has compressive stress in the range of 0.1 to 2
Gdynes/cm2 and has a WERR of less than about 2.
11. A method according to claim 9, in which: said step of stress
conversion and said step of annealing are related such that the
resulting material has compressive stress in the range of 0.1 to 2
Gdynes/cm2 and has a WERR of less than about 2.
12. A method according to claim 9, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
13. A method according to claim 10, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
14. A method according to claim 11, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
15. A method of forming an integrated circuit containing a set of
circuit elements and a set of isolation trenches comprising the
steps of: providing a silicon substrate; etching said set of
trenches in said silicon substrate; filling said set of trenches
with a spin on trench dielectric material containing silazane;
heating said substrate at a temperature of less than about 450 deg
C.; converting the stress in said trench dielectric material from
tensile stress to compressive stress by heating in an ambient
containing H2O at a temperature between about 450 deg C. and about
900 deg C.; annealing said substrate by heating in an ambient
containing O2 at a temperature above 800 deg C.; and completing
said integrated circuit.
16. A method according to claim 15, in which: said step of stress
conversion and said step of annealing are related such that the
resulting material has compressive stress in the range of 0.1+2
Gdynes/cm2 and has a WERR of less than about 2.
17. A method according to claim 16, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is no
greater than a design value.
18. A method according to claim 17, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
19. A method of forming an integrated circuit containing a set of
thermally sensitive vertical transistor DRAM cells having a thermal
budget associated therewith and a set of isolation trenches,
comprising the steps of: providing a silicon substrate; forming at
least one vertical transistor DRAM cell having a thermal budget
prior to forming the isolation structure; etching said set of
trenches in said silicon substrate; filling said set of trenches
with a spin on trench dielectric material containing silazane;
heating said substrate at a temperature of less than about 450 deg
C.; converting the stress in said trench dielectric material from
tensile stress to compressive stress by heating in an ambient
containing H2O at a temperature between about 450 deg C. and about
900 deg C.; annealing said substrate by heating in an ambient
containing O2 at a temperature above 800 deg C.; and completing
said integrated circuit.
20. A method according to claim 19, in which the time of the stress
conversion step and the time of the anneal step are related such
that the thermal budget of the vertical transistor DRAM cell is not
exceeded.
21. A method according to claim 19, in which: said step of stress
conversion and said step of annealing are related such that the
resulting material has compressive stress in the range of 0.1 to 2
Gdynes/cm2 and has a WERR of less than about 2.
22. A method according to claim 20, in which: said step of stress
conversion and said step of annealing are related such that the
resulting material has compressive stress in the range of 0.1 to 2
Gdynes/cm2 and has a WERR of less than about 2.
23. A method according to claim 20, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
24. A method according to claim 21, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
25. A method according to claim 22, in which: the step of heating
said substrate in an ambient containing O2 is performed for an
adjustment time such that the WERR of the final material is made
substantially equal to a design value.
26. An integrated circuit containing a set of thermally sensitive
circuit elements having a thermal budget associated therewith and a
set of isolation trenches in a silicon substrate, in which: said
set of trenches have an aspect ratio of at least four and have been
filled with a spin on trench dielectric material containing
silazane; said substrate has been heated at a temperature of less
than about 450 deg C.; the stress in said trench dielectric
material is compressive stress that was converted from tensile
stress to compressive stress by heating in an ambient containing
H2O at a temperature between about 450 deg C. and about 900 deg C.;
and said substrate has been annealed by heating in an ambient
containing O2 at a temperature above 800 deg C. until Si--N bonds
at the bottom of said trench are substantially converted to Si--O
bonds, in which the time of the stress conversion step and the time
of the anneal step are related such that the thermal budget of the
thermally sensitive component is not exceeded; and said step of
stress conversion and said step of annealing are related such that
the resulting material has compressive stress in the range of 0.1
to 2 Gdynes/cm2, whereby the operation of transistors adjacent to
said set of trenches is not affected and has a WERR of less than
about 2.
27. A circuit according to claim 26, in which the time of the
stress conversion step and the time of the anneal step were related
such that the thermal budget of the thermally sensitive component
was not exceeded.
28. A circuit according to claim 26, in which: said step of stress
conversion and said step of annealing were related such that the
resulting material has compressive stress in the range of 0.1 to 2
Gdynes/cm2 and has a WERR of less than about 2.
29. A circuit according to claim 26, in which: a subset of
isolation trenches surround transistor areas containing a
transistor; and the time and temperature of the stress conversion
step is such that the stress in the dielectric trench material is
not greater than a design limit value.
30. A circuit according to claim 29, in which: the time and
temperature of the stress conversion step is such that the stress
in the dielectric trench material is substantially equal to a
design value.
31. A circuit according to claim 26, in which: the time and
temperature of the stress conversion step and the annealing steps
are such that the stress in the dielectric trench material is
substantially equal to that of oxide deposited by the HDP
technique.
32. A circuit according to claim 29, in which: the time and
temperature of the stress conversion step and the annealing steps
are such that the stress in the dielectric trench material is
substantially equal to that of oxide deposited by the HDP
technique.
Description
BACKGROUND OF INVENTION
[0001] The field of the invention is that of filling high aspect
ratio trenches in integrated circuit processing.
[0002] As ground rule dimensions shrink in integrated circuits, the
problem of filling high aspect ratio trenches increases, in
particular for isolation trenches used in the shallow trench
isolation process, STI, that is commonly used in advanced
processing.
[0003] The industry-standard filling material and process has been
silicon oxide, SiO2, deposited with the high density plasma, HDP,
technique. This method has been widely adopted because it produces
a high quality material that has good filling properties. Designers
of integrated circuits have adapted their structural and material
specifications to this process and material.
[0004] Since silicon is piezo-electric, the properties of field
effect transistors, FETs, are affected by the stress on the
transistor converts the stress in the material from tensile to
compressive.
[0005] Another aspect of the invention is a stress conversion step
followed by an anneal in a dry ambient.
[0006] Another aspect of the invention is a first heating step in a
steam ambient followed by the anneal in a dry ambient.
[0007] Another aspect of the invention is the ability to relate
total allowed device temperature budget and the annealing step to
tune the stress and wet etch rate of the final material.
BRIEF DESCRIPTION OF DRAWINGS
[0008] FIGS. 1A-1C illustrate a portion of a substrate in the
course of the invention.
[0009] FIGS. 2A, 2B illustrate an optional step of applying an HDP
cap layer.
[0010] FIG. 3 illustrates the filling of an aperture with a
reentrant profile.
[0011] FIG. 4 shows a graph of material stress resulting from
different treatments.
[0012] FIG. 5 shows a graph of relative etch rates resulting from
different treatments.
[0013] FIG. 6 shows a graph of relative etch rates resulting from
different treatments.
[0014] FIG. 7 shows a graph of material composition resulting from
different treatments.
DETAILED DESCRIPTION
[0015] The basic sequence in an SOD application is illustrated in
FIG. 1, in which a silicon substrate 10 having a pad nitride/oxide
20 has a set of apertures that have been etched in it by any
convenient process, e.g. a reactive ion etch. Two sizes of
apertures are shown to illustrate that actual wafers will have a
variety of values for the spacing between apertures and the width
of the apertures, as well as different depths. The variation may
result from fluctuations in a single etching process that may
depend, for example, on the pattern density or it may result from
the simultaneous filling of apertures formed in two different
processes.
[0016] On the right of FIG. 1A, aperture 34 has a width 48 and a
depth 46, giving an aspect ratio of 46/48. Apertures 32 have a
width 44 and a depth 42, giving an aspect ratio 42/44. It is
evident that the aspect ratio of the apertures 32 will be higher
than that of aperture 34, so that the process in question will need
to accommodate a range of aspect ratios.
[0017] In the course of the process, a trench dielectric material
filling substance, referred to as a spin-on dielectric (SOD) or
spin-on glass (SOG) will be applied to the wafer, which is rotated
to spread the material quite uniformly over the surface. The
material, which has a suitably low viscosity, will penetrate into
the various apertures and overfill, with a top surface 52 above the
top surface of pad 20. The result is shown in FIG. 1B.
[0018] The wafer is then planarized by CMP or by an etchback step
to remove the excess overfill material, as shown in FIG. 1C.
[0019] FIG. 1C also shows an extra thickness of oxide 57 formed
along the sides of the apertures by annealing the material in an
oxidizing ambient. A conventional step of annealing in an ambient
containing water vapor converts the Nitrogen and Hydrogen in the
silazane to ammonia and molecular Hydrogen that escapes from the
material, leaving a residue that is largely silicon oxide. The
presence of oxygen in the ambient assists in converting Si--N bonds
to Si--O bonds. The properties of the final material will depend on
the degree to which this conversion has been accomplished.
[0020] FIGS. 2A and 2B illustrate an optional aspect of the
invention, in which the silazane fill 54 is recessed by any
conventional etch and a cap layer 62 of HDP is deposited by
standard techniques and planarized with CMP.
[0021] Those skilled in the art will appreciate that the process
will be more consistent and the results better if the stress of the
silazane layer 54 is close to that of HDP layer 62.
[0022] Spin-on materials have the well known property that they
fill various aperture profiles that a process such as chemical
vapor deposition cannot fill. Referring now to FIG. 3, there is
illustrated an aperture 310 having a reentrant profile, meaning
that there is at least one level where the transverse dimension B
is less than the corresponding transverse dimension A at or near
the top of the aperture. This occurs by design in the case of a
trench capacitor or by accident when a divot has been formed on a
wall that is intended to be smooth.
[0023] FIG. 3C illustrates the result of a CVD application, with a
void 325 that has been formed in the body of material 320'. In
contrast, FIG. 3B shows the result of a spin-on application that
fills the aperture uniformly.
[0024] It is well known in the art that the industry standard
material for isolation trenches, referred to as shallow trench
isolation, or STI, is High Density Plasma-assisted oxide (HDP
oxide), which will not fill apertures uniformly when the aspect
ratio is more than about 4 (assuming a vertical trench sidewall
profile).
[0025] In modern processing, there is very strong pressure to
increase the density of features on a chip, so that the aspect
ratio is constantly increasing. Process engineers are now working
on filling trenches with aspect ratios in the range of about 10 and
planning on filling trenches with much higher aspect ratios.
[0026] Various complex and expensive schemes are in use to fill
high aspect ratio trenches that involve depositing a portion of the
total material, cleaning out the upper portion of the aperture so
that new material is not blocked, then filling a second portion,
etc.
[0027] Process engineers go to this effort in spite of the much
better filling properties of spin-on materials because no spin-on
material is currently acceptable. In the case of isolation
trenches, it is not enough that the filled trench insulate--i.e.
not conduct current. Process integration requires that the steps in
the process and the properties of the resulting material must be
consistent with the rest of the process and structure.
[0028] Since the processes in use at the present time have been
developed to be consistent with the properties of HDP oxide, it
would require a great deal of effort to alter those current
processes. It would be highly advantageous if a spin-on process
could be developed that would emulate the material properties of
the HDP material.
[0029] The inventors have realized that it is possible to tune the
stress, composition and wet etch resistance of a spin-on material
to be similar to those of HDP oxide.
[0030] Poly-silazane processed according to the manufacturer's
recommendations produces a final material that has properties very
different from those of HDP, having poor etch resistance, tensile
stress and low density.
[0031] According to the invention, the sequence of processing steps
is:
[0032] Spin-on silazane having a molecular weight in the range of
2000-4000 dissolved in a solvent such as dibutyl ether;
[0033] Pre-bake in O2 ambient (400-700 Torr) at a temperature in
the range 100-450 deg C. for a period of 20-120 min;
[0034] Perform a first anneal in water vapor at a temperature in
the range 450-800 deg C. for a period of 20-120 min;
[0035] In case temperature budget of prior levels allows: Perform a
second anneal in an oxygen ambient without water vapor (400-700
Torr) at a temperature between 800-1200 deg C. for a period of 20
-120 min.
[0036] Planarize the resulting film by CMP.
[0037] For deep STI trenches (aspect ratio>6), an additional
step is an extra anneal in water vapor at a temperature in the
range 450-800 deg C. for a period of 20-120 min after CMP to ensure
that material at the bottom of the trench is oxidized and converted
from Si--N bonding to Si--O bonding.
[0038] It is an advantageous feature of the invention that the
parameters of the final product can be varied by varying the
processing parameters. Illustratively, the final material is high
quality oxide with low impurity contamination; has a wet etch
removal ratio (WERR) at 900 deg C. of less than 1.5; has
compressive film stress in the range of 0.1 to 2 Gdyne/cm2; can be
planarized by CMP with a standard slurry; is thermally stable at
temperatures greater than 1000 deg C.; and has thickness uniformity
(<1% sigma) superior to HDP oxide.
[0039] Referring now to FIG. 4, the graph shows the material stress
in a silazane film annealed with steam and with oxygen ambients.
Point 410 shows a typical value for HDP oxide. Curve 420 shows the
result of a steam anneal between 700 and 900 deg C. As can be seen,
the points at 800 deg C. and 900 deg C. are quite close to HDP,
while the result of films annealed in an oxygen ambient (curve 430)
have a tensile stress.
[0040] FIG. 5 shows corresponding curves for the wet etch rate
ratio i.e. the ratio of the etch rate of the film in question to
the rate of thermal oxide. The etch material is buffered
hydrofluoric acid (BHF). The results, on curve 520, of the steam
anneal at 800 and 900 deg C. are again very similar to the results
of HDP oxide, point 510, while the results of the oxygen anneal,
curve 530, are much higher (having less etch resistance).
[0041] FIG. 6 shows corresponding results for the refractive index
of the resulting oxide. The refractive index is a measure of
material density as well as silicon to oxygen stoichometric
ratio.
[0042] Again, curve 620 (the steam anneal) is closer to point 610,
typical of HDP oxide, while the points on curve 630, the oxygen
anneal, are considerably different.
[0043] FIG. 7 shows the composition of films after anneals at two
different temperatures (in steam). The residual concentration of C
(curve C), N (curve NSi) and hydrogen (Curve H) are much higher at
700 deg C. than at 1000 deg C.
[0044] While very high temperature steam anneal (1000 C) produces
the film with low impurity levels it is obviously can not be used
if prior levels junctions have lower temperature budget
restrictions. In the case of a vertical transistor, the STI is
often done after the transistor has been formed and for example any
prolonged (>10 min) anneal above 900 C is prohibited assuming
100 nm vertical DRAM groundrule.
[0045] Another well known issue with high temperature steam
oxidation of silicon is the formation of defects which decrease
activation energy for dopant diffusion (such as B, P, As, etc) and
subsequent increase in their diffusion coefficients (so called
oxygen enhanced diffusion (OED)). This effect in turn causes even
bigger unwanted changes in prior p-n junction profiles.
[0046] It has been also found, that steam oxidation above a
temperature of 800 deg C. produces excessive oxidation of the
silicon in the wafer (either bulk, epitaxial or SOI) that can
degrade the parameters of the transistor that will be formed in the
active area. Thick oxide film (>300 A) grows on an STI sidewall
(especially the top corner portion) and creates stress in adjacent
active areas as well as increases the number of defects. Defects
are easily formed in the top STI corner, after pad SiN strip and
subsequent etch and anneal processing steps. The stress in the
active areas may vary according to the circuit design. What is
beneficially provided by the present invention is that the new
trench material does not change the stress that the transistor was
designed for.
[0047] Once a silazane film is subjected to a first 800 C steam
anneal it is beneficial to proceed with a second anneal in oxygen
at temperatures>800 C. Such an anneal further decreases the wet
etch rate ratio (to about 1.1 of that of thermal oxide) and keeps
film stress compressive within the range of 0.5-2 Gdyne/cm2.
[0048] The properties of the final film can be adjusted or tuned by
varying the time of the steam anneal and of the oxygen anneal.
[0049] While the invention has been described in terms of a single
preferred embodiment, those skilled in the art will recognize that
the invention can be practiced in various versions within the
spirit and scope of the following claims.
* * * * *