U.S. patent application number 13/260173 was filed with the patent office on 2012-01-26 for composition for metal plating comprising suppressing agent for void free submicron feature filling.
This patent application is currently assigned to BASF SE. Invention is credited to Charlotte Emnet, Alexandra Haag, Dieter Mayer, Roman Benedikt Raether, Cornelia Roeger-Goepfert.
Application Number | 20120018310 13/260173 |
Document ID | / |
Family ID | 42935669 |
Filed Date | 2012-01-26 |
United States Patent
Application |
20120018310 |
Kind Code |
A1 |
Roeger-Goepfert; Cornelia ;
et al. |
January 26, 2012 |
COMPOSITION FOR METAL PLATING COMPRISING SUPPRESSING AGENT FOR VOID
FREE SUBMICRON FEATURE FILLING
Abstract
Composition comprising a source of metal ions and at least one
suppressing agent obtainable by reacting a) an amine compound
comprising at least three active amino functional groups with b) a
mixture of ethylene oxide and at least one compound selected from
C3 and C4 alkylene oxides.
Inventors: |
Roeger-Goepfert; Cornelia;
(Schwetzingen, DE) ; Raether; Roman Benedikt;
(Speyer, DE) ; Emnet; Charlotte; (Stuttgart,
DE) ; Haag; Alexandra; (Hemhofen, DE) ; Mayer;
Dieter; (Darmstadt, DE) |
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
42935669 |
Appl. No.: |
13/260173 |
Filed: |
March 31, 2010 |
PCT Filed: |
March 31, 2010 |
PCT NO: |
PCT/EP10/54281 |
371 Date: |
October 4, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61256328 |
Oct 30, 2009 |
|
|
|
Current U.S.
Class: |
205/118 ;
205/261; 205/296 |
Current CPC
Class: |
C23C 18/31 20130101;
C25D 7/123 20130101; H05K 3/423 20130101; C25D 3/58 20130101; C23C
18/32 20130101; H01L 21/2885 20130101; H01L 21/76877 20130101; C25D
3/38 20130101 |
Class at
Publication: |
205/118 ;
205/261; 205/296 |
International
Class: |
C25D 3/38 20060101
C25D003/38; C25D 5/02 20060101 C25D005/02 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 7, 2009 |
EP |
09157540.7 |
Claims
1-15. (canceled)
16. A composition, comprising: a source of at least one metal ion;
and at least one suppressing agent obtained by a method comprising
reacting a) an amine compound comprising at least three active
amino functional groups with b) a mixture of ethylene oxide and at
least one compound selected from the group consisting of a C3
alkylene oxide and a C4 alkylene oxide, wherein a content of
ethylene oxide and any C3 to C4 alkylene oxide in the at least one
suppressing agent is from 30 to 70 wt %.
17. The composition of claim 16, wherein the at least one metal ion
comprises copper ions.
18. The composition of claim 16, wherein the at least one
suppressing agent has a formula (I): ##STR00002## wherein R.sup.1
radicals are each independently a copolymer of ethylene oxide and
at least one selected from the group consisting of a C3 alkylene
oxide and a C4 alkylene oxide, wherein the copolymer is a random
copolymer; R.sup.2 radicals are each independently selected from
the group consisting of R.sup.1 radicals and an alkylene; X and Y
are spacer groups independently and X for each repeating unit
independently is selected from the group consisting of a C1
alkylene, a C2 alkylene, a C3 alkylene, a C4 alkylene, a C5
alkylene, a C6 alkylene and a Z--(O--Z).sub.m, wherein each of a Z
radical is independently selected from the group consisting of a C2
alkylene, a C3 alkylene, a C4 alkylene, a C5 alkylene, and a C6
alkylene; n is an integer equal to or greater than 0; and m is an
integer equal to or greater than 1.
19. The composition of claim 18, wherein X and Y independently, and
X for each repeating unit independently, are selected from the
group consisting of a C1 alkylene, a C2 alkylene, a C3 alkylene and
a C4 alkylene.
20. The composition of claim 16, wherein the amine compound is at
least one selected from the group consisting of a diethylene
triamine, a 3-(2-aminoethyl)aminopropylamine, a
3,3'-iminodi(propylamine), a N,N-bis(3-aminopropyl)methylamine, a
bis(3-dimethylaminopropyl)amine, a triethylenetetraamine and a N,N
`-bis(3-aminopropyl)ethylenediamine.
21. The composition of claim 16, wherein the at least one compound
selected from the group consisting of a C3 alkylene oxide and a C4
alkylene oxide is a propylene oxide.
22. The composition of claim 16, wherein the molecular weight
M.sub.w of the at least one suppressing agent is 6000 g/mol or
more.
23. The composition of claim 22, wherein the molecular weight
M.sub.w of the at least one suppressing agent is from 7000 to 19000
g/mol.
24. The composition of claim 16, further comprising at least one
accelerating agent.
25. The composition of claim 16, further comprising at least one
leveling agent.
26. A method of depositing a metal on a substrate, the method
comprising: contacting the substrate with a metal plating bath
comprising the composition of claim 16, wherein the substrate
comprises at least one feature having an aperture size of 30
nanometers or less.
27. A process, depositing a metal layer on a substrate, the process
comprising: a) contacting a metal plating bath comprising a
composition of claim 16 with the substrate; and b) applying a
current density to the substrate for a time sufficient to deposit
the metal layer onto the substrate.
28. The process of claim 27, wherein the substrate comprises at
least one submicrometer sized feature and the deposition is
performed to fill the at least one submicrometer sized feature.
29. The process of claim 28, wherein the at least one
submicrometer-sized feature has at least one selected from the
group consisting of an aperture size from 1 to 30 nm and an aspect
ratio of 4 or more.
30. The composition of claim 17, wherein the amine compound is at
least one selected from the group consisting of a diethylene
triamine, a 3-(2-aminoethyl)aminopropylamine, a
3,3'-iminodi(propylamine), a N,N-bis(3-aminopropyl)methylamine, a
bis(3-dimethylaminopropyl)amine, a triethylenetetraamine and a
N,N'-bis(3-aminopropyl)ethylenediamine.
31. The composition of claim 17, wherein the at least one compound
selected from the group consisting of a C3 alkylene oxide and a C4
alkylene oxide is a propylene oxide.
32. The composition of claim 17, wherein the molecular weight
M.sub.w of the at least one suppressing agent is 6000 g/mol or
more.
33. The composition of claim 32, wherein the molecular weight
M.sub.w of the at least one suppressing agent is from 7000 to 19000
g/mol.
34. The composition of claim 17, further comprising at least one
accelerating agent.
35. The composition of claim 17, further comprising at least one
leveling agent.
Description
[0001] Filling of small features, such as vias and trenches, by
copper electroplating is an essential part of the semiconductor
manufacture process. It is well known, that the presence of organic
substances as additives in the electroplating bath can be crucial
in achieving a uniform metal deposit on a substrate surface and in
avoiding defects, such as voids and seams, within the copper
lines.
[0002] One class of additives are the so-called suppressors or
suppressing agents. Suppressors are used to provide a substantially
bottom-up filling of small features like vias or trenches. The
smaller the features are the more sophisticated the additives have
to be to avoid voids and seams. In literature, a variety of
different suppressing compounds have been described. The mostly
used class of suppressors are polyether compounds like polyglycols
or polyalkylene oxides like ethylene oxide propylene oxide
copolymers.
[0003] US 2005/0072683 A1 discloses high molecular weight
surfactants inhibiting the electrodeposition like alkyl
polyoxyethylene amines, particularly ethylenediamine ethylene oxide
(EO) propylene oxide (PO) block copolymers in combination with a
further polyethylene glycol (PEG) suppressor.
[0004] WO2004/016828 A2 discloses additives called antimisting
agents prepared by polyalkoxylation of amine compounds like
triethanolamine, ethylenediamine or diethylenetriamine. Alkoxylated
triethanolamine compounds were mentioned to be preferred and were
used in the examples.
[0005] US 2006/0213780 A1 discloses amine-based copolymers of EO/PO
copolymers having at least 70% PO content. The copolymers are
mentioned to have block, alternating or random structure. A
preferred amine is ethylenediamine.
[0006] U.S. Pat. No. 6,444,110 B2 discloses an electroplating
solution which may comprise, besides a huge variety of additives
called surfactants, nitrogen containing additives like ethoxylated
amines, polyoxyalkylene amines, alkanol amines, amides like those
provided by BASF under the trademark TETRONIC.RTM., all of those
being EO/PO block copolymers of ethylene diamine. In the examples
only polyglycol type suppressors were used.
[0007] EP 440 027 A2 discloses, as suppressors, polyoxyalkylated
diamine additives. Alkoxylated diamines are identified to be the
most preferred additives. U.S. Pat. No. 4,347,108 A discloses, as
suppressors, those provided by BASF under the trademark
TETRONIC.RTM., all of those being EO/PO block copolymers of
ethylene diamine.
[0008] WO 2006/053242 A1 discloses amine-based polyoxyalkylene
suppressors. The amine may be methylamine, ethylamine, propylamine,
ethylendiamine, diethylenetriamine, diaminopropane,
diethyleneglykol diamin or triethylenglycol diamine. The copolymers
may have block, alternating or random structure. Compounds provided
by BASF under the trademark TETRONIC.RTM., all of those being EO/PO
block copolymers of ethylene diamine, and having a molecular mass
of up to 5500 g/mol are described to be preferred. The block
copolymers of EO and PO are used in the examples.
[0009] US 2005/0045485 A1 discloses amine-based polyalkylene oxide
copolymers, including diamines, triamines.
[0010] US 2006/0213780 A1 discloses amine-based copolymers, e.g.
ethylenediamine or laurylamine based EO, PO or BuO copolymers.
[0011] Up to now, although sometimes speculatively mentioned in the
prior art, amine-based random EO/PO copolymers, or other
polyoxyalkylene copolymers, have never been used in the prior art.
Furthermore, although sometimes speculatively mentioned,
amine-based polyoxyalkylene polymers having at least 3 amine
functional groups have also never been used in the prior art.
Furthermore, although sometimes speculatively covered by wide
ranges mentioned in the prior art, amine-based polyoxyalkylene
polymers having a molecular weight M.sub.w of 6000 g/mol or more at
least 3 amine functional groups have also never been used in the
prior art. Those compounds are not believed to be commercially
available in the market at the priority date of this
application.
[0012] With further decreasing aperture size of the features like
vias or trenches to dimensions of below 100 nanometers and even
below 50 nanometers, respectively, the filling of the interconnects
with copper becomes especially challenging, also since the copper
seed deposition prior to the copper electrodeposition might exhibit
inhomogeneity and non-conformity and thus further decreases the
aperture sizes particularly at the top of the apertures. Especially
apertures with a seed overhang at the top opening or convex-shaped
apertures are challenging to fill and require an especially
effective copper growth suppression at the side wall of the feature
and the opening of the aperture.
[0013] FIG. 3 shows a seeded substrate exhibiting impact of the
seed on the opening of the features to be filled. The seed is shown
by the light grey layer on the dark grey structures. Since there is
an increasing seed overhang issue with further shrinking feature
sizes, as depicted in FIG. 3, there is a serious risk of pinch-off
void formation in the upper half of the trench close to the opening
if the suppressor does not completely avoid sidewall copper growth
(2'' in FIGS. 2a to 2c). As can be seen the openings are reduced to
less than the half of the width without the seed layer resulting in
effective aperture sizes of about 18 nanometer to 16 nanometer,
respectively. The seeded feature has a convex shape.
[0014] It is therefore an object of the present invention to
provide a copper electroplating additive having good superfilling
properties, in particular suppressing agents capable of providing a
substantially voidless and seamless filling of features on the
nanometer and on the micrometer scale with a metal electroplating
bath, preferably a copper electroplating bath. It is a further
object of the present invention to provide a copper electroplating
additive capable of providing a substantially voidless and seamless
filling of features having a convex shape.
[0015] Surprisingly, it has now been found, that the use of
amine-based polyoxyalkylene suppressing agents based on amines
having at least three amino functional groups in combination with
random oxyalkylene copolymers show extraordinary superfilling
properties, particularly if used to fill in features having
extremely small aperture sizes and/or high aspect ratios. The
present invention provides a new class of highly effective, strong
suppressing agents that cope with the seed overhang issue and
provide substantially defect free trench filling despite a
non-conformal copper seed.
[0016] Therefore the present invention provides a composition
comprising a source of metal ions and at least one suppressing
agent obtainable by reacting an amine compound comprising at least
three active amino functional groups with a mixture of ethylene
oxide and at least one compound selected from C3 and C4 alkylene
oxides.
[0017] The advantage of the invention is that suppressing agents
are provided that result in a extraordinarily pronounced bottom-up
fill copper growth while perfectly suppressing the sidewall copper
growth, both leading to a flat growth front and thus providing
substantially defect free trench or via fill. The strong sidewall
copper growth suppression of the invention enables non-conformal
copper seeded features to be substantially void free filled.
Moreover the invention provides an overall homogeneous bottom-up
fill in neighboring features of dense feature areas.
[0018] The suppressing agents according to the present invention
are particularly useful for filling of small features, particularly
those having aperture sizes of 30 nanometer or below.
[0019] The suppressing agent is obtainable by reacting an amine
compound containing at least three active amino functional groups
with a mixture of ethylene oxide and at least one compound selected
from C3 and C4 alkylene oxides. In this way random copolymers of
ethylene oxide and the at least one further C3 and C4 alkylene
oxides are generated starting from the active amino functional
groups of the amine compound. In the following ethylene oxide is
also referred to as Ea
[0020] The amine compound containing at least three active amino
functional groups is also referred to as the "amine starter".
[0021] According to the present invention active amino functional
groups are those being able to start an polyalkoxy chain by
reacting with the alkylene oxides, i.e. primary amino functional
groups --NH2 or secondary amino functional groups --NH--, depending
on its position in the molecule. Tertiary or quarternary amino or
ammonium groups, respectively, may be present in the amine compound
but since they are not able to start an alkylene oxide chain they
are no active amino functional groups. Generally terminal amino
functional groups are primary ones and non-terminal amino
functional groups are secondary ones.
[0022] Preferably at least five hydrogen atoms bonded to nitrogen
are present in the amine starter. This leads to at least five
alkylene oxide copolymer chains present in the suppressing
agent.
[0023] Preferably the suppressing agent is selected from compounds
of formula I
##STR00001##
wherein [0024] the R.sup.1 radicals are each independently selected
from a copolymer of ethylene oxide and at least one further C3 to
C4 alkylene oxide, said copolymer being a random copolymer. [0025]
the R.sup.2 radicals are each independently selected from R.sup.1
or alkyl, preferably C1 to C6 alkyl, most preferably methyl or
ethyl. [0026] X and Y are spacer groups independently, and X for
each repeating unit independently, selected from C1 to C6 alkylen
and Z--(O--Z)m, wherein the Z radicals are each independently
selected from C2 to C6 alkylen, [0027] n is an integer equal to or
greater than 1. [0028] m is an integer equal to or greater than
1,
[0029] Preferably spacer groups X and Y are independently, and X
for each repeating unit independently, selected from C1 to C4
alkylene. Most preferably X and Y are independently, and X for each
repeating unit independently, selected from methylene (--CH2-) or
ethylene (--C2H4-).
[0030] Preferably Z is selected from C2 to C4 alkylene, most
preferably from ethylene or propylene.
[0031] Preferably n is an integer from 1 to 10, more preferably
from 1 to 5, most preferably from 1 to 3. Preferably m is an
integer from 1 to 10, more preferably from 1 to 5, most preferably
from 1 to 3.
[0032] In a preferred embodiment the amine compound is selected
from diethylene triamine, (3-(2-aminoethyl)aminopropylamine,
3,3'-iminodi(propylamine), N,N-bis(3-aminopropyl)methylamine,
bis(3-dimethylaminopropyl)amine, triethylenetetraamine and
N,N'-bis(3-aminopropyl)ethylenediamine or mixtures thereof.
Particularly preferred is diethylene triamine.
[0033] The C3 to C4 alkylene oxides may be propylene oxide (PO),
butylene oxide (BuO) or any isomers thereof.
[0034] In another preferred embodiment the C3 to C4 alkylene oxide
is selected from propylene oxide (PO). In this case EO/PO copolymer
side chains are generated starting from the active amino functional
groups
[0035] The content of ethylene oxide in the copolymer of ethylene
oxide and the further C3 to C4 alkylene oxide can generally be from
about 5% by weight to about 95% by weight, preferably from about
30% by weight to about 70% by weight, particularly preferably
between about 35% by weight to about 65% by weight.
[0036] The molecular weight M.sub.w of the suppressing agent may be
between about 500 g/mol to about 30000 g/mol. Preferably the
molecular weight M.sub.w should be about 6000 g/mol or more,
preferably from about 6000 g/mol to about 20000 g/mol, more
preferably from about 7000 g/mol to about 19000 g/mol, and most
preferably from about 9000 g/mol to about 18000 g/mol. Preferred
total amounts of alkylene oxide units in the suppressing agent may
be from about 120 to about 360, preferably from about 140 to about
340, most preferably from about 180 to about 300.
[0037] Typical total amounts of alkylene oxide units in the
suppressing agent may be about 110 ethylene oxide units (E0) and 10
propylene oxide units (PO), about 100 EO and 20 PO, about 90 EO and
30 PO, about 80 EO and 40 PO, about 70 EO and 50 PO, about 60 EO
and 60 PO, about 50 EO and 70 PO, about 40 EO and 80 PO, about 30
EO and 90 PO, about 100 EO and 10 butylene oxide (BuO) units, about
90 EO and 20 BO, about 80 EO and 30 BO, about 70 EO and 40 BO,
about 60 EO and 50 BO or about 40 EO and 60 BO to about 330 EO and
30 PO units, about 300 EO and 60 PO, about 270 EO and 90 PO, about
240 EO and 120 PO, about 210 EO and 150 PO, about 180 EO and 180
PO, about 150 EO and 210 PO, about 120 EO and 240 PO, about 90 EO
and 270 PO, about 300 EO and 30 butylene oxide (BuO) units, about
270 EO and 60 BO, about 240 EO and 90 BO, about 210 EO and 120 BO,
about 180 EO and 150 BO, or about 120 EO and 180 BO.
[0038] Preferably the composition further comprises at least one
accelerating agent and/or at least one leveling agent.
[0039] A further embodiment of the present invention is the use of
a metal plating bath comprising a composition as described above
for depositing the metal on substrates comprising features having
an aperture size of 30 nanometers or less.
[0040] A further embodiment of the present invention is a process
for depositing a metal layer on a substrate by
[0041] a) contacting a metal plating bath comprising a composition
according to the present invention with the substrate, and
[0042] b) applying a current density to the substrate for a time
sufficient to deposit a metal layer onto the substrate.
[0043] Preferably the substrate comprises submicrometer sized
features and the deposition is performed to fill the submicrometer
sized features. Most preferably the submicrometer-sized features
have an (effective) aperture size from 1 to 30 nanometers and/or an
aspect ratio of 4 or more. More preferably the features have an
aperture size of 25 nanometers or below, most preferably of 20
nanometers or below.
[0044] The aperture size according to the present invention means
the smallest diameter or free distance of a feature before plating,
i.e. after copper seed deposition. The terms "aperture" and
"opening" are used herein synonymously. A convex shape is a feature
having an aperture size being at least 25%, preferably 30%, most
preferably 50% smaller than the biggest diameter or free distance
of thea feature before plating.
[0045] The plating bath according to the present invention is
particular suitable for features having high aspect ratios of 4 or
more, particularly of 6 or more.
[0046] A wide variety of metal plating baths may be used with the
present invention. Metal electroplating baths typically contain a
metal ion source, an electrolyte, and a polymeric suppressing
agent.
[0047] The metal ion source may be any compound capable of
releasing metal ions to be deposited in the electroplating bath in
sufficient amount, i.e. is at least partially soluble in the
electroplating bath. It is preferred that the metal ion source is
soluble in the plating bath. Suitable metal ion sources are metal
salts and include, but are not limited to, metal sulfates, metal
halides, metal acetates, metal nitrates, metal fluoroborates, metal
alkylsulfonates, metal arylsulfonates, metal sulfamates, metal
gluconates and the like. It is preferred that the metal is copper.
It is further preferred that the source of metal ions is copper
sulfate, copper chloride, copper acetate, copper citrate, copper
nitrate, copper fluoroborate, copper methane sulfonate, copper
phenyl sulfonate and copper p-toluene sulfonate. Copper sulfate
pentahydrate and copper methane sulfonate are particularly
preferred. Such metal salts are generally commercially available
and may be used without further purification.
[0048] Besides metal electroplating the compositions may be used in
electroless deposition of metal containing layers. The compositions
may particularly used in the deposition of barrier layers
containing Ni, Co, Mo, W and/or Re. In this case, besides metal
ions, further elements of groups III and V, particularly B and P
may be present in the composition for electroless deposition and
thus co-deposited with the metals.
[0049] The metal ion source may be used in the present invention in
any amount that provides sufficient metal ions for electroplating
on a substrate. Suitable metal ion metal sources include, but are
not limited to, tin salts, copper salts, and the like. When the
metal is copper, the copper salt is typically present in an amount
in the range of from about 1 to about 300 g/L of plating solution.
It will be appreciated mixtures of metal salts may be electroplated
according to the present invention. Thus, alloys, such as
copper-tin having up to about 2 percent by weight tin, may be
advantageously plated according to the present invention. The
amounts of each of the metal salts in such mixtures depend upon the
particular alloy to be plated and is well known to those skilled in
the art.
[0050] In general, besides the metal ion source and at least one of
the suppressing agents according to the present invention the
present metal electroplating compositions preferably include
electrolyte, i. e. acidic or alkaline electrolyte, one or more
sources of metal ions, optionally halide ions, and optionally other
additives like accelerators and/or levelers. Such baths are
typically aqueous. The water may be present in a wide range of
amounts. Any type of water may be used, such as distilled,
deionized or tap.
[0051] The electroplating baths of the present invention may be
prepared by combining the components in any order. It is preferred
that the inorganic components such as metal salts, water,
electrolyte and optional halide ion source, are first added to the
bath vessel followed by the organic components such as leveling
agents, accelerators, suppressors, surfactants and the like.
[0052] Typically, the plating baths of the present invention may be
used at any temperature from 10 to 65 degrees C. or higher. It is
preferred that the temperature of the plating baths is from 10 to
35 degrees C. and more preferably from 15 degrees to 30 degrees
C.
[0053] Suitable electrolytes include such as, but not limited to,
sulfuric acid, acetic acid, fluoroboric acid, alkylsulfonic acids
such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic
acid and trifluoromethane sulfonic acid, arylsulfonic acids such as
phenyl sulfonic acid and toluenesulfonic acid, sulfamic acid,
hydrochloric acid, phosphoric acid, tetraalkylammonium hydroxide,
preferably tetramethylammonium hydroxide, sodium hydroxide,
potassium hydroxide and the like. Acids are typically present in an
amount in the range of from about 1 to about 300 g/l, alkaline
electrolytes are typically present in an amount of about 0.1 to
about 20 g/l or to yield a pH of 8 to 13 respectively, and more
typically to yield a pH of 9 to 12.
[0054] Such electrolytes may optionally contain a source of halide
ions, such as chloride ions as in copper chloride or hydrochloric
acid. A wide range of halide ion concentrations may be used in the
present invention such as from about 0 to about 500 ppm. Typically,
the halide ion concentration is in the range of from about 10 to
about 100 ppm based on the plating bath. It is preferred that the
electrolyte is sulfuric acid or methanesulfonic acid, and
preferably a mixture of sulfuric acid or methanesulfonic acid and a
source of chloride ions. The acids and sources of halide ions
useful in the present invention are generally commercially
available and may be used without further purification.
[0055] Any accelerators may be advantageously used in the plating
baths according to the present invention. Accelerators useful in
the present invention include, but are not limited to, compounds
comprising one or more sulphur atom and a sulfonic/phosphonic acid
or their salts.
[0056] The generally preferred accelerators have the general
structure MO.sub.3X--R.sup.21--(S).sub.n--R.sup.22, with: [0057] M
is a hydrogen or an alkali metal (preferably Na or K) [0058] X is P
or S [0059] n=1 to 6 [0060] R.sup.21 is selected from C1-C8 alkyl
group or heteroalkyl group, an aryl group or a heteroaromatic
group. Heteroalkyl groups will have one or more heteroatom (N, S,
O) and 1-12 carbons. Carbocyclic aryl groups are typical aryl
groups, such as phenyl, naphtyl. Heteroaromatic groups are also
suitable aryl groups and contain one or more N, O or S atom and 1-3
separate or fused rings. [0061] R.sup.22 is selected from H or
(--S--R.sup.21'XO.sub.3M), with R.sup.21' being identical or
different from R.sup.21.
[0062] More specifically, useful accelerators include those of the
following formulae:
MO.sub.3S--R.sup.21--SH
MO.sub.3S--R.sup.21--S--S--R.sup.21'--SO.sub.3M
MO.sub.3S--Ar--S--S--Ar--SO.sub.3M
with R.sup.21 is as defined above and Ar is Aryl.
[0063] Particularly preferred accelerating agents are: [0064] SPS:
bis-(3-sulfopropyl)-disulfide disodium salt [0065] MPS:
3-mercapto-1-propansulfonic acid, sodium salt
[0066] Other examples of accelerators, used alone or in mixture,
include, but are not limited to: MES (2-Mercaptoethanesulfonic
acid, sodium salt); DPS (N,N-dimethyldithiocarbamic acid
(3-sulfopropylester), sodium salt); UPS
(3-[(amino-iminomethyl)-thio]-1-propylsulfonic acid); ZPS
(3-(2-benzthiazolylthio)-1-propanesulfonic acid, sodium salt);
3-mercapto-propylsulfonicacid-(3-sulfopropyl)ester; methyl-(
.omega.-sulphopropyl)-disulfide, disodium salt; methyl-(
.omega.-sulphopropy)-trisulfide, disodium salt.
[0067] Such accelerators are typically used in an amount of about
0.1 ppm to about 3000 ppm, based on the total weight of the plating
bath. Particularly suitable amounts of accelerator useful in the
present invention are 1 to 500 ppm, and more particularly 2 to 100
ppm.
[0068] Any additional suppressor may be advantageously used in the
present invention. Suppressors useful in the present invention
include, but are not limited to, polymeric materials, particularly
those having heteroatom substitution, and more particularly oxygen
substitution. It is preferred that the suppressor is a
polyalkyleneoxide. Suitable suppressors include polyethylene glycol
copolymers, particularly polyethylene glycol polypropylene glycol
copolymers. The arrangement of ethylene oxide and propylene oxide
of suitable suppressors may be block, alternating, gradient, or
random. The polyalkylene glycol may comprise further alkylene oxide
building blocks such as butylene oxide. Preferably, the average
molecular weight of suitable suppressors exceeds about 2000 g/mol.
The starting molecules of suitable polyalkylene glycol may be alkyl
alcohols such as methanol, ethanol, propanol, n-butanol and the
like, aryl alcohols such as phenols and bisphenols, alkaryl
alcohols such as benzyl alcohol, polyol starters such as glycol,
glycerin, trimethylol propane, pentaerythritol, sorbitol,
carbohydrates such as saccharose, and the like, amines and
oligoamines such as alkyl amines, aryl amines such as aniline,
triethanol amine, ethylene diamine, and the like, amides, lactams,
heterocyclic amines such as imidazol and carboxylic acids.
Optionally, polyalkylene glycol suppressors may be functionalized
by ionic groups such as sulfate, sulfonate, ammonium, and the
like.
[0069] When suppressors are used, they are typically present in an
amount in the range of from about 1 to about 10,000 ppm based on
the weight of the bath, and preferably from about 5 to about 10,000
ppm.
[0070] Leveling agents can advantageously be used in the metal
plating baths according to the present invention. The terms
"leveling agent" and "leveler" are used herein synonymously.
[0071] Suitable leveling agents include, but are not limited to,
one or more of polyethylene imine and derivatives thereof,
quaternized polyethylene imine, polyglycine, poly(allylamine),
polyaniline, polyurea, polyacrylamide,
poly(melamine-co-formaldehyde), reaction products of amines with
epichlorohydrin, reaction products of an amine, epichlorohydrin,
and polyalkylene oxide, reaction products of an amine with a
polyepoxide, polyvinylpyridine, polyvinylimidazole,
polyvinylpyrrolidone, or copolymers thereof, nigrosines,
pentamethyl-para-rosaniline hydrohalide, hexamethyl-pararosaniline
hydrohalide, trialkanolamines and their derivatives or compounds
containing a functional group of the formula N--R--S, where R is a
substituted alkyl, unsubstituted alkyl, substituted aryl or
unsubstituted aryl. Typically, the alkyl groups are (C1-C6)alkyl
and preferably (C1-C4)alkyl. In general, the aryl groups include
(C6-C20)aryl, preferably (C6-C10)aryl. Such aryl groups may further
include heteroatoms, such as sulfur, nitrogen and oxygen. It is
preferred that the aryl group is phenyl or napthyl. The compounds
containing a functional group of the formula N--R--S are generally
known, are generally commercially available and may be used without
further purification.
[0072] In such compounds containing the N--R--S functional group,
the sulfur ("S") and/or the nitrogen ("N") may be attached to such
compounds with single or double bonds. When the sulfur is attached
to such compounds with a single bond, the sulfur will have another
substituent group, such as but not limited to hydrogen,
(C1-C12)alkyl, (C2-C12)alkenyl, (C6-C20)aryl, (C1-C12)alkylthio,
(C2-C12)alkenylthio, (C6-C20)arylthio and the like. Likewise, the
nitrogen will have one or more substituent groups, such as but not
limited to hydrogen, (C1-C12)alkyl, (C2-C12)alkenyl, (C7-C10)aryl,
and the like. The N--R--S functional group may be acyclic or
cyclic. Compounds containing cyclic N--R--S functional groups
include those having either the nitrogen or the sulfur or both the
nitrogen and the sulfur within the ring system.
[0073] By "substituted alkyl" is meant that one or more of the
hydrogens on the alkyl group is replaced with another substituent
group, such as, but not limited to, cyano, hydroxy, halo,
(C1-C6)alkoxy, (C1-C6)alkylthio, thiol, nitro, and the like. By
"substituted aryl" is meant that one or more hydrogens on the aryl
ring are replaced with one or more substituent groups, such as, but
not limited to, cyano, hydroxy, halo, (C1-C6)alkoxy, (C1-C6)alkyl,
(C2-C6)alkenyl, (C1-C6)alkylthio, thiol, nitro, and the like.
"Aryl" includes carbocyclic and heterocyclic aromatic systems, such
as, but not limited to, phenyl, naphthyl and the like.
[0074] Polyalkanolamines, alkoxylated polyalkanolamines,
functionalized polyalkanolamines, and functionalized alkoxylated
polyalkanolamines are particularly preferred levelling agents in
copper electroplating baths. Such Polyalkanolamines are described
in European patent application No. 08172330.6, which is
incorporated herein by reference.
[0075] Polyalkanolamines can be obtained by condensing at least one
trialkanolamine of the general formula N(R.sup.11--OH).sub.3 (Ia)
and/or at least one dialkanolamine of the general formula
R.sup.12--N(R.sup.11--OH).sub.2 (Ib) to give a polyalkanolamine(II)
(stage A),
where [0076] the R.sup.11 radicals are each independently selected
from a divalent, linear and branched aliphatic hydrocarbon radical
having from 2 to 6 carbon atoms, and [0077] the R.sup.12 radicals
are each selected from hydrogen and aliphatic, cycloaliphatic and
aromatic hydrocarbon radicals, all of which may be linear or
branched, having from 1 to 30 carbon atoms.
[0078] The alkanolamine can be used as such or may optionally be
alkoxylated, functionalized or alkoxylated and functionalized to
get alkoxylated polyalkanolamines (III), functionalized
polyalkanolamines (IV) or functionalized alkoxylated
polyalkanolamines (V).
[0079] Alkoxylated polyalkanolamines (III) can be obtained by
alkoxylating polyalkanolamine (II) with C.sub.2- to
C.sub.12-alkylene oxides, styrene oxide, glycidol, or glycidyl
ethers with the proviso that the average degree of alkoxylation is
from 0.1 to 200 per OH group and--where present--secondary amino
group (stage B).
[0080] Functionalized polyalkanolamines (IV) can be obtained by
functionalizing polyalkanolamine (II) with suitable
functionalization reagents which are capable of reaction with
hydroxyl groups and/or amino groups (stage C).
[0081] Functionalized alkoxylated polyalkanolamines (V) can be
obtained by functionalizing alkoxylated polyalkanolamine (III) with
suitable functionalization reagents which are capable of reaction
with hydroxyl groups and/or amino groups (stage D).
[0082] The trialkanolamines (Ia) and/or dialkanolamines (Ib) used
in stage (A) have the general formulae N(R.sup.11--OH).sub.3 (Ia)
and R.sup.12--N(R.sup.11--OH).sub.2 (Ib).
[0083] The R.sup.11 radicals are in each case independently a
divalent linear or branched aliphatic hydrocarbon radical having
from 2 to 6 carbon atoms, preferably 2 or 3 carbon atoms.
[0084] Examples of such radicals comprise ethane-1,2-diyl,
propane-1,3-diyl, propane-1,2-diyl, 2-methylpropane-1,2-diyl,
2,2-dimethylpropane-1,3-diyl, butane-1,4-diyl, butane-1,3-diyl
(=1-methylpropane-1,3-diyl), butane-1,2-diyl, butane-2,3-diyl,
2-methylbutane-1,3-diyl, 3-methylbutane-1,3-diyl
(=1,1-dimethylpropane-1,3-diyl), pentane-1,4-diyl,
pentane-1,5-diyl, pentane-2,5-diyl, 2-methylpentane-2,5-diyl
(=1,1-dimethylbutane-1,3-diyl) and hexane-1,6-diyl. The radicals
are preferably ethane-1,2-diyl, propane-1,3-diyl or
propane-1,2-diyl.
[0085] The R.sup.12 radical is hydrogen and/or linear or branched
aliphatic, cycloaliphatic and/or aromatic hydrocarbon radicals
having from 1 to 30 carbon atoms, preferably from 1 to 20 carbon
atoms and more preferably from 1 to 10 carbon atoms. Aromatic
radicals may of course also have aliphatic substituents. R.sup.12
is preferably hydrogen or aliphatic hydrocarbon radicals having
from 1 to 4 carbon atoms.
[0086] Examples of preferred trialkanolamines (Ia) comprise
triethanolamine, triisopropanolamine and tributan-2-olamine,
particular preference is given to triethanolamine.
[0087] Examples of preferred dialkanolamines (Ib) comprise
diethanolamine, N-methyl-diethanolamine,
N,N-bis(2-hydroxypropyl)-N-methylamine,
N,N-bis(2-hydroxybutyl)-N-methylamine, N-isopropyldiethanolamine,
N-n-butyldiethanolamine, N-sec-butyldiethanolamine,
N-cyclohexyldiethanolamine, N-benzyldiethanolamine,
N-4-tolyldiethanolamine or N,N-bis(2-hydroxyethyl)aniline.
Particular preference is given to diethanolamine.
[0088] In addition to the trialkanolamines (Ia) and/or
dialkanolamines (Ib) it is optionally possible to use further
components (Ic) having two hydroxyl and/or amino groups for the
polycondensation.
[0089] The polycondensation of components (Ia) and/or (Ib) and
optionally (Ic) can be carried out by methods known in principle to
those skilled in the art while heating the components, with
elimination of water. Suitable methods are disclosed, for example,
by EP 441 198 A2. It will be appreciated that it is in each case
also possible to use mixtures of different components (Ia), (Ib) or
(Ic).
[0090] The condensation is performed typically at temperatures of
from 120 to 280 degree C., preferably from 150 to 260 degree C. and
more preferably from 180 to 240 degree C.
[0091] The water formed is preferably distilled off. The reaction
time is typically from 1 to 16 h, preferably from 2 to 8 h. The
degree of condensation can be controlled in a simple manner through
the reaction temperature and time.
[0092] The polycondensation is preferably carried out in the
presence of an acid, preferably phosphorous acid (H.sub.3PO.sub.3)
and/or hypophosphorous acid (H.sub.3PO.sub.2). Preferred amounts
are from 0.05 to 2% by weight, preferably from 0.1 to 1% by weight,
based on the components to be condensed. In addition to the acid,
it is also possible to use additional catalysts, for example, zinc
halides or aluminum sulfate, if appropriate in a mixture with
acetic acid, as disclosed, for example by U.S. Pat. No.
4,505,839.
[0093] The viscosity of the resulting polyalkanolamines (II) is
typically in the range from 1000 to 50 000 mPas, preferably from
2000 to 20 000 mPas and more preferably from 3000 to 13000 mPas
(each measured on the undiluted product at 20 degree C.).
[0094] The mean molar mass M.sub.n (number average) of the
resulting polyalkanolamines (II) is typically in the range from 250
to 50 000 g/mole, preferably from 500 to 40 000 g/mole, more
preferably from 1000 to 20 000 g/mole and most preferably from 1000
to 7500 g/mole.
[0095] The mean molar mass M.sub.w (weight average) of the
resulting polyalkanolamines (II) is typically in the range from 250
to 50 000 g/mole, preferably from 500 to 30 000 g/mole, more
preferably from 1000 to 20 000 g/mole.
[0096] The resulting polyalkanolamine (II) preferably has a
polydispersity (M.sub.w/M.sub.n) in the range of 1 to 10, and in
particular in the range of 1 to 5.
[0097] The polyalkanolamines (II) can optionally be alkoxylated in
a second stage (B). In this step, the OH groups and any secondary
amino groups present react with alkylene oxides to form terminal
polyether groups.
[0098] Polyalkanolamines (II) can optionally be functionalized in a
further reaction step (C). An additional functionalization can
serve to modify the properties of the polyalkanolamines (II). To
this end, the hydroxyl groups and/or amino groups present in the
polyalkanolamines (II) are converted by means of suitable agents
which are capable of reaction with hydroxyl groups and/or amino
groups. This forms functionalized polyalkanolamines (IV).
[0099] The alkoxylated polyalkanolamines (III) can optionally be
functionalized in a further reaction step (D). An additional
functionalization can serve to modify the properties of the
alkoxylated polyalkanolamines (III). To this end, the hydroxyl
groups and/or amino groups present in the alkoxylated
polyalkanolamines (III) are converted by means of suitable agents
which are capable of reaction with hydroxyl groups and/or amino
groups. This forms functionalized alkoxylated polyalkanolamines
(V).
[0100] In general, the total amount of leveling agents in the
electroplating bath is from 0.5 ppm to 10000 ppm based on the total
weight of the plating bath. The leveling agents according to the
present invention are typically used in a total amount of from
about 0.1 ppm to about 1000 ppm based on the total weight of the
plating bath and more typically from 1 to 100 ppm, although greater
or lesser amounts may be used. The electroplating baths according
to the present invention may include one or more optional
additives. Such optional additives include, but are not limited to,
accelerators, suppressors, surfactants and the like. Such
suppressors and accelerators are generally known in the art. It
will be clear to one skilled in the art which suppressors and/or
accelerators to use and in what amounts.
[0101] A large variety of additives may typically be used in the
bath to provide desired surface finishes for the Cu plated metal.
Usually more than one additive is used with each additive forming a
desired function. Advantageously, the electroplating baths may
contain one or more of accelerators, levelers, sources of halide
ions, grain refiners and mixtures thereof. Most preferably the
electroplating bath contains both, an accelerator and a leveler in
addition to the suppressor according to the present invention.
Other additives may also be suitably used in the present
electroplating baths.
[0102] The present invention is useful for depositing a metal
layer, particularly a copper layer, on a variety of substrates,
particularly those having submicron and variously sized apertures.
For example, the present invention is particularly suitable for
depositing copper on integrated circuit substrates, such as
semiconductor devices, with small diameter vias, trenches or other
apertures. In one embodiment, semiconductor devices are plated
according to the present invention. Such semiconductor devices
include, but are not limited to, wafers used in the manufacture of
integrated circuits.
[0103] The general process of copper electrodeposition on
semiconductor integrated circuit substrates is described with
respect to FIGS. 1 and 2 without restricting the invention
thereto.
[0104] FIG. 1a shows a dielectric substrate 1 seeded with a copper
layer 2a. With reference to FIG. 1b a copper layer 2' is deposited
onto the dielectric substrate 1 by electrodeposition. The trenches
2c of the substrate 1 are filled and an overplating of copper 2b,
also referred to as "overburden", is generated on top of the whole
structured substrate. During the process, after optional annealing,
the overburden of copper 2b is removed by chemical mechanical
planarization (CMP), as depicted in FIG. 1c.
[0105] A key aspect when filling the trenches 2c of the substrate 1
with copper by electrodeposition is to achieve a copper layer that
is free of defects, especially free of voids and seams. This can be
realized by initiating the copper growth at the bottom of the
trench with the copper growing up to the mouth of the trench while
suppressing copper growth at the sidewalls of the trench. This
manner of trench filling, the so-called super-filling or
bottom-up-filling, depicted in FIG. 2a, is sought to achieve by
adding certain additives to the plating bath: the accelerator and
the suppressor. It is a sensitive interplay between these two
additives that has to be carefully adjusted to obtain a trench
filling free of any defects.
[0106] Bottom-up-filling as shown in FIG. 2a can be achieved with
the accelerator preferably accumulating and adsorbing on the copper
bottom of the trench and thus boosting the copper growth 2''', and
with the suppressor adsorbing on the sidewalls of the trench
suppressing the copper growth 2''. Depending on the chemical
structure of the suppressor and thus on its suppressing ability,
the trench filling can proceed with variably shaped copper growth
fronts 2'''', depicted in FIGS. 2a to 2c. A perfectly working
suppressor with complete sidewall coverage and full sidewall growth
suppression 2'' is shown in FIG. 2a. In this case the growth front
2'''' is flat with solely growing bottom-up copper 2'''. A less
effective suppressor results in a copper growth front 2''''
depicted in FIG. 2b. Slight sidewall copper growth 2'' with
predominant bottom-up copper growth 2''' gives an overall U-shaped
growth front 2''''. A weak suppressor evolves a V-shaped growth
front 2'''' due to significant sidewall copper growth 2'', as
depicted in FIG. 2c. A V-shaped copper growth front 2''''
implicates a serious risk of void formation when the trench is
filled. With a perfectly conformal copper seeded trench the
U-shaped copper growth front 2'''' as shown in FIG. 2b might
provide satisfying trench filling. But since there is an increasing
seed overhang issue and/or convex-shaped features with further
shrinking feature sizes, as depicted in FIG. 3, there is a serious
risk of pinch-off void formation in the upper half of the trench
close to the opening if the suppressor does not completely avoid
sidewall copper growth 2''. The present invention provides a new
class of highly effective, strong suppressing agents that cope with
the seed overhang issue and provide defect free trench filling
despite a non-conformal copper seed.
[0107] The advantage of the invention is that suppressing agents
are provided that result in a extraordinarily pronounced bottom-up
fill copper growth while perfectly suppressing the sidewall copper
growth, both leading to a flat growth front and thus providing
defect free trench fill. The strong sidewall copper growth
suppression of the invention enables non-conformal copper seeded
features and/or convex-shaped features to be substantially void
free filled. Moreover the invention provides an overall homogeneous
bottom-up fill in neighboring features of dense feature areas.
[0108] Typically, substrates are electroplated by contacting the
substrate with the plating baths of the present invention. The
substrate typically functions as the cathode. The plating bath
contains an anode, which may be soluble or insoluble. Optionally,
cathode and anode may be separated by a membrane. Potential is
typically applied to the cathode. Sufficient current density is
applied and plating performed for a period of time sufficient to
deposit a metal layer, such as a copper layer, having a desired
thickness on the substrate. Suitable current densities include, but
are not limited to, the range of 1 to 250 mA/cm.sup.2. Typically,
the current density is in the range of 1 to 60 mA/cm.sup.2 when
used to deposit copper in the manufacture of integrated circuits.
The specific current density depends on the substrate to be plated,
the leveling agent selected and the like. Such current density
choice is within the abilities of those skilled in the art. The
applied current may be a direct current (DC), a pulse current (PC),
a pulse reverse current (PRC) or other suitable current.
[0109] In general, when the present invention is used to deposit
metal on a substrate such as a wafer used in the manufacture of an
integrated circuit, the plating baths are agitated during use. Any
suitable agitation method may be used with the present invention
and such methods are well-known in the art. Suitable agitation
methods include, but are not limited to, inert gas or air sparging,
work piece agitation, impingement and the like. Such methods are
known to those skilled in the art. When the present invention is
used to plate an integrated circuit substrate, such as a wafer, the
wafer may be rotated such as from 1 to 150 RPM and the plating
solution contacts the rotating wafer, such as by pumping or
spraying. In the alternative, the wafer need not be rotated where
the flow of the plating bath is sufficient to provide the desired
metal deposit.
[0110] Metal, particularly copper, is deposited in apertures
according to the present invention without substantially forming
voids within the metal deposit. By the term "without substantially
forming voids", it is meant that 95% of the plated apertures are
void-free. It is preferred that 98% of the plated apertures are
void-free, mostly preferred is that all plated apertures are
void-free.
[0111] While the process of the present invention has been
generally described with reference to semiconductor manufacture, it
will be appreciated that the present invention may be useful in any
electrolytic process where metal filled small features that are
substantially free of voids are desired. Such processes include
printed wiring board manufacture. For example, the present plating
baths may be useful for the plating of vias, pads or traces on a
printed wiring board, as well as for bump plating on wafers. Other
suitable processes include packaging and interconnect manufacture.
Accordingly, suitable substrates include lead frames,
interconnects, printed wiring boards, and the like.
[0112] Plating equipment for plating semiconductor substrates are
well known. Plating equipment comprises an electroplating tank
which holds Cu electrolyte and which is made of a suitable material
such as plastic or other material inert to the electrolytic plating
solution. The tank may be cylindrical, especially for wafer
plating. A cathode is horizontally disposed at the upper part of
tank and may be any type substrate such as a silicon wafer having
openings such as trenches and vias. The wafer substrate is
typically coated with a seed layer of Cu or other metal or a metal
containing layer to initiate plating thereon. A Cu seed layer may
be applied by chemical vapor deposition (CVD), physical vapor
deposition (PVD), or the like. An anode is also preferably circular
for wafer plating and is horizontally disposed at the lower part of
tank forming a space between the anode and cathode. The anode is
typically a soluble anode.
[0113] These bath additives are useful in combination with membrane
technology being developed by various tool manufacturers. In this
system, the anode may be isolated from the organic bath additives
by a membrane. The purpose of the separation of the anode and the
organic bath additives is to minimize the oxidation of the organic
bath additives.
[0114] The cathode substrate and anode are electrically connected
by wiring and, respectively, to a rectifier (power supply). The
cathode substrate for direct or pulse current has a net negative
charge so that Cu ions in the solution are reduced at the cathode
substrate forming plated Cu metal on the cathode surface. An
oxidation reaction takes place at the anode. The cathode and anode
may be horizontally or vertically disposed in the tank.
[0115] Metal, particularly copper, is deposited in apertures
according to the present invention without substantially forming
voids within the metal deposit. By the term "without substantially
forming voids", it is meant that 95% of the plated apertures are
void-free. It is preferred that the plated apertures are
void-free.
[0116] While the process of the present invention has been
generally described with reference to semiconductor manufacture, it
will be appreciated that the present invention may be useful in any
electrolytic process where a substantially void-free copper deposit
is desired. Accordingly, suitable substrates include lead frames,
interconnects, printed wiring boards, and the like.
[0117] All percent, ppm or comparable values refer to the weight
with respect to the total weight of the respective composition
except where otherwise indicated. All cited documents are
incorporated herein by reference.
[0118] The following examples shall further illustrate the present
invention without restricting the scope of this invention.
EXAMPLES
[0119] Six N-containing EO-PO copolymers have been synthesized by
polyalkoxylation of the respective N-containing starting molecules.
The compositions of suppressors 1-6 are given in Table 1.
TABLE-US-00001 TABLE 1 EO PO Fill Sup- Starter (number of number/
number/ arrange- perfor- pressor N atoms) starter starter ment
mance 1 Diethylenetriamine (3) 60 60 random + 2 Diethylenetriamine
(3) 120 120 random + 3 Diethylenetriamine (3) 180 180 random + 4
Triethylenetetraamine 120 120 random + (4) 5 Ethylenediamine (2)
120 120 random - (compar- ative example) 6 Diethylenetriamine 120
120 EO-PO - (compar- (3) block ative example)
[0120] The amine number was determined according to DIN 53176 by
titration of a solution of the polymer in acetic acid with
perchloric acid.
[0121] The molecular weight distribution d was determined by size
exclusion chromatography (GPC) with THF as eluent and using PSS SDV
columns as solid phase.
Example 1
Synthesis of Suppressor 1
[0122] Diethylenetriamine (389 g) and water (19.5 g) were placed
into a 2 L autoclave at 70.degree. C. After nitrogen neutralization
ethylene oxide (830 g) was added in portions at 90.degree. C. over
a period of 8 h 30 min. To complete the reaction, the mixture was
allowed to post-react for 3 h. Then the temperature was decreased
to 60.degree. C. and the mixture was stirred overnight. Then the
reaction mixture was stripped with nitrogen and volatile compounds
were removed in vacuo at 80.degree. C. A highly viscous light
yellow intermediate product (1240 g) having an amine number of 9.12
mmol/g was obtained.
[0123] The intermediate product (48.5 g) and aqueous potassium
hydroxide solution (concentration: 50 w % KOH; 1.45 g) were placed
into a 21 autoclave at 80.degree. C. After nitrogen neutralization
the solvent was removed for 2 h at 100.degree. C. under vacuo
(<10 mbar). Then the pressure was increased to 2 bar and a
mixture of ethylene oxide (330 g) and propylene oxide (479 g) was
added in portions at 140.degree. C. over a period of 10 h 30 min.
To complete the reaction, the mixture was allowed to post-react for
7 h at the same temperature. Then, the temperature was decreased to
60.degree. C. and the mixture was stirred overnight. Subsequently,
the reaction mixture was stripped with nitrogen and volatile
compounds were removed in vacuo at 80.degree. C. Suppressor 1 was
obtained as a light brown liquid (867 g) having an amine number of
0.527 mmol/g.
Example 2
Synthesis of Suppressor 2
[0124] For the synthesis of suppressor 2 suppressor 1 was used as a
starting material. Suppressor 1 (323 g) was placed into a 21
autoclave at 80.degree. C. After nitrogen neutralization the
solvent was removed for 20 min at 80-120.degree. C. under vacuo
(<10 mbar). Then the pressure was increased to 2 bar and a
mixture of ethylene oxide (158 g) and propylene oxide (207 g) was
added in portions at 140.degree. C. over a period of 7 h. To
complete the reaction, the mixture was allowed to post-react for 7
h at the same temperature. Then, the temperature was decreased to
60.degree. C. and the mixture was stirred over the weekend.
Subsequently, the reaction mixture was stripped with nitrogen and
volatile compounds were removed in vacuo at 80.degree. C.
Suppressor 2 was obtained as a light brown liquid (694 g) having an
amine number of 0.243 mmol/g. GPC: d =1.20.
Example 3
Synthesis of Suppressor 3
[0125] Diethylenetriamine (203 g) and water (10.1 g) were placed
into a 21 autoclave. After nitrogen neutralization ethylene oxide
(830 g) was added in portions at 90.degree. C. over a period of 5
h. To complete the reaction, the mixture was allowed to post-react
overnight. Then the reaction mixture was stripped with nitrogen and
volatile compounds were removed in vacuo at 100.degree. C. A highly
viscous light yellow intermediate product (631 g) having an OH
number of 852 mg KOH/g was obtained.
[0126] The intermediate product (20.0 g) was diluted in water (30
g) and this solution and aqueous potassium hydroxide solution
(concentration: 50 w % KOH; 0.60 g) were placed into a 2 L
autoclave. The solvent was removed at 120.degree. C. for 2 h under
vacuo (<10 mbar). After nitrogen neutralization the pressure was
increased to 2 bar and a mixture of ethylene oxide (477 g) and
propylene oxide (647 g) was added in portions at 140.degree. C. The
mixture was allowed to post-react overnight and, subsequently, the
reaction mixture was stripped with nitrogen. Then, Ambosol (33.6 g)
and Hyflow (2.2 g) were added and residual volatile components were
removed at 100.degree. C. and at <10 mbar for 2 h at the rotary
evaporator. After filtration Suppressor 3 was obtained as a yellow
liquid (1120 g). GPC: d=1.08; amine number: 0.16 mmol/g.
Example 4
Synthesis of Suppressor 4
[0127] Triethylenetetramine (509 g) and water (25.5 g) were placed
into a 5 l autoclave at 80.degree. C. After nitrogen neutralization
the pressure was increased to 2 bar and ethylene oxide (721 g) was
added in portions at 110.degree. C. over a period of 8 h 10 min. To
complete the reaction, the mixture was allowed to post-react for 6
h. Then the mixture was stirred at 80.degree. C. overnight and
subsequently stripped with nitrogen. After removal of volatile
compounds in vacuo at 80.degree. C. a highly viscous yellow
intermediate product (1220 g) having an amine number of 10.1 mmol/g
was obtained.
[0128] The intermediate product (38.8 g) was diluted in water (30
g) and this solution and aqueous potassium hydroxide solution
(concentration: 50 w % KOH; 0.60 g) were placed into a 2 L
autoclave. The solvent was removed at 120.degree. C. for 3 h under
vacuo (<10 mbar). After nitrogen neutralization the pressure was
increased to 2 bar and a mixture of ethylene oxide (432 g) and
propylene oxide (600 g) was added in portions at 140.degree. C. The
mixture was allowed to post-react overnight and, subsequently,
stripped with nitrogen. Residual volatile components were removed
at the rotary evaporator. Suppressor 4 was obtained as a yellow
liquid (1070 g). GPC: d=1.14; amine number: 0.37 mmol/g.
Example 5
Synthesis of Suppressor 5
[0129] Ethylenediamine (42.1 g) and water (8.4 g) were placed into
a 0.31 autoclave. After nitrogen neutralization the reaction
mixture was stirred at 80.degree. C. for 2 h. Then, ethylene oxide
(721 g) was added in portions at 80.degree. C. and the mixture was
allowed to post-react overnight. After stripping with nitrogen and
removal of volatile compounds in vacuo an intermediate product (166
g) was obtained.
[0130] The intermediate product (16.5 g) and aqueous potassium
hydroxide solution (concentration: 50 w % KOH; 3.4 g) were placed
into a 2 L autoclave. The solvent was removed at 90.degree. C. for
2 h under vacuo (<10 mbar). After nitrogen neutralization the
pressure was increased to 2.2 bar and a mixture of ethylene oxide
(357 g) and propylene oxide (487 g) was added in portions at
120.degree. C. The mixture was allowed to post-react at 120.degree.
C. for 4 h and, subsequently, at 80.degree. C. overnight. Residual
volatile components were removed at the rotary evaporator for 1 h
at 80.degree. C. Suppressor 5 was obtained as an orange liquid (847
g). GPC: d=1.10; amine number: 0.18 mmol/g.
Example 6
Synthesis of Suppressor 6
[0131] Diethylentriamine (382 g) and water (19.1 g) were placed
into a 2 L autoclave at 70.degree. C. After nitrogen neutralization
ethylene oxide (814 g) was added in portions at 90.degree. C. over
a period of 8 h. To complete the reaction, the mixture was allowed
to post-react for 3 h. Then the temperature was decreased to
60.degree. C. and the mixture was stirred overnight. Then the
reaction mixture was stripped with nitrogen and volatile compounds
were removed in vacuo at 80.degree. C. A highly viscous light
yellow intermediate product (1180 g) was obtained.
[0132] The intermediate product (79.7 g) and aqueous potassium
hydroxide solution (concentration: 40 w % KOH; 2.99 g) were placed
into a 2 L autoclave at 80.degree. C. After nitrogen neutralization
the solvent was removed for 2 h at 100.degree. C. under vacuo
(<10 mbar). Then the pressure was increased to 2 bar and
ethylene oxide (1266 g) was added in portions at 120.degree. C.
over a period of 11 h. To complete the reaction, the mixture was
allowed to post-react for 3 h at the same temperature. Then, the
temperature was decreased to 60.degree. C. and the mixture was
stirred overnight. Subsequently, the reaction mixture was stripped
with nitrogen and volatile compounds were removed in vacuo at
80.degree. C. A second intermediate product was obtained as a brown
solid (1366 g) having an amine number of 0.584 mmol/g.
[0133] The second intermediate product (311 g) was placed into a 2
L autoclave at 80.degree. C. After nitrogen neutralization the
solvent was removed for 1 h at 100.degree. C. under vacuo (<10
mbar). Then the pressure was increased to 2 bar and propylene oxide
(397 g) was added in portions at 140.degree. C. over a period of 4
h 10 min. To complete the reaction, the mixture was allowed to
post-react for 3 h at the same temperature. Then, the temperature
was decreased to 60.degree. C. and the mixture was stirred
overnight. Subsequently, the reaction mixture was stripped with
nitrogen and volatile compounds were removed in vacuo at 80.degree.
C. Suppressor 6 was obtained as a light brown liquid (705 g) having
an amine number of 0.258 mmol/g. GPC: d=1.47.
[0134] FIG. 3 shows the feature sizes of the copper seeded wafer
substrate that was used for electroplating with the different
plating baths described in the following sections. After copper
seed deposition the trenches had a width of 15.6 to 17.9 nanometer
at the trench opening, a width of 34.6 to 36.8 nanometer at half
height of the trench, and were 176.4 nanometer deep.
Example 7
[0135] A plating bath was prepared by combining DI water, 40 g/l
copper as copper sulfate, 10 g/l sulfuric acid, 0.050 g/l chloride
ion as HCl, 0.028 g/l of SPS and 3.00 ml/l of a 3.8 wt % solution
in DI water of suppressor 1 as prepared in example 1.
[0136] A copper layer was electroplated onto a wafer substrate with
feature sizes shown in FIG. 3 provided with a copper seed layer by
contacting the wafer substrate with the above described plating
bath at 25 degrees C. applying a direct current of -5 mA/cm.sup.2
for 3 s or 6 s respectively. The thus electroplated copper layer
was investigated by scanning electron micrograph (SEM)
inspection.
[0137] The results are shown in FIGS. 4a and 4b which provide SEM
images of the copper filled trenches. The neighboring trenches are
almost equally filled without exhibiting voids or seams. The SEM
image after 6 s plating, depicted in FIG. 4b, shows compared to the
3 s plating result (FIG. 4a) no significant copper deposition over
the dielectric between the neighboring trenches but copper growth
in the trenches.
Example 8
[0138] A plating bath was prepared by combining DI water, 40 g/l
copper as copper sulfate, 10 g/l sulfuric acid, 0.050 g/l chloride
ion as HCl, 0.028 g/l of SPS and 2.00 ml/l of a 5.3 wt % solution
in DI water of suppressor 2 as prepared in example 2.
[0139] A copper layer was electroplated onto a wafer substrate with
feature sizes shown in FIG.
[0140] 3 provided with a copper seed layer by contacting the wafer
substrate with the above described plating bath at 25 degrees C.
applying a direct current of -5 mA/cm.sup.2 for 3 s. The thus
electroplated copper layer was investigated by SEM inspection.
[0141] The result is shown in FIG. 5 providing the SEM image of
partly filled trenches exhibiting the bottom-up filling with almost
no copper deposition on the sidewall of the trenches. The
neighboring trenches are almost equally filled without exhibiting
voids or seams. The strong suppressing effect on the trench
sidewalls can be clearly seen since the small feature openings are
still obvious and did not close while filling the trenches. During
the 3 s plating there was no significant amount of copper deposited
at the trench sidewalls close to the opening thus avoiding
formation of pinch-off voids.
Example 9
[0142] A plating bath was prepared by combining DI water, 40 g/l
copper as copper sulfate, 10 g/l sulfuric acid, 0.050 g/l chloride
ion as HCl, 0.028 g/l of SPS, and 7.00 ml/l of a 5.3 wt % solution
in DI water of suppressor 3 as prepared in example 3.
[0143] A copper layer was electroplated onto a wafer substrate with
feature sizes shown in FIG. 3 provided with a copper seed layer by
contacting the wafer substrate with the above described plating
bath at 25 degrees C. applying a direct current of -5 mA/cm.sup.2
for 3 s. The thus electroplated copper layer was investigated by
SEM inspection.
[0144] FIG. 6 shows the SEM image of the resulting electroplated
copper layer. The trenches are partly filled without voids or
seams, and a flat copper growth front in the trenches can be seen
clearly indicating the bottom-up filling. The copper deposition on
the sidewalls of the trenches is negligible small showing the
strong suppression of the copper growth at the sidewalls of the
trenches. All feature openings are still open.
Example 10
[0145] A plating bath was prepared by combining DI water, 40 g/l
copper as copper sulfate, 10 g/l sulfuric acid, 0.050 g/l chloride
ion as HCl, 0.028 g/l of SPS, and 5.00 ml/l of a 5.0 wt % solution
in DI water of suppressor 4 as prepared in example 4.
[0146] A copper layer was electroplated onto a wafer substrate with
feature sizes shown in FIG. 3 provided with a copper seed layer by
contacting the wafer substrate with the above described plating
bath at 25 degrees C. applying a direct current of -5 mA/cm.sup.2
for 3 s or 6 s, respectively. The thus electroplated copper layer
was investigated by SEM inspection.
[0147] The result is shown in FIGS. 7a and 7b which exhibit a SEM
image of the almost filled trenches after 3 s (FIG. 7a) as well as
of the fully filled trenches after 6 s (FIG. 7b). Both figs. show
neighboring trenches that are almost equally filled with copper
without exhibiting voids or seams. Comparing the 6 s plating result
(FIG. 7b) to the result after 3 s plating (FIG. 7a) no significant
copper deposition over the dielectric between the neighboring
trenches occurred but copper growth within the trenches.
Comparative Example 11
[0148] A plating bath was prepared by combining DI water, 40 g/l
copper as copper sulfate, 10 g/l sulfuric acid, 0.050 g/l chloride
ion as HCl, 0.028 g/l of SPS, and 5.00 ml/l of a 5.0 wt % solution
in DI water of suppressor 5 as prepared in example 5.
[0149] A copper layer was electroplated onto a wafer substrate with
feature sizes shown in FIG. 3 provided with a copper seed layer by
contacting the wafer substrate with the above described plating
bath at 25 degrees C. applying a direct current of -5 mA/cm.sup.2
for 3 s. The thus electroplated copper layer was investigated by
SEM inspection.
[0150] The resulting SEM image is shown in FIG. 8 which exhibits
neighboring trenches that are unequally partly filled with copper.
The trenches do not exhibit a flat and well-defined growth front
parallel to the trench bottom but a diffuse growth front indicating
that copper was significantly deposited on the sidewalls of the
trenches. Some trenches are already closed due to the sidewall
copper growth resulting in voids. In this example the copper
deposition is slower compared to examples 7-10.
Comparative Example 12
[0151] A plating bath was prepared by combining DI water, 40 g/l
copper as copper sulfate, 10 g/l sulfuric acid, 0.050 g/l chloride
ion as HCl, 0.028 g/l of SPS, and 5.00 m1/I of a 5.0 wt % solution
in DI water of suppressor 6 as prepared in example 6.
[0152] A copper layer was electroplated onto a wafer substrate with
feature sizes shown in FIG. 3 provided with a copper seed layer by
contacting the wafer substrate with the above described plating
bath at 25 degrees C. applying a direct current of -5 mA/cm.sup.2
for 3 s. The thus electroplated copper layer was investigated by
SEM inspection.
[0153] The resulting SEM image is shown in FIG. 9 which exhibits
neighboring trenches that are unequally partly filled with copper.
The trenches do not exhibit a flat and well-defined growth front
parallel to the trench bottom but a growth front distributed over
the whole surface of the trenches indicated by the slit-shaped
wholes in the trenches. Several trenches are already closed at the
openings of the trenches due to significant sidewall copper growth
resulting in void formation. In this example the copper deposition
is slower compared to examples 7-10.
* * * * *