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IIIHIIIHIHIIIHIIIH USOO5217586A
United States Patent (19) 11) Patent Number: 5,217,586
Datta et al. 45) Date of Patent: Jun. 8, 1993
54 ELECTROCHEMICAL TOOL FOR Primary Examiner-Donald R. Valentine
UNIFORM METAL REMOVAL DURING Attorney, Agent, or Firm-Scully, Scott, Murphy &
ELECTROPOLISHING Presser
75) Inventors: Madhav Datta, Yorktown Heights; 57 ABSTRACT
by Bri, Briarcliff The present invention relates to an electropolishing tool
s O. N. Y. for the removal of metal from a workpiece, said electro
73) Assignee: International Business Machines polishing tool comprising a container means for retain
Corporation, Armonk, N.Y. ing an electrolytic solution, a cathode assembly in the
21) Appl. No.: 819,298 shape of a pyramid the height of which is adjustable, a
power supply means including a negative terminal and
(22 Filed: Jan. 9, 1992 a positive terminal with said negative terminal being
51) Int. C.’............................ C25F 3/16; C25F 7/00 electrically connectable to said cathode assembly, a
52 U.S. C. .............................. 204/129.6; 204/129.9; plate means for holding the workpiece and for forming
204/129.95; 204/224 M an electrical connection to the workpiece, said plate
58 Field of Search ...................... 204/129.55, 129.65, means connected to the positive terminal of said power
204/224M, 129.9, 129.95, 129.6 supply means, and an enclosure means placed over the
(56) References Cited workpiece leaving only the surface of the workpiece
which is to be polished exposed to the electrolytic solu
U.S. PATENT DOCUMENTS tion such that when the workpiece is secured to said
2,868,705 1/1959 Baier et al. ....................... 204/140.5 plate means and said cathode assembly is connected to
3,240,685 2/1962 Maissel ......... ... 204/129.5X the negative terminal of said power supply means and is
3,325,384 6/1967 Frantzen ........................ 20/129.55 placed over the said enclosure means directly facing the
3,713,998 1/1973 Kenney .......................... 204/224 M
4,127,459 11/1978 Juner ...........
4,247,377 1/1981 Eckler et al. .....
,
..... 204/129.65
workpiece enclosed therein, that portion of the work
piece exposed to the electrolytic solution undergoes
4.303482 12/1981 Bihne et al... 204/1296.5x electropolishing.
4,548,685 10/1985 Suemitsu et al. .................... 204/146
4,882,019 11/1989 Lewy ............................... 204/129.1 20 Claims, 1 Drawing Sheet
U.S. Patent June 8, 1993 5,217,586

40
 5,217,586
1 2
solution, and a filtered DC power source. Depending
ELECTROCHEMICAL TOOL FOR UNIFORM upon the application, however, the electropolishing
METAL REMOVAL DURING process may or may not involve pumping of the electro
ELECTROPOLISHING lyte. Although pumping is required to remove reaction
TECHNICAL FIELD
products from the surfaces of the anode and cathode, in
some cases pumping of the electrolyte may introduce
The present invention relates to an electrochemical hydrodynamic instabilities which in turn may lead to
tool to be used for the removal of thin film metal during localized non-uniform metal dissolution. In the majority
the process of electropolishing. More particularly, the 10
of applications found in the literature, electropolishing
present invention describes an apparatus and technique has been used for the finishing of large parts where
for uniform metal removal during the planarization of a non-uniformities up to the levels of microns have not
double layer metallurgy (DLM) structure by electro been a matter of concern. Consequently, the pumping of
polishing. The present invention is applicable to the the electrolyte has been effectively used as a means of
planarization of multilayer copper interconnection for enhancing reaction product removal in the electropol
thin film modules of varying sizes and shapes. The metal 15 ishing process.
is electrochemically etched from a substrate as part of a In accordance with the most accepted theory behind
manufacturing procedure for multilayer thin film wir the process of electropolishing, the high points of the
ling. metal surface are those which are most readily oxidized
PRIOR ART 20 as the electric current density is higher at the projec
The process of micromilling is a well documented tions located on the specimen. In a relatively short
conventional method used for the mechanical polishing amount of time, the oxidized material is then thereupon
of various workpieces. Although the process of mi dissolved in the electrolyte or otherwise removed from
cromilling is presently being employed for the planari the surface, resulting in the disappearance of any irregu
zation of DLM structures, it has several disadvantages 25 larities which had existed on the surface. In any event,
which are associated with its use. To begin with, prob the selective solution of the high points of the metal
lems exist relating to the alignment and the levelling of surface tend to produce a smooth finish which is compa
the parts to be micromilled. Secondly, induced stresses rable or superior to the mechanically buffed surface
created by the process lead to problems of cracking and afforded by the micromilling technique. It is also noted
delamination of the workpiece. In addition, there exists 30 that all mechanical methods of polishing, including
the possibility of the contamination of the dielectric those used for metallographic samples, produce a thin
layer with copper due to the smearing action which surface layer of work-hardened metal. Electropolish
takes place during the process of micromilling. Further ing, on the other hand, provides a stain-free surface
more, the micromilling technique involves high capital which is especially suitable for obtaining microscopi
investment while the operation itself is labor intensive 35 cally flat surfaces.
with potential yield problems. Going back to the theory behind the process, it is
An alternate cost effective planarization technique to believed that in the anodic treatment of metals, a vis
that of micromilling is the method of electropolishing. cous layer or film of high electrical resistivity is formed
Electropolishing is a technique which can produce on the surface of the anode being treated during the
smooth surfaces on a variety of metals through the use passage of current through the electrolyte. Because the
of electrochemical means. Copper and its alloys, stain electrolyte is of comparatively low electrical resistance,
less steel, steel, brass, aluminum, silver, nickel chro the formation of a layer of comparatively high resis
mium, zinc, gold and many other alloys may be electro tance on the anode surface causes the anodic potential
polished. Electropolishing as a means of metallographic in the different regions of the surface being treated to
specimen preparation is a process that has been gaining 45 vary according to the extent to which these regions
increasing acceptance due to a number of distinct ad project into said layer. This in turn causes the salient
vantages which the process has over mechanical polish points on the surface of the specimen to fuse at a rate
ing. These advantages include the rapidity at which the according to their depth, thereby levelling off said
workpiece or specimen may be polished, the elimination points until an equipotential condition is attained over
of cold-worked surfaces, the ultimate flatness of the
polished area and the fact that the electropolishing step the surface. It is at this latter stage that the surface of the
can often be accomplished in one and the same opera workpiece will be levelled and smoothed off.
tion with an etching step. In addition, as stated above, There are a number of variables in the process of
the process of electropolishing can be applied to a wide electrolytic polishing. They include current density (or
variety of metals and alloys. 55 voltage), time, temperature and choice of electrolyte.
Electropolishing relates to the art of electrolytically The determination of these parameters require actual
treating metal to clean, level, smooth, polish and/or laboratory tests. The optimum parameters for a particu
protect the surface thereof. Through the use of electro lar process will depend a great deal on the metal which
lytic action, the process of electropolishing removes is to be electropolished. For example, a wide variety of
minute projections and irregularities on the surface of a 60 electrolytes may be used for the electropolishing pro
specimen. Essentially, electropolishing is the reverse of cess per se. Highly concentrated solutions of sulfuric
the process of electroplating. In the vast majority of and/or phosphoric and/or chromic acids are used fre
electroplating processes, metal (and hydrogen) are de quently for electropolishing. A typical electrolyte for
posited on the cathode and dissolved from the anode. In stainless steel contains phosphoric acid and butyl alco
electropolishing, on the other hand, the workpiece is 65 hol. Phosphoric acid based electrolytes can also be
made the anode and tends to be dissolved. Electropol effectively used for the electropolishing of copper (see
ishing equipment usually consists of a polishing cell W. J. McTegart, "The Electrolytic And Chemical Pol
which contains a circulating pump and the electrolytic ishing Of Metals', Pergamon Press, London (1956)).
 5,217,586
3 4.
For various examples of the electropolishing process, FIG. 2b is a side view of the cathode assembly of
see U.S. Pat. Nos. 2,868,705; 4,127,459; and 4,882,019. FIG. 2a.
Although these references involve the conventional FIG.2c is a side view of the cathode assembly of the
process of electropolishing, they are related to methods tool of the subject invention having a conically-shaped
and apparatus for polishing large parts. By choosing a 5 configuration to form the pyramid-like structure.
suitable electrolyte and electrochemical parameters, the DETAILED DESCRIPTION OF THE
skilled artisan can obtain high speed metal removal PREFERRED EMBODIMENT OF THE
from a surface to provide a microfinished surface. How INVENTION
ever, in order for the process of electropolishing to be
effectively employed in thin film planarization work, a 10 Electropolishing is the anodic removal of metal from
particular concern has to be the non-uniform removal of a workpiece and involves the generation of metalions at
metal which may occur during the process. the surface thereof. The reaction can be represented by
SUMMARY OF THE INVENTION the following equation:
The present invention relates to an electropolishing 15 MM2 r
tool for the removal of metal from a workpiece, said
electropolishing tool comprising a container means for As the current is increased, the rate of metalion genera
retaining an electrolytic solution; a cathode assembly tion increases. These metal ions are then transported
having a pyramid-like form or shape, the height of from the anodic surface of the workpiece into the bulk
which is adjustable; a power supply means including a 20 electrolyte. In electrochemical systems, transport pro
negative terminal and a positive terminal, said negative cesses involve migration, diffusion and convection.
terminal being electrically connectable to said cathode When dealing with a strong electrolyte, the migration
assembly; a plate means for holding the workpiece and and convection effects are negligible at the anodic sur
for forming an electrical connection to the workpiece, face. Consequently, electropolishing takes place under
said plate means connected to the positive terminal of 25 conditions when the metal dissolution reaction is diffu
said power supply means; and an enclosure means sion controlled. That is, the transport of the material
placed over the workpiece leaving only the surface of under these conditions mainly takes place by diffusion.
the workpiece which is to be polished exposed to the This "mass transport" takes place such that a concentra
electrolytic solution such that when the workpiece is tion gradient of metal ions occur near the anodic sur
secured to said plate means and said cathode assembly is 30 face. This layer is known as the diffusion layer. The
connected to the negative terminal of said power supply electropolishing occurs under conditions when the
means and said cathode assembly is placed opposite the metal dissolution process reaches its limiting value (due
said enclosure means directly facing the workpiece to the exceeding of the solubility limit) such that a salt
enclosed therein, that portion of the workpiece exposed film is formed.
to the electrolytic solution undergoes electropolishing. 35 The tool and the method of the present invention
The present invention also relates to a method for involves the electropolishing of thin films in which
electropolishing of a workpiece comprising the steps of uniformity is desired at the micron level. This requires
mounting a workpiece on a plate means in a container making sure that a viscous layer of uniform thickness is
filled with a stationary electrolytic solution; positioning present at the surface as the formation of a uniformly
a cathode assembly opposite to and facing towards the 40 distributed surface film over the workpiece is a key
workpiece, the cathode assembly being in the shape of factor to obtaining uniform metal removal during elec
pyramid the height of which is adjustable; making the tropolishing. Besides the ability to form a uniform vis
sample and said cathode assembly respectively an anode cous layer, other key factors which determine the uni
and cathode in an electrical circuit; placing an enclosure formity of metal removal during the process of electro
means over the workpiece leaving only the surface of 45 polishing include maintaining a uniform solution com
the workpiece which is to be polished exposed to the position as well as solution resistance. In a parallel plate
electrolytic solution; and continuously conducting an electrolytic cell, the metal dissolution at the edges of a
electric current through the electrical circuit under workpiece is much higher than at the center due to the
conditions effective to electropolish the surface of the lack of uniformity of the above-mentioned parameters.
workpiece. It is also important to note that during the process of
The present invention employs two preferred varia electropolishing and depending upon the chosen operat
tions of the cathode assembly. In the first embodiment, ing conditions, hydrogen gas evolves at the cathode
the cathode assembly consists of rings or plates that are while oxygen gas may evolve at the anode. Under the
fixed one above the other to form the pyramid-like work conditions employed by the present invention (i.e.
shape described above. In the second embodiment, the 55 current ranging from 5 to 10 Amps), oxygen gas evolu
cathode assembly is comprised of a conically-shaped tion is at a minimum. This not only ensures high metal
structure. In addition, two methods are described for removal efficiency but also minimizes instabilities at the
determining the end-point of the electropolishing pro surface due to oxygen bubbles that may grow and de
cess for planarization. tach thus causing hydrodynamic instabilities due to
60 bubble dynamics. In a similar fashion, interference from
BRIEF DESCRIPTION OF THE DRAWINGS
the evolution of hydrogen gas at the cathode also needs
FIG. 1 is a schematic drawing of the electrochemical to be eliminated. By positioning the cathode assembly
tool of the subject invention for the uniform removal of above the anode sample, any hydrogen bubbles formed
metal during the electropolishing process. will move upwards through the electrolyte and not
FIG.2a is a bottom view of the cathode assembly of 65 disturb the sample positioned below it. Also, using a
the tool of the subject invention consisting of plates that cathode assembly in the form of a pyramid allows for
are fixed one above the other to form a pyramid-like the easy escape of any hydrogen gas and minimizes the
shape. disturbance of the stable hydrodynamic situation.
 5,217,586
5 6
In the electropolishing tool of the present invention, present invention employs conditions which result in
variations in these parameters at the surface of the the uniform metal removal over the entire workpiece,
workpiece can be minimized or eliminated altogether. the end point can be easily determined by coulometry.
Metal dissolution uniformity is achieved by the present The coulometric method may involve electropolishing
invention through the use of a cathode assembly of the up to a point at which 0.5 to 1 micron of copper is left
shape of a pyramid the height of which can be adjusted which can then be removed by "kiss polishing' (very
and through the use of an enclosure over the workpiece short duration mechanical or chemical-mechanical pol
to ensure the establishment of stationary conditions and ishing.
to minimize current concentration at the edges. A second method in determining the endpoint of
FIG. 1 schematically shows the electropolishing tool 10 electropolishing for planarization is to tailor the bath
of the present invention. It consists of a container means chemistry to include small concentrations of nitric acid
(10) which is filled with the electrolyte (12). Workpiece such that the last layers of copper can be removed after
(22) is fixed on a plate means (14) connected to the current stoppage by chemical etching.
positive terminal of a power supply means. An enclo The following example is provided to further illus
sure means (16) is properly placed over the workpiece 15 trate the present invention.
(22) such that only the surface that is to be planarized is EXAMPLE
exposed to the electrolyte (12). The electrolyte (12)
within the enclosures means (16) is stationary. This 5 inch diameter silicon wafers plated with 20 micron
particular arrangement achieves three goals. First, the thick copper were electropolished using the electropol
hydrodynamic instabilities at the dissolving anode are 20 ishing tool of the present invention. The thickness of the
minimized. Second, the current concentration at the plated material before and after electropolishing was
edges of the workpiece are also minimized and third, determined by a four point probe, i.e. an instrument
the arrangement described hereinabove ensures the which measures thickness by measuring the effective
formation of a viscous layer. A vent (20) is also present resistance of the material. Through the use of this
for the escape of gases which may form during the 25 method, uniformity of metal removal by electropolish
electropolishing method. ing was determined. Constant current experiments were
The cathode assembly (18) shown in FIG. 1 is placed performed using concentrated phosphoric acid as the
opposite the enclosure means (16) directly facing the electrolyte and current ranging between about 5 and
workpiece (14). The cathode assembly (18) consists of about 40 Amps (or current density ranging between
rings or plates (30) that are fixed one above the other as 30 about 40 and about 320 mA/cm2). Operating at low
shown in FIGS. 2a and 2b. This type of pyramid struc currents resulted in better uniformity and better current
ture compensates for possible current concentration at efficiency for metal dissolution. At high currents, oxy
the edges. As illustrated in FIG. 2c, another embodi gen evolution occurred simultaneously with metal dis
ment of the cathode assembly may be in the form of a solution. Consequently, current efficiency for metal
circular cone (40). The rings and/or plates or circular 35 removal at high currents was significantly low. Opti
cone should be constructed of a material which is sub mum results were obtained at a current from about 5 to
stantially corrosion resistant to the electrolyte and about 10 Amps (or at a current density from about 40 to
which will not be damaged by the electrolyte. For a about 80 mA/cm2).
phosphoric acid electrolyte, stainless steel and nickel The time of operation at a given current can easily be
are preferable materials. The size and the number of 40 estimated from Faraday's Law, which for a given mate
rings/plates required to get optimum results can be rial and operating conditions, varies linearly with the
determined experimentally or can be determined by thickness of the metal to be dissolved. Cell voltage
mathematical modeling. One being of ordinary skill in during constant current operation depended on the
the art would appreciate that the size of the rings/plates concentration of the electrolyte (i.e., its conductivity)
will depend on the size of the workpiece being polished. 45 and the anode-cathode spacing. It was found that con
The thickness of the rings will depend on the current centrated phosphoric acid (85%) was preferable as
distribution as determined by the properties of the elec lower concentrations of acid resulted in the evolution of
trolyte being used, i.e. concentration, conductivity, etc., more oxygen under otherwise similar conditions.
and the metal dissolution reaction rate at different loca With respect to the cathode assembly, ring thickness
tions of the sample. Generally, the cathode assembly 50 of one inch each and three rings of different diameters
made of rings or plates will consist of two to six rings or (5 inches, 3 inches and 1 inch) were used and the cath
plates, of uniform thickness and decreasing diameter. ode-anode separation was maintained at a minimum of 3
The container means, the plate means and the enclo inches. It should be noted that a relatively larger anode
sure means can be constructed of PVC as this material cathode distance is not desirable as it would require
can withstand acids very well, is less expensive than 55 higher cell voltage and consequently higher power
other materials, and is easy to machine. However, simi consumption. A very small interelectrode spacing, on
lar materials can be used such as teflon, glass, PVDF, the other hand, will lead to interferences from anodic
and the like. and cathodic reaction products. The stack of rings was
The present invention is useful for the electropolish later replaced by a circular cone cathode assembly
ing of thin films of almost any material that is electri 60 which was two inches in height and had a five inch
cally conducting (including conducting ceramics). The diameter. One skilled in the art will understand that the
electrochemical tool described herein is ideal to obtain dimensions of the cone will vary according to the sam
uniform current distribution during the planarization of ple size. It was found that the circular cone cathode
multilayer copper interconnection for thin film modules assembly was easier to install and resulted in better
of varying sizes and shapes. For such an application, 65 uniformity. It also helped in the easy escape of hydro
two different methods may be easily employed for the gen gas bubbles which were generated at the cathode.
determination of the end-point of the electropolishing While the invention has been particularly shown and
for planarization. As the electrochemical tool of the described with respect to a preferred embodiment
 5,217,586
7 8
thereof, it will be understood by those skilled in the art 8. The electropolishing tool of claim 6 wherein said
that the foregoing and other changes in form and details circular cone cathode assembly is made of nickel.
may be made therein without departing from the spirit 9. The electropolishing tool of claim 1 wherein said
and scope of the invention. container means, said plate means and said enclosures
Having thus described our invention, what we claim means are made of PVC.
as new, and desire to secure by Letters Patent is: 10. The electropolishing tool of claim 1 wherein said
1. An electropolishing tool for the removal of metal container means is made of glass.
from a workpiece, said electropolishing tool compris 11. A method for electropolishing a workpiece con
ing: prising the steps of:
a container means for retaining an electrolytic solu O mounting a workpiece on a plate means in a container
tion; filled with an electrolytic solution;
a cathode assembly positionable within said container positioning a cathode assembly over and facing
means, said cathode assembly being in the form of towards the workpiece, the cathode assembly
a pyramid shape the height of which is adjustable; being in the shape of a pyramid, the height of
a power supply means including a negative terminal 15. which is adjustable;
and a positive terminal, said negative terminal making the sample and said cathode assembly respec
being electrically connectable to said cathode as tively an anode and cathode in an electrical circuit;
sembly; positioning an enclosure means within said container
a plate means for holding the workpiece and for means such that only the surface of the workpiece
forming an electrical connection to the workpiece, 20 which is to be polished is exposed to the electro
said plate means connected to the positive terminal lytic solution, said electrolytic solution contained
of said power supply means; and in said enclosure means remaining stationary dur
an enclosure means positioned within said container ing the electropolishing method; and
means, said enclosure means adapted to enclose continuously conducting an electric current through
said workpiece and to contain a portion of electro 25 the electrical circuit under conditions effective to
lyte solution to be placed in said container means electropolish the surface of the workpiece exposed
such that only the surface of the workpiece to be to the electrolytic solution.
polished will be exposed to electrolytic solution 12. A method according to claim 11 wherein the
when said solution is placed in said container electrolytic solution comprises phosphoric acid.
means and said electrolytic solution when con 30 13. A method according to claim 12 wherein the
tained in said enclosure means remains stationary phosphoric acid electrolytic solution is 85% phosphoric
during operation of said tool, and such that said acid.
cathode assembly is positioned to directly face the 14. A method according to claim 11 wherein the
workpiece when enclosed in said enclosure means. current density ranges from about 40 to about 320
2. The electropolishing tool according to claim 1 35 mA/cm2.
wherein said cathode assembly consists of rings or 15. A method according to claim 11 wherein the
plates that are fixed one above the other to form a current density ranges from about 40 to about 80
pyramid shape the height of which is adjustable. mA/cm2.
3. The electropolishing tool according to claim 2 16. A method according to claim 11 wherein the
wherein the rings or plates are made of stainless steel. cathode assembly consists of rings or plates that are
4. The electropolishing tool according to claim 2 fixed one above the other to form a pyramid shape.
wherein the rings or plates are made of nickel. 17. A method according to claim 16 wherein the
5. The electropolishing tool according to claim 2 cathode assembly consists of two to six rings or plates of
wherein the cathode assembly consists of two to six uniform thickness and decreasing diameter.
rings, of uniform thickness and decreasing diameter. 45 18. A method according to claim 11 wherein the
6. The electropolishing tool according to claim 1 cathode assembly is in the form of a circular cone.
wherein said cathode assembly is in the form of a circu 19. A method according to claim 11 wherein the
lar cone. workpiece is a thin film module.
7. The electropolishing tool of claim 6 wherein said 20. A method according to claim 11 wherein the
circular cone cathode assembly is made of stainless 50 workpiece is a double layer metallurgy structure.
steel.

55

65
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5, 217,586
DATED : June 8 lSO)3
NVENTORS) : Madhav Datta et al.
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby
corrected as shown below:

Column 4 line lb : " M-> M2t --Xr "

should read -- M --> M2t + Ze --

Signed and Sealed this

Third Day of May, 1994

At est: (a team
BRUCE LEHMAN

Attesting Officer Commissioner of Patents and Trademarks

 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5, 217,586
DATED : June 8 lSO)3
NVENTORS) : Madhav Datta et al.
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby
corrected as shown below:

Column 4 line lb : " M-> M2t --Xr "

should read -- M --> M2t + Ze --

Signed and Sealed this

Third Day of May, 1994

At est: (a team
BRUCE LEHMAN

Attesting Officer Commissioner of Patents and Trademarks

 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5, 217,586
DATED : June 8 lSO)3
NVENTORS) : Madhav Datta et al.
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby
corrected as shown below:

Column 4 line lb : " M-> M2t --Xr "

should read -- M --> M2t + Ze --

Signed and Sealed this

Third Day of May, 1994

At est: (a team
BRUCE LEHMAN

Attesting Officer Commissioner of Patents and Trademarks