U.S. patent application number 12/230293 was filed with the patent office on 2009-03-12 for apparatus and method for removing photoresist from a substrate.
Invention is credited to Sangjun Choi, Donggyun Han, Woosung Han, Changki Hong, Hyungho Ko, Hyosan Lee.
Application Number | 20090065032 12/230293 |
Document ID | / |
Family ID | 33536298 |
Filed Date | 2009-03-12 |
United States Patent
Application |
20090065032 |
Kind Code |
A1 |
Han; Donggyun ; et
al. |
March 12, 2009 |
Apparatus and method for removing photoresist from a substrate
Abstract
An apparatus and method for removing photoresist from a
substrate, which includes treating the photoresist with a first
reactant to cause swelling, cracking or delamination of the
photoresist, treating the photoresist with a second reactant to
chemically alter the photoresist, and subsequently removing the
chemically altered photoresist with a third reactant. In one
example, the first reactant is supercritical carbon dioxide
(SCCO.sub.2), the second reactant is ozone vapor, and the third
reactant is deionized water.
Inventors: |
Han; Donggyun; (Yongin-si,
KR) ; Han; Woosung; (Seoul, KR) ; Hong;
Changki; (Seongnam-si, KR) ; Choi; Sangjun;
(Seoul, KR) ; Ko; Hyungho; (Seoul, KR) ;
Lee; Hyosan; (Suwon-si, KR) |
Correspondence
Address: |
HARNESS, DICKEY & PIERCE, P.L.C.
P.O. BOX 8910
RESTON
VA
20195
US
|
Family ID: |
33536298 |
Appl. No.: |
12/230293 |
Filed: |
August 27, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10712775 |
Nov 14, 2003 |
7431855 |
|
|
12230293 |
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Current U.S.
Class: |
134/61 |
Current CPC
Class: |
H01L 21/02043 20130101;
H01L 21/31138 20130101; Y10S 438/906 20130101 |
Class at
Publication: |
134/61 |
International
Class: |
B32B 38/10 20060101
B32B038/10 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 26, 2003 |
KR |
2003-0042133 |
Claims
1.-30. (canceled)
31. An apparatus for removing photoresist from a substrate,
comprising: at least one chamber for treating the photoresist with
a first reactant to cause swelling, cracking or delamination of the
photoresist, for treating the photoresist with a second reactant to
chemically alter the photoresist, for rinsing the substrate, for
drying the substrate and for holding the substrate; and transfer
means for transferring the substrate between chambers.
32. The apparatus of claim 31, said apparatus including a single
chamber for treating the photoresist with the first reactant to
cause swelling, cracking or delamination of the photoresist, and
for treating the photoresist with the second reactant to chemically
alter the photoresist.
33. The apparatus of claim 31, said apparatus including a separate
chamber for treating the photoresist with the first reactant to
cause swelling, cracking or delamination of the photoresist, and
for treating the photoresist with the second reactant to chemically
alter the photoresist.
34. The apparatus of claim 31, said apparatus including a separate
chamber for each operation.
35. The apparatus of claim 31, said transfer means including a
robotic arm.
36. The apparatus of claim 31, wherein the photoresist is formed by
ion implantation.
37. The apparatus of claim 36, wherein the ion implantation was
performed at a dose of 3.times.10.sup.15 ions/cm.sup.2 or
higher.
38. The apparatus of claim 31, wherein the first reactant is
supercritical carbon dioxide (SCCO.sub.2).
39. The apparatus of claim 38, wherein the supercritical carbon
dioxide (SCCO.sub.2) is at a temperature of 100-150.degree. C. and
a pressure of 150-200 bar.
40. The apparatus of claim 31, wherein the second reactant is an
ozone-based reactant.
41. The apparatus of claim 40, wherein the ozone-based reactant is
ozone vapor.
42. The apparatus of claim 41, wherein the ozone vapor is at a
temperature of 105-115.degree. C. and a pressure of 60-80 kPa.
43. The apparatus of claim 41, wherein the concentration of the
ozone in an ozone generator is 90,000 ppm or greater.
44. The apparatus of claim 31, wherein the rinse is a deionized
water rinse.
45. The apparatus of claim 31, wherein the first reactant is
supercritical carbon dioxide (SCCO.sub.2) and the second reactant
is ozone, said single chamber including a heater jacket, a carbon
dioxide (CO.sub.2) source, a supercritical carbon dioxide
(SCCO.sub.2) generator, a supercritical carbon dioxide (SCCO.sub.2)
circulator, a carbon dioxide (CO.sub.2) feedback, an ozone gas
generator, a vapor generator, and an exhaust.
46. The apparatus of claim 45, wherein the supercritical carbon
dioxide (SCCO.sub.2) generator includes a carbon dioxide (CO.sub.2)
pressure pump and a carbon dioxide (CO.sub.2) heater.
47. The apparatus of claim 31, wherein the first reactant is
supercritical carbon dioxide (SCCO.sub.2) and a first of the
separate chambers includes a heater jacket, a carbon dioxide
(CO.sub.2) source, a supercritical carbon dioxide (SCCO.sub.2)
generator, a supercritical carbon dioxide (SCCO.sub.2) circulator,
and a carbon dioxide (CO.sub.2) feedback.
48. The apparatus of claim 47, wherein the supercritical carbon
dioxide (SCCO.sub.2) generator includes a carbon dioxide (CO.sub.2)
pressure pump and a carbon dioxide (CO.sub.2) heater.
49. The apparatus of claim 47, wherein the second reactant is an
ozone-based reactant, and a first of the separate chambers includes
a heater jacket, an ozone gas generator, a vapor generator, and an
exhaust.
50. The apparatus of claim 49, wherein the ozone-based reactant is
ozone vapor.
Description
BACKGROUND OF THE INVENTION
[0001] Photoresist is an organic polymer which becomes soluble when
exposed to light. Photoresist is used in many applications within
various industries, such as the semiconductor, biomedical
engineering, holographic, electronics, and nanofabrication
industries. As an example, photoresist is used to help define
circuit patterns during chip fabrication in the semiconductor
industry. The use of photoresist prevents etching or plating in the
area the photoresist covers (this is also know as resist).
[0002] The removal of photoresist, commonly known as "stripping" is
preceded by plasma ashing, etching, or other manufacturing steps.
These steps can degrade or carbonize the photoresist and leave a
photoresist reside that is difficult to remove by current stripping
methods. In particular, ion implantation with a dose of
3.times.10.sup.15 ions/cm.sup.2 or higher creates a photoresist
exhibiting a hard outer crust covering a soft core. FIG. 1A
illustrates a cross-sectional view and FIG. 1B illustrates a top
view of a photoresist exhibiting a hard outer crust 40' caused by
ion implantation. As illustrated in FIGS. 1A and 1B, the hard outer
40' crust may be on the order of 200 to 300 .ANG. thick.
[0003] FIG. 2 is a cross-sectional view illustrating the ion
implantation step. FIG. 2 illustrates a substrate 110, a gate
electrode 10, an insulation film 11, and n-region of a source/drain
region 20, a spacer 30, a photoresist pattern 40, and a well 50.
When the photoresist pattern 40 is exposed to ion implantation 45,
a hard outer crust 40' is formed on the photoresist pattern 40.
[0004] Residue may also be a problem. FIG. 3A illustrates a
cross-section view and FIG. 3B illustrates a top view of a
photoresist exhibiting residue after an etching process or a
chemical mechanical polishing (CMP) process. FIG. 3A illustrates a
substrate 110, an etched player 60, a photoresist pattern 70, and a
hard outer crust 70', which is formed when the photoresist pattern
70 is exposed to ion implantation 75, FIGS. 3A and 3B illustrate
residue 80 and an organic defect 90.
[0005] Conventionally, photoresist has been removed by a plasma
ashing process followed by a stripping process. The plasma ashing
process utilizes O.sub.2 plasma which may cause damage to the
sublayer and thereby degrade the electrical performance of the
underlying semiconductor device. The stripping process requires
high quantities of toxic and/or corrosive chemicals to remove
photoreactive polymers or photoresist from chip surfaces.
[0006] In order to overcome these problems, other stripping methods
have been developed including organic and/or inorganic stripping
solvents with supercritical carbon dioxide (SCCO.sub.2) or ozone
(O.sub.3) gas. Techniques which remove resist using SCCO.sub.2
utilize a densified CO.sub.2 cleaning composition which includes
CO.sub.2 and at least one cosolvent such as a surfactant, alcohol,
or amine. However, the methods utilizing SCCO.sub.2 and a cosolvent
are incapable of dissolving a hard outer crust of a photoresist
caused by ion implantation.
[0007] A second method for removing photoresist or other organic
material from a substrate such as a semiconductor wafer includes
partially immersing the substrate in a solvent, for example,
deionized water, in a reaction chamber, injecting an oxidizing gas,
for example, ozone, into the reaction chamber and rotating or
otherwise moving the substrate through the solvent to coat a thick
film of solvent over the organic component on the substrate surface
and expose the solvent-coated component to the ozone gas to remove
the organic material from the surface. Again, the resist removal
techniques utilizing ozone are incapable of dissolving a hard outer
crust caused by an ion implantation step. FIG. 4 illustrates a
failure of a resist removal techniques using ozone to remove a hard
outer crust of the photoresist caused by ion implantation with a
dose of 3.times.10.sup.15 ions/cm.sup.2 or higher.
SUMMARY OF THE INVENTION
[0008] In exemplary embodiments, the present invention is directed
to a method of removing photoresist from a substrate, which
includes treating the photoresist with a first reactant to cause
swelling, cracking or delamination of the photoresist, treating the
photoresist with a second reactant to chemically alter the
photoresist, and subsequently removing the chemically altered
photoresist with a third reactant.
[0009] In exemplary embodiments, the present invention is directed
to a method of removing photoresist from a substrate, which
includes treating the photoresist with supercritical carbon dioxide
(SCCO.sub.2), treating the photoresist with an ozone-based
reactant, and removing the photoresist with deionized water.
[0010] In exemplary embodiments, the present invention is directed
to a method of removing photoresist from a substrate, which
includes loading the substrate into a chamber, injecting a first
reactant into the chamber and converting the first reactant to
supercritical condition, maintaining contact between the substrate
and the supercritical first reactant, depressurizing the chamber,
injecting a second reactant into the chamber, maintaining contact
between the substrate and the second reactant, purging the chamber
and unloading the substrate, removing the photoresist, and drying
the substrate.
[0011] In exemplary embodiments, the present invention is directed
to an apparatus for removing photoresist from a substrate, which
includes at least one chamber for treating the photoresist with a
first reactant to cause swelling, cracking or delamination of the
photoresist, for treating the photoresist with a second reactant to
chemically alter the photoresist, for rinsing the substrate, for
drying the substrate and for holding the substrate and a transfer
device for transferring the substrate between chambers.
[0012] In exemplary embodiments, the present invention may also be
used to remove normal photoresist in addition to the hard outer
crust. Still further, exemplary embodiments of the present
invention do not damage the underlying photoresist. Still further,
exemplary embodiments of the present invention do not use organic
contaminants or leave an organic residue.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The present invention will become more fully understood from
the detailed description given below and the accompanying drawings,
which are given for purposes of illustration only, and thus do not
limit the invention.
[0014] FIG. 1A illustrates a cross-sectional view and FIG. 1B
illustrates a top view of a photoresist exhibiting a hard outer
crust 40' caused by ion implantation.
[0015] FIG. 2 is a cross-sectional view illustrating a conventional
ion implantation step.
[0016] FIG. 3A illustrates a cross-section view and FIG. 3B
illustrates a top view of a photoresist exhibiting residue after a
conventional etching process or a conventional chemical mechanical
polishing (CMP) process.
[0017] FIG. 4 illustrates the failure of conventional resist
removal techniques using ozone to remove a hard outer crust of the
photoresist caused by ion implantation with a dose of
3.times.10.sup.15 ions/cm.sup.2 or higher.
[0018] FIG. 5 illustrates an apparatus for removing photoresist
from a substrate in accordance with an exemplary embodiment of the
present invention.
[0019] FIG. 6 illustrates an SCCO.sub.2 treatment chamber of FIG. 1
and associated elements in accordance with an exemplary embodiment
of the present invention.
[0020] FIG. 7 illustrates the ozone vapor treatment chamber of FIG.
5 in an exemplary embodiment of the present invention.
[0021] FIG. 8A illustrates a flow chart of an exemplary method of
the present invention and FIG. 8B illustrates an exemplary pressure
versus time graph for the flowchart of FIG. 8A.
[0022] FIG. 9A illustrates a flow chart of an exemplary embodiment
of the present invention taking place in a monolithic chamber and
FIG. 9B illustrates the corresponding pressure versus time
plot.
[0023] FIG. 10 illustrates a phase diagram for CO.sub.2,
illustrating the pressure versus temperature region at which
CO.sub.2 becomes supercritical.
[0024] FIG. 11 illustrates a method of the present invention in
accordance with another exemplary embodiment.
DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS
[0025] FIG. 5 illustrates an apparatus for removing photoresist
from a substrate in accordance with an exemplary embodiment of the
present invention. As illustrated in FIG. 5, the apparatus includes
at least one chamber 100. At least one substrate is provided in at
least one chamber 100. The substrate 110 may be provided via a
cassette 120. The apparatus may also include a transfer chamber
200, an SCCO.sub.2 treatment chamber 300, an ozone vapor treatment
chamber 400, a rinse (or bath) chamber 500, and drying chamber 600.
The substrate 110 may be moved from chambers 100 to 600 via a
mechanical or electromechanical device, such as robotic arm
210.
[0026] FIG. 6 illustrates the SCCO.sub.2 treatment chamber 300 of
FIG. 5 and associated elements in accordance with an exemplary
embodiment of the present invention. FIG. 6 illustrates the
SCCO.sub.2 treatment chamber 300, a wafer plate 301, a heater
jacket 305, a CO.sub.2 cylinder 310, a CO.sub.2 inlet conduit 312,
a CO.sub.2 pressure pump 314, and a CO.sub.2 heater 316. FIG. 6
also illustrates an SCCO.sub.2 generator 317, one or more CO.sub.2
control valves 318, 328, 338, 348, an exhausted CO.sub.2 reservoir
320, an exhausted CO.sub.2 outlet conduit 322, a circulation
conduit 332, a circulation pump 334, and a CO.sub.2 return 342.
[0027] FIG. 7 illustrates the ozone vapor treatment chamber 400 of
FIG. 5 in an exemplary embodiment of the present invention. FIG. 7
illustrates the ozone vapor treatment chamber 400, a wafer plate
401, a heater jacket 405, an ozone gas generator 410, an ozone gas
inlet conduit 412, and an ozone control valve 418. FIG. 7 further
illustrates a vapor generator 420, a vapor inlet conduit 422, and a
vapor control valve 428. The ozone vapor treatment chamber 400
further includes an exhausted gas reservoir 430, an exhausted gas
outlet conduit 432, and an exhausted gas control valve 438.
[0028] FIG. 8A illustrates a flow chart of an exemplary method of
the present invention and FIG. 8B illustrates a pressure versus
time graph for the flowchart of FIG. 8A. At step 42, a substrate
110 is loaded in the SCCO.sub.2 treatment chamber 300. At step 44,
CO.sub.2 is injected into the SCCO.sub.2 treatment chamber 300 and
CO.sub.2 is converted to SCCO.sub.2. At step 46, the SCCO.sub.2 is
maintained in contact with the substrate 110. At step 48, the
SCCO.sub.2 treatment chamber 300 is depressurized and the wafer 110
is removed. At step 50, the substrate 110 is loaded into the ozone
vapor treatment chamber 400 and at step 50, ozone vapor is injected
into the ozone vapor treatment 400 under desired conditions. At
step 54, the ozone vapor is maintained in contact with the
substrate 110. In step 56, the ozone vapor chamber 400 is purged
and the substrate 110 is removed. At step 58, the substrate 110 is
moved to a rinse or bath chamber 500 for rinsing and at step 60,
the substrate 110 is moved to the drying chamber 600 for
drying.
[0029] Although FIG. 5 of the present application illustrates a
multi-chamber apparatus, the teachings of the present invention may
also be applied to a monolithic chamber apparatus.
[0030] FIG. 9A illustrates a flow chart of an exemplary embodiment
of the present invention taking place in a monolithic chamber and
FIG. 9B illustrates the corresponding pressure versus time
plot.
[0031] As shown in FIG. 9A, in step 62, the substrate 110 is loaded
into the monolithic chamber. In step 64, CO.sub.2 is injected into
the monolithic chamber and converted to SCCO.sub.2. At step 66, the
SCCO.sub.2 is maintained in contact with the substrate 110. At step
68, the monolithic chamber is depressurized and at step 70, ozone
vapor is injected. At step 72, the ozone vapor is maintained in
contact with the substrate 110 and in step 74, the monolithic
chamber is purged and the substrate 110 is unloaded. Subsequently,
as indicated in step 76 and 78, the substrate 110 may be rinsed and
dried outside the monolithic chamber.
[0032] FIG. 10 illustrates a phase diagram for CO.sub.2,
illustrating the pressure versus temperature region at which
CO.sub.2 becomes supercritical.
[0033] FIG. 11 illustrates a method of the present invention in
accordance with another exemplary embodiment. As illustrated at
step 802, a substrate 110 is placed in the pressure chamber. At
step 804, the pressure chamber is sealed. At step 806, the pressure
chamber is pressurized with CO.sub.2 and at step 808, the CO.sub.2
is converted to SCCO.sub.2 by increasing the pressure and
temperature. For CO.sub.2 to become critical, the pressure must be
above 73 bar and the temperature above 31.degree. C., as
illustrated in FIG. 10. At step 810, the SCCO.sub.2 is maintained
in contact with the substrate 110. Step 810 causes swelling,
cracking and/or delamination of the photoresist on the substrate
110. In an exemplary embodiment, the temperature is maintained
about 100.degree. C. and the pressure is maintained about 150 bar.
At step 812, the chamber is depressurized to normal atmospheric
pressure and vented. At step 814, the substrate 110 is transferred
to a second pressure chamber and at step 816 that pressure chamber
is sealed. At step 818, the second pressure chamber is pressurized
to elevated pressure. In an exemplary embodiment, the pressure is
above 60 kPa.
[0034] Further, at step 818, ozone gas and water vapor are provided
at elevated temperature. In an exemplary embodiment, the ozone gas
is provided at a temperature of about 105.degree. C. and water
vapor is provided at a temperature of about 115.degree. C. At step
820, the reaction is maintained until the photoresist is converted
into a water-soluble product and at step 822, the second chamber is
depressurized to normal atmosphere and vented. At step 824, the
substrate is rinsed and the water-soluble product removed.
[0035] An exemplary embodiment of the method of the present
invention includes three steps. The first step is a treatment with
a first reactant, to cause swelling, cracking, or delamination of a
photoresist, the second step is treatment with a second reactant to
chemically alter the photoresist, and the third step is removing
the chemically altered photoresist with a third reactant. In an
exemplary embodiment, the first reactant is SCCO.sub.2, the second
reactant is an ozone-based reactant, and the third reactant is
deionized water. In other exemplary embodiments, the ozone-based
reactant is ozone vapor, in another exemplary embodiment, highly
concentrated ozone vapor. In other exemplary embodiments, the ozone
vapor has a concentration equal to or greater than 90,000 ppm. In
other exemplary embodiments, the ozone-based reactant is ozone gas
mixed with water vapor
[0036] Another exemplary embodiment of the method of the present
invention includes three steps. The first step is a treatment with
SCCO.sub.2, the second step is treatment with an ozone-based
reactant, and the third step is a rinsing step. For each of these
three steps, exemplary process conditions may be maintained. With
respect to the SCCO.sub.2 treatment step, the temperature within
the chamber may be maintained between 100 and 150.degree. C. and
the pressure between 150 and 200 bars. With respect to the highly
saturated ozone vapor treatment statement, the temperature of the
chamber may be maintained at 105.degree. C. and the temperature of
the vapor at 115.degree. C. In an exemplary embodiment, a
temperature gap between the chamber and the vapor is in the range
of about 10.degree. C. to 15.degree. C. and a pressure gap is
between 60 kPa and 80 kPa. It is noted that a pressure higher than
80 kPa may be maintained, as long as proper safety precautions are
observed. With respect to the concentration of the ozone gas, in an
exemplary embodiment, the concentration is 90,000 ppm or greater at
the ozone generator.
[0037] It is noted that the arrangement of the apparatuses
illustrated in FIGS. 5-7 is exemplary, and could be modified, to
add, replace, or delete elements, as would be known to one of
ordinary skill in the art. It is further noted that the methods
illustrated in FIGS. 8A, 9A, and 11 are also exemplary, and various
steps could be added, replaced, or deleted, as would also be known
to one of ordinary skill in the art.
[0038] The invention being thus described, it will be obvious that
the same may be varied in many ways. Such variations are not to be
regarded as a departure from the spirit and scope of the invention,
and all such modifications as would be obvious to one skilled in
the art are intended to be included within the scope of the
following claims.
* * * * *