Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
2002-06-25
2003-07-29
Webb, Gregory E. (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
For cleaning a specific substrate or removing a specific...
C510S176000, C510S178000
Reexamination Certificate
active
06599870
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to chemical formulations used in semiconductor wafer fabrication and particularly to chemical formulations, including at least boric acid and one or more organic amines and water, that are utilized to remove residue from wafers following a resist plasma ashing step.
2. Description of the Prior Art
The prior art teaches the utilization of various chemical formulations to remove residue and clean wafers following a photoresist ashing step. Generally, these prior art chemical formulations include strong reagents such as strong acids or strong bases to help remove unwanted inorganic residues. However, such strong reagents can cause unwanted further removal of metal or insulator layers remaining on the wafer and are therefore undesirable in many instances. There is therefore a need for chemical formulations which effectively remove residue following a resist ashing step which do not attack and potentially degrade delicate structures which are meant to remain on a wafer.
SUMMARY OF THE INVENTION
The present invention comprises formulations for stripping wafer residues which originate from a halogen based plasma metal etching followed by oxygen plasma ashing. The formulations contain the following general components (percentages are by weight):
Boric Acid
2-17%
Organic amine or mixture of amines
35-70%
Water
20-45%
Glycol solvent (optional)
0-5%
Chelating agent (optional)
0-17%
The preferred amines are:
Monoethanolamine (MEA)
Triethanolamine (TEA)
It is an advantage of the present invention that it effectively removes inorganic residues following a plasma ashing step.
It is another advantage of the present invention that it effectively removes metal halide and metal oxide residues following plasma ashing.
It is a further advantage of the present invention that it effectively removes inorganic residue from a semiconductor wafer following plasma ashing without containing a strong acid or a strong base.
These and other features and advantages of the present invention will become understood to those of ordinary skill in the art upon review of the following detailed description of the preferred embodiments.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Typical steps in the fabrication of semiconductor wafers involve the creation of metalized layers or insulating layers having patterned resist layers formed thereon. Such a wafer may then be exposed to plasmas (such as halogen based plasmas) to remove exposed metal or insulator. Thereafter, a plasma ashing step is conducted (typically using an oxygen based plasma) in which the remaining resist is removed from the wafer. The result is a patterned metal layer or a patterned insulator layer.
This series of steps generally results in a residue which must be removed from the wafer prior to further fabrication steps. The residue following the plasma ashing step is predominantly composed of inorganic compounds such as metal halides and metal oxides.
Various chemical formulations are currently used to remove the inorganic compound residues. These formulations are generally holdovers from older semiconductor fabrication wet chemical resist removal processes that were used prior to the introduction of the resist plasma ashing technology. The prior formulations thus typically contain strong acids or strong bases to remove residues. The present invention comprises chemical formulations for the removal of inorganic compound residues, where the formulations do not contain the strong acids or strong bases of the prior art formulations.
The present invention comprises new formulations for stripping wafer residues which originate from high density plasma metal etching followed by plasma ashing. The formulations contain boric acid, one or more amines and water or another solvent as primary ingredients with a glycol solvent and/or a chelating agent as optional ingredients.
The preferred formulations utilize the following general components percentages are by weight):
Boric Acid
2-17%
Organic amine or mixture of amines
35-70%
Water
20-45%
Glycol solvent (optional)
0-5%
Chelating agent (optional)
0-17%
The preferred amines are:
Monoethanolamine (MEA)
Triethanolamine (TEA)
The utilization of boric acid in combination with amines is a unique feature of this invention. These formulations provided good stripping performance which can be enhanced by the addition of optional chelating agents and solvents.
The chelating agents are preferably weakly to moderately acidic and contain combinations of two functional groups which include carboxylic acids, aromatic hydroxyl groups, amides, ketones, and aldehydes such that the two groups in the chelating agent are in close proximity to each other.
Preferred chelating agents are:
Catechol
C
6
H
4
(OH)
2
Lactic acid
CH
3
CH(OH)CO
2
H
Other acceptable chelating agents are:
Acetoacetamide
CH
3
COCH
2
CONH
2
Salicylaldehyde
2-(HO)C
6
H
4
CHO
Examples of preferred formulations are:
Boric acid
17%
Monoethanolamine
45%
Water
32%
Catechol
6%
Boric acid
15%
Monoethanolamine
43%
Water
34.8%
Lactic acid
6.2%
Boric acid
10%
Triethanolamine
38%
Water
35%
Acetoacetamide
17%
Boric acid
15%
Monoethanolamine
35%
Water
35%
Salicylaldehyde
15%
Boric acid
15%
Monoethanolamine
40%
Water
45%
Boric acid
12%
Monoethanolamine
45%
Triethanolamine
10%
Water
33%
Boric acid
17%
Monoethanolamine
40%
Water
38%
Ethylene Glycol
5%
The inventors expect that other closely related ingredients would be expected to show comparable performance to those utilized in the preferred formulations.
These include:
A. Other organic amines are expected to be suitable:
B. Other glycol solvents are expected to be suitable.
C. Other chelating agents which are also weakly to moderately acidic and are structurally similar to those claimed are also expected to be suitable.
D. It would also be expected that inclusion of optional components such as surfactants, stabilizers, corrosion inhibitors, buffering agents, and cosolvents would constitute obvious additions to those practiced in the art.
The formulations of the present invention are particularly useful on wafers which have been etched with chlorine- or fluorine-containing plasmas followed by oxygen plasma ashing. The residues generated by this type of processing typically contain inorganic materials such as, but not limited to, aluminum oxide and titanium oxide. These residues are often difficult to dissolve completely without causing corrosion of metal and titanium nitride features required for effective device performance.
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Guan George
Nguyen Long
Wojtczak William A.
Advanced Technology & Materials Inc.
Chappuis Margaret
Hultquist Steven J.
Webb Gregory E.
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