Aqueous phosphoric acid compositions for cleaning semiconductor devices
First Claim
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1. An aqueous semiconductor cleaning solution comprising:
- at least about 75% by weight water;
from about 0.5% to about 10% by weight phosphoric acid;
at least one alkaline compound selected from the group consisting of;
a quaternary ammonium hydroxide;
a hydroxylamine derivative having the structural formula;
wherein R3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and
wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C4-C7 ring; and
a mixture thereof; and
optionally one or more other acid compounds, one or more fluoride-containing compounds, and/or one or more alkanolamines having the structural formula;
wherein R1, R1′
, R2, R2′
, and R3 are, independently in each case, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms;
wherein Z is a group having the formula -(-Q-CR1R1′
-CR2R2′
-)m-, such that m is a whole number from 0 to 3 (i.e., when m=0, there is no atom between the -CR2 R2′
- group and the -OR3 group in the formula above), R1, R1′
, R2, and R2′
+0'"'"'MAY be independently defined in each repeat unit, if m>
1, within the parameters set forth for these moieties above, and Q may be independently defined in each repeat unit, if m>
1, each Q being independently either -O- or -NR3-; and
wherein X and Y are, independently in each case, hydrogen, a C1-C7 linear, branched, or cyclic hydrocarbon, or a group having the formula -CR1R1′
-CR2 R2′
-Z-F, with F being either -O-R3 or -NR3R4, where R4 is defined similarly to R1, R1′
, R2, R2′
, and R3 above and with Z, R1, R1′
, R2, R2′
, and R3 defined as above, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C4-C7 ring.
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Abstract
The present invention relates to dilute aqueous solutions containing phosphoric acid and methods for cleaning plasma etch residue from semiconductor substrates including such dilute aqueous solutions. The solution according to the invention may advantageous contain an alkaline compound, one or more other acid compounds, and/or a fluoride-containing compound and may optionally contain additional components such as organic solvents, chelating agents, amines, and/or surfactants.
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Citations
31 Claims
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1. An aqueous semiconductor cleaning solution comprising:
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at least about 75% by weight water;
from about 0.5% to about 10% by weight phosphoric acid;
at least one alkaline compound selected from the group consisting of;
a quaternary ammonium hydroxide;
a hydroxylamine derivative having the structural formula;
wherein R3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and
wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C4-C7 ring; and
a mixture thereof; and
optionally one or more other acid compounds, one or more fluoride-containing compounds, and/or one or more alkanolamines having the structural formula;
wherein R1, R1′
, R2, R2′
, and R3 are, independently in each case, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms;
wherein Z is a group having the formula -(-Q-CR1R1′
-CR2R2′
-)m-, such that m is a whole number from 0 to 3 (i.e., when m=0, there is no atom between the -CR2 R2′
- group and the -OR3 group in the formula above), R1, R1′
, R2, and R2′
+0'"'"'MAY be independently defined in each repeat unit, if m>
1, within the parameters set forth for these moieties above, and Q may be independently defined in each repeat unit, if m>
1, each Q being independently either -O- or -NR3-; and
wherein X and Y are, independently in each case, hydrogen, a C1-C7 linear, branched, or cyclic hydrocarbon, or a group having the formula -CR1R1′
-CR2 R2′
-Z-F, with F being either -O-R3 or -NR3R4, where R4 is defined similarly to R1, R1′
, R2, R2′
, and R3 above and with Z, R1, R1′
, R2, R2′
, and R3 defined as above, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C4-C7 ring. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23)
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24. A dilute aqueous cleaner and residue remover comprising:
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water, optionally in a mixture with one or more polar organic solvents, wherein the water is present at least about 75% by weight;
phosphoric acid or salt thereof, present in an amount from about 0.1% to about 6% by weight of 85% phosphoric acid;
optionally, a quaternary ammonium compound, present in the solution in an amount from about 0.2% to about 5% by weight;
optionally, a hydroxylamine derivative, present in the solution in an amount from about 0. 1% to about 5 % by weight not including the counterion of the hydroxylamine derivative salt, if present;
optionally, an alkanolamine, present in the solution in an amount from about 0.2% to about 5% by weight;
optionally, a fluoride-containing compound, present in the solution in an amount from about 0.001% to about 0.5 % by weight;
optionally, an other acid compound, present in the solution in an amount from about 0.05% to about 6% by weight;
optionally, a chelating agent, present in the solution in an amount from about 0. 1% to about 8% by weight;
optionally, a surfactant, present in the solution in an amount from about 0.01% to about 3% by weight.
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25. A dilute aqueous cleaner and residue remover consisting essentially of:
- about 1.5% to about 2.5% by weight of phosphoric acid;
about 0.5% to about 1% by weight of a hydroxylamine derivative, preferably hydroxylamine; and
about 0.005% to about 0.04% by weight of a fluoride-containing compound, preferably ammonium bifluoride.
- about 1.5% to about 2.5% by weight of phosphoric acid;
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26. A dilute aqueous cleaner and residue remover consisting essentially of:
- about 1.5% to about 2.5% by weight of phosphoric acid;
about 0.5% to about 1% by weight of a hydroxylamine derivative;
about 0.005% to about 0.04% by weight of a fluoride-containing compound; and
about 0.05% to about 0.2% by weight of a surfactant.
- about 1.5% to about 2.5% by weight of phosphoric acid;
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27. A dilute aqueous cleaner and residue remover consisting essentially of:
- about 1.5% to about 2.5% by weight of phosphoric acid;
about 0.5% to about 1% by weight of a hydroxylamine derivative, preferably hydroxylamine; and
about 0.005% to about 0.1% by weight of a fluoride-containing compound, preferably ammonium fluoride.
- about 1.5% to about 2.5% by weight of phosphoric acid;
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28. A dilute aqueous cleaner and residue remover consisting essentially of:
- about 1.5% to about 2.5% by weight of phosphoric acid;
about 0.5% to about 1% by weight of a hydroxylamine derivative;
about 0.005% to about 0.1 % by weight of a fluoride-containing compound; and
about 5% to about 15% by weight of a polar organic solvent.
- about 1.5% to about 2.5% by weight of phosphoric acid;
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29. A dilute aqueous cleaner and residue remover consisting essentially of:
- about 1.5% to about 2.5% by weight of phosphoric acid; and
about 0.5% to about 1.5% by weight of a quaternary ammonium salt.
- about 1.5% to about 2.5% by weight of phosphoric acid; and
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30. A dilute aqueous cleaner and residue remover consisting essentially of:
- about 1.5% to about 4% by weight of 85% phosphoric acid;
about 0.3% to about 4% by weight of oxalic acid dihydrate;
about 0.3% to about 4% by weight of a monofunctional organic acid;
about 90% to about 99% by weight of water; and
optionally between about 0.1% and about 1% of a chelator, wherein the formulation contains substantially no organic solvents and SARA 3 hazardous compounds.
- about 1.5% to about 4% by weight of 85% phosphoric acid;
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31. A dilute aqueous cleaner and residue remover consisting essentially of:
- optionally about 0.5% to about 6% by weight of 85% phosphoric acid;
about 2% to about 12% by weight of oxalic acid dihydrate;
optionally about 0.2% to about 15% by weight of a monofunctional organic acid;
optionally between about 0.05% and 1.5% by weight of ammonium hydroxide, an alkyl ammonium hydroxide substituted with 2 or 3 alkyl moieties independently selected from methyl and ethyl moieties, or a mixture thereof;
optionally between about 0.1% and about 1% of a chelator; and
water wherein the formulation contains substantially no organic solvents and SARA 3 hazardous compounds.
- optionally about 0.5% to about 6% by weight of 85% phosphoric acid;
Specification