Nanoelectronic and microelectronic cleaning compositions
View Patent ↗Nanoelectronic and microelectronic cleaning corn positions for cleaning nanoelectronic and microelectronic substrates under supercritical fluid state conditions, and particularly cleaning compositions useful with and having improved compatibility with nanoelectronic and microelectronic substrates characterized by silicon dioxide, sensitive low-n or high-K dielectrics and copper, tungsten, tantalum, nickel, gold, cobalt, palladium, platinum, chromium, ruthenium, rhodium, iridium, hafnium, titanium, molybdenum, tin and other metallization, as well as substrates of A1 or Al(Cu) metallizations and advanced interconnect technologies, are provided by nanoelectronic and microelectronic cleaning compositions.
1. A cleaning composition suitable for cleaning nanoelectronic and microelectronic substrates under supercritical fluid conditions, said composition comprising (1) a supercritical main fluid reaching a supercritical fluid state at a temperature of 250° C. or less and a pressure of 600 bars or less (592.2 atm, 8702.3 psi), and (2) as a secondary fluid, a modifier formulation selected from the group consisting of following formulations:
a) a formulation comprising:
an oxidizing agent;
a polar organic solvent selected from the group consisting of sulfones, sulfolenes, and selenones;
an alkaline base of the formula R 4 N + OH − wherein each R is independently a substituted or unsubstituted alkyl group of 1 to 22 carbon atoms:
water; and
q chelating or metal complexing agent selected from the group consisting of trans-1,2-cyclohexanediamine tetraacetic acid (CyDTA), ethylenediamine tetraacetic acid (EDTA), stannates, pyrophosphates, ethane-1-hydroxy-1,1-diphosphonate, ethylenediamine tetra(methylene phosphonic acid) (EDTMP), diethylenetriamine penta(methylene phosphonic acid), and triethylenetetramine hexa(methylene phosphonic acid);
and optionally one or more of the following components:
an acid;
a corrosion-inhibiting co-solvent;
an oxidizer stabilizing agent;
a corrosion-inhibiting agent;
a metal corrosion inhibitor;
a fluoride compound; and
a surfactant;
b) a silicate free formulation comprising:
a polar organic solvent selected from the group consisting of sulfones, sulfolenes and selenones; and
a strong alkaline base of the formula R 4 N + OH − wherein each R is independently a substituted or unsubstituted alkyl group of 1 to 22 carbon atoms;
water; and
q chelating or metal complexinq agent selected from the group consisting of trans-1,2-cyclohexanediamine tetraacetic acid (CyDTA), ethylenediamine tetraacetic acid (EDTA), stannates, pyrophosphates, ethane-1-hydroxy-1,1-diphosphonate, ethylenediamine tetra(methylene phosphonic acid) (EDTMP), diethylenetriamine penta(methylene phosphonic acid), and triethylenetetramine hexa(methylene phosphonic acid);
and optionally one or more of the following components:
an acid;
a corrosion-inhibiting co-solvent;
an oxidizer stabilizing agent;
a corrosion-inhibiting agent;
a metal corrosion inhibitor;
a fluoride compound; and
a surfactant;
c) a formulation comprising:
one or more non-ammonium producing strong base of the formula [(R) 4 N +] p [X − g ], where each R is independently a substituted or unsubstituted alkyl of from 1 to 22 carbon atoms; and X=OH or a suitable salt anion, and p and q are equal and are integer of from 1 to 3;
one or more corrosion inhibiting solvent compounds, said corrosion inhibiting solvent compound having at least two sites capable of complexing with metals and selected from the group consisting of ethylene glycol, diethylene glycol, glycerol, diethylene glycol dimethyl ether, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 4-(2-hydroxyethyl)morpholine, 2-(methylamino)ethanol, 2-amino-2-methyl-1-propanol, 1-amino-2-propanol, 2-(2-aminoethoxy)-ethanol, N-(2-hydroxyethyl) acetamide, N-(2-hydroxyethyl) succinimide and 3-(diethylamino)-1,2-propanediol;
and optionally one or more of the following components:
water or other organic co-solvent;
a steric hindered amine or alkanolamine;
an organic or inorganic acid;
an other metal corrosion inhibitor compounds;
a surfactant;
a metal ion free silicate compound;
a metal chelating agent; and
a fluoride compound;
d) a formulation comprising:
one or more non-ammonium producing, non-HF producing fluoride salt of the formula (R) 4 N + F 31 , where each R is independently a substituted or unsubstituted alkyl of from 1 to 22 carbon atoms;
sulfolane, dimethyl sulfoxide and 1-(2-hydroxyethyl)-2- pyrrolidinone as organic solvents;
and optionally one or more of the following components:
a metal corrosion inhibiting solvent;
a steric hindered amine or alkanolamine;
an organic or inorganic acid; from about 0 to 40% by weight of an other metal corrosion inhibitor compound;
a surfactant;
a metal ion free silicate compound; and from about 0 to 5% by weight of a metal chelating agent; and
e) a formulation comprising:
one or more non-ammonium producing strong base of the formula [(R) 4 N + ] p [X − g ], where each R is independently a substituted or unsubstituted alkyl of from 1 to 22; carbon atoms; and X=OH or a suitable salt anion, and p and g are equal and are integer of from 1 to 3;
one or more steric hindered amide, solvents selected from the group consisting of acetamide, dimethyl formamide (DMF), N,N′-dimethyl acetamide (DMAc), benzamide, N-methyl-2-pyrrolidinone (NMP), 1,5-dimethyl-2-pyrrolidinone, 1,3-dimethyl-2-piperidone, 1-(2-hydroxyethyl)-2-pyrrolidinone, and 1,5-dimethyl 2-piperidone;
one or more ther organic co-solvent selected from the group consisting of dimethyl sulfoxide (DMSO), sulfolane (SFL), and dimethyl piperidone;
and optionally one or more of the following components:
a steric hindered amine or alkanolamine;
an organic or inorganic acid;
of an other metal corrosion inhibitor compounds;
a surfactant;
a metal ion free silicate compound;
a metal chelating agent; and
a fluoride compound.
2. A cleaning composition of claim 1 wherein the composition comprise from about 5%, to about 20% by weight of the secondary fluid modifier formulation component (2) based on the weight of the supercritical main fluid component (1).
3. A cleaning composition according to claim 1 wherein the supercritical main fluid comprises carbon dioxide.
4. A cleaning composition according to claim 3 wherein the secondary fluid modifier formulation comprises a formulation of sulfolane, water, tetramethylammonium hydroxide, trans-1, 2-cyclohexanediamine tetraacetic acid, and hydrogen peroxide.
5. A cleaning composition according to claim 3 wherein the secondary fluid modifier formulation comprises a formulation of sulfolane, water, ethylene glycol, tetramethylammonium hydroxide, trans-1,2-cyclohexanediamine tetraacetic acid, and hydrogen peroxide.
6. A cleaning composition according to claim 3 wherein the secondary fluid modifier formulation comprises a formulation of sulfolane, water, tetramethylammonium hydroxide, ethylenediamine tetra (methylene phosphonic acid, ethylene glycol, and hydrogen peroxide.
7. A process for cleaning a nanoelectronic or microelectronic substrate of photoresist or residue, the process comprising contacting the substrate for a time and at supercritical fluid conditions with a cleaning composition sufficient to clean the substrate, wherein the cleaning composition comprises (1) a supercritical main fluid reaching a supercritical fluid state at a temperature of 250° C. or less and a pressure of 600 bars or less (592.2 atm, 8702.3 psi), and (2) as a secondary fluid, a modifier formulation wherein the second fluid modifier comprises a formulation selected from the group consisting of the following formulations:
a) a formulation comprising:
an oxidizing agent;
a polar organic solvent selected from the group consisting of sulfones, sulfolenes, and selenones;
an alkaline base of the formula R 4 N + OH − wherein each R is independently a substituted or unsubstituted alkyl group of 1 to 22 carbon atoms:
water; and
q chelating or metal complexing agent selected from the group consisting of trans-1,2-cyclohexanediamine tetraacetic acid (CyDTA), ethylenediamine tetraacetic acid (EDTA), stannates, pyrophosphates, ethane-1-hydroxy-1,1-diphosphonate, ethylenediamine tetra(methylene phosphonic acid) (EDTMP), diethylenetriamine penta(methylene phosphonic acid), and triethylenetetramine hexa(methylene phosphonic acid).
and optionally one or more of the following components:
an acid;
a corrosion-inhibiting co-solvent;
an oxidizer stabilizing agent;
a corrosion-inhibiting agent;
a metal corrosion inhibitor;
a fluoride compound; and
a surfactant;
b) a silicate free formulation comprising:
a polar organic solvent selected from the group consisting of sulfones, sulfolenes and selenones; and
a strong alkaline base of the formula R 4 N + OH − wherein each R is independently a substituted or unsubstituted alkyl group of 1 to 22 carbon atoms;
water; and
q chelating or metal complexing agent selected from the group consisting of trans-1,2-cyclohexanediamine tetraacetic acid (CvDTA), ethylenediamine tetraacetic acid (EDTA), stannates, pyrophosphates, ethane-1-hydroxy-1,1-diphosphonate, ethylenediamine tetra(methylene phosphonic acid) (EDTMP), diethylenetriamine penta(methylene phosphonic acid), and triethylenetetramine hexa(methylene phosphonic acid);
and optionally one or more of the following components:
an acid;
a corrosion-inhibiting co-solvent;
an oxidizer stabilizing agent;
a corrosion-inhibiting agent;
a metal corrosion inhibitor;
a fluoride compound; and
a surfactant;
c) a formulation comprising:
one or more non-ammonium producing strong base of the formula [(R) 4 N +] p [X − g ], where each R is independently a substituted or unsubstituted alkyl of from 1 to 22 carbon atoms; and X=OH or a suitable salt anion, and p and q are equal and are integer of from 1 to 3;
one or more corrosion inhibiting solvent compounds, said corrosion inhibiting solvent compound having at least two sites capable of complexing with metals and selected from the group consisting of ethylene glycol, diethylene qlycol, glycerol, diethylene glycol dimethyl ether, monoethanolamine, diethanolamine, triethanolamine, N,N -dimethylethanolamine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 4-(2-hydroxyethyl)morpholine, 2-(methylamino)ethanol, 2-amino-2-methyl-1-propanol, 1-amino-2-propanol, 2-(2-aminoethoxy)-ethanol, N-(2-hydroxyethyl) acetamide, N-(2-hydroxyethyl) succinimide and 3-(diethylamino)-1,2-propanediol;
and optionally one or more of the following components:
water or other organic co-solvent;
a steric hindered amine or alkanolamine;
an organic or inorganic acid;
an other metal corrosion inhibitor compounds;
a surfactant;
a metal ion free silicate compound;
a metal chelating agent; and
a fluoride compound;
d) a formulation comprising:
one or more non-ammonium producing, non-HF producing fluoride salt of the formula (R) 4 N + F 31 , where each R is independently a substituted or unsubstituted alkyl of from 1 to 22 carbon atoms;
sulfolane, dimethyl sulfoxide and 1-(2-hydroxyethyl)-2- pyrrolidinone as organic solvents;
and optionally one or more of the following components:
a metal corrosion inhibiting solvent;
a steric hindered amine or alkanolamine;
an organic or inorganic acid;
from about 0 to 40% by weight of an other metal corrosion inhibitor compound;
a surfactant;
a metal ion free silicate compound; and from about 0 to 5% by weight of a metal chelating agent; and
e) a formulation comprising:
one or more non-ammonium producing strong base of the formula [(R) 4 N +] p [X − g ], where each R is independently a substituted or unsubstituted alkyl of from 1 to 22 carbon atoms; and X=OH or a suitable salt anion, and p and q are equal and are integer of from 1 to 3;
one or more steric hindered amide solvents selected from the group consisting of acetamide, dimethyl formamide (DMF), N,N′-dimethyl acetamide (DMAc), benzamide, N-methyl-2-pyrrolidinone (NMP), 1,5-dimethyl-2-pyrrolidinone, 1,3-dimethyl-2-piperidone, 1-(2-hydroxyethyl)-2-pyrrolidinone, and 1,5-dimethyl 2-piperidone;
one or more other organic co-solvent selected from the group consisting of dimethyl sulfoxide (DMSO), sulfolane (SFL), and dimethyl piperidone;
and optionally one or more of the following components:
a steric hindered amine or alkanolamine;
an organic or inorganic acid;
of an other metal corrosion inhibitor compounds;
a surfactant.;
a metal ion free silicate compound;
a metal chelating agent; and
a fluoride compound.
8. A process for cleaning a nanoelectronic or microelectronic substrate of photoresist or residue according to claim 7 , wherein the composition comprise from about 5%, to about 20% by weight of the secondary fluid modifier formulation component (2) based on the weight of the supercritical main fluid component (1).
9. A process for cleaning a nanoelectronic or microelectronic substrate of photoresist or residue according to claim 7 , wherein the supercritical main fluid comprises carbon dioxide.
10. A process for cleaning a nanoelectronic or microelectronic substrate of photoresist or residue according to claim 9 , wherein the secondary fluid modifier formulation comprises a formulation of sulfolane, water, tetramethylammonium hydroxide, trans-1,2-cyclohexanediamine tetraacetic acid, and hydrogen peroxide.
11. A process for cleaning a nanoelectronic or microelectronic substrate of photoresist or residue according to claim 9 , wherein the secondary fluid modifier formulation comprises a formulation of sulfolane, water, ethylene glycol, tetramethylammonium hydroxide, trans-1,2-cyclohexanediamine tetraacetic acid, and hydrogen peroxide.
12. A process for cleaning a nanoelectronic or microelectronic substrate of photoresist or residue according to claim 9 , wherein the secondary fluid modifier formulation comprises a formulation of sulfolane, water, tetramethylammonium hydroxide, ethylenediamine tetra (methylene phosphonic acid, ethylene glycol, and hydrogen peroxide.
13. A cleaning composition according to claim 3 comprising:
tetramethylammonium fluoride, sulfolane, dimethyl sulfoxide and 1-(2-hydroxyethyl)-2-pyrrolidinone.
14. A process for cleaning a nanoelectronic or microelectronic substrate of photoresist or residue according to claim 9 , wherein the secondary fluid modifier formulation comprises a formulation of tetramethylammonium fluoride, sulfolane, dimethyl sulfoxide and 1-(2-hydroxyethyl)-2- pyrrolidinone.