Ni:NiGe:Ge selective etch formulations and method of using same
Compositions and methods for selectively removing unreacted metal material (e.g., unreacted nickel) relative to metal germanide (e.g., NiGe), metal-III-V materials, and germanium from microelectronic devices having same thereon. The compositions are substantially compatible with other materials present on the microelectronic device such as low-k dielectrics and silicon nitride.
1. A composition comprising about 0.01 wt % to about 10 wt % of at least one non-oxidizing acid, about 0.01 wt % to about 10 wt % of at least one unreacted metal dissolution agent, about 0.01 wt % to about 5 wt % of at least one germanium passivation agent, about 0.01 wt % to about 5 wt % of at least one metal germanide passivation agent, and about 70 wt % to about 99.96 wt % of at least one solvent,
wherein the at least one non-oxidizing acid comprises a species selected from the group consisting of methanesulfonic acid, oxalic acid, citric acid, tartaric acid, picolinic acid, succinic acid, lactic acid, sulfosuccinic acid, benzoic acid, propionic acid, formic acid, oxalic acid, maleic acid, malonic acid, fumaric acid, malic acid, ascorbic acid, mandelic acid, heptanoic acid, butyric acid, valeric acid, glutaric acid, phthalic acid, hypophosphorous acid, 5-sulfosalicylic acid, hydrochloric acid, and combinations thereof, preferably oxalic acid, 5 sulfosalicylic acid, or combinations thereof;
wherein the unreacted metal dissolution agent comprises a species selected from the group consisting of ammonium sulfite monohydrate, ammonium sulfate, ammonium hypophosphite, tetrabutyl ammonium cyanate, sodium sulfite, potassium sulfite, sodium erythorbate, tocopherol, naringenin, glutathione, and combinations thereof;
wherein the germanium passivation agent comprises a species selected from the group consisting of boric acid, ammonium biborate, ammonium pentaborate, sodium tetraborate, 3-hydroxy-2-naphthoic acid, malonic acid, alkyltrimethylammonium chloride, alkyltrimethylammonium bromide, decyltrimethylammonium chloride, carnitine, betaine, and combinations thereof;
wherein the metal germanide passivation agent comprises a species selected from the group consisting of 2-isopropylmalic acid, 2-propylmalic acid, 3-(4-hydroxyphenyl)lactic acid, 3-propylmalic acid, 4 hydroxymandelic acid, 2-hydroxyoctanoic acid, mandelic acid, squaric acid, 2-oxo-carboxylic acids, 5-sulfosalicylic acid, ethyl thioglycolate, 1,2-ethanedithiol, cysteine, methionine, dibenzothiophene, S-adenosylmethionine, taurine, glutathione, thiolactic acid, thiosalicylic acid, 2,2′-thiodiacetic acid, 3,3′-thiodipropionic acid, thioglycolic acid, dithiodiglycolic acid, 2,2′-(ethylenedithio)diacetic acid, 3-methoxybutyl thioglycolate, methyl thioglycolate, and combinations thereof and wherein the composition selectively removes unreacted metal relative to metal germanide, metal-III-V materials and germanium from the microelectronic device having the same thereon; and
wherein the solvent comprises a species selected from the group consisting of water, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, 2-ethyl-1-hexanol, heptanol, octanol, and higher alcohols, 4-methyl-2-pentanol, ethylene glycol, propylene glycol, butylene glycol, butylene carbonate, ethylene carbonate, propylene carbonate, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and combinations thereof.
2. The composition of claim 1 , wherein the at least one non-oxidizing acid comprises oxalic acid, 5-sulfosalicylic acid, or combinations thereof.
3. The composition of claim 1 , wherein the unreacted metal dissolution agent comprises ammonium sulfite monohydrate.
4. The composition of claim 1 , wherein the solvent comprises water.
5. The composition of claim 1 , wherein the germanium passivation agent comprises ammonium biborate.
6. The composition of claim 1 , wherein the pH is in a range from 0 to about 5.
7. The composition of claim 1 , wherein the composition is substantially devoid of chemical mechanical polishing abrasive, hydrogen peroxide, nitric acid, sulfuric acid, sulfonic acid and derivatives thereof, and combinations thereof.
8. A method of selectively removing unreacted metal material relative to metal germanide, metal-III-V materials, and germanium from microelectronic devices having the same thereon, said method comprising contacting the microelectronic device with a composition, wherein the composition comprises at least one non-oxidizing acid, at least one unreacted metal dissolution agent, at least one germanium passivation agent, at least one metal germanide passivation agent, and at least one solvent, wherein the metal germanide passivation agent comprises a species selected from the group consisting of 2-isopropylmalic acid, 2-propylmalic acid, 3-(4-hydroxyphenyl)lactic acid, 3-propylmalic acid, 4 hydroxymandelic acid, 2-hydroxyoctanoic acid, mandelic acid, squaric acid, 2-oxo-carboxylic acids, salicylic acid, 5-sulfosalicylic acid, ethyl thioglycolate, 1,2-ethanedithiol, cysteine, methionine, dibenzothiophene, S-adenosylmethionine, taurine, glutathione, thiolactic acid, thiosalicylic acid, 2,2′-thiodiacetic acid, 3,3′-thiodipropionic acid, thioglycolic acid, dithiodiglycolic acid, 2,2′-(ethylenedithio)diacetic acid, 3-methoxybutyl thioglycolate, methyl thioglycolate, and combinations thereof, and wherein unreacted metal material is selectively removed relative to metal germanide, metal-III-V materials and germanium from the microelectronic device having the same thereon.
9. The method of claim 8 , wherein the unreacted metal is nickel.
10. The method of claim 8 , wherein the metal germanide is nickel germanide.
11. The method of claim 8 , wherein the selectively of removal of unreacted metal:metal germanide is greater than 1:1.
12. The method of claim 8 , wherein the selectively of removal of unreacted metal:germanium is greater than 1:1.