Metrology of bilayer photoresist processes
View Patent ↗A method for patterning a substrate is provided, which comprises (a) providing a substrate; (b) applying a first layer comprising a first photo resist to the substrate; (c) applying a second layer comprising a second photo resist over the first layer; (d) patterning the second layer; and (e) inspecting the patterned second layer with an inspection tool; wherein at least one of the first and second layers comprises a contrasting agent which increases the contrast between the first and second layers to the inspection tool.
1. A method for patterning a substrate, comprising:
providing a substrate;
applying a first layer, comprising a first photoresist, to the substrate;
applying a second layer, comprising a second photo resist, over the first layer;
patterning the second layer; and
inspecting the patterned second layer with an inspection tool;
wherein at least one of the first and second layers comprises a contrasting agent which increases the contrast between the first and second layers to the inspection tool.
2. The method of claim 1 , wherein the inspection tool is an e-beam inspection tool, wherein the contrasting agent is an electrically conductive material, and wherein the contrast is electrical contrast.
3. The method of claim 2 , wherein the electrically conductive material is an electrically conductive oligomer or polymer.
4. The method of claim 3 , wherein the electrically conductive material is a polymer selected from the group consisting of polyaniline salts, polyaniline bases, polypyrroles and polythiophenes.
5. The method of claim 3 , wherein the electrically conductive material is a polymer derived from the monomer
wherein:
Q is selected from the group consisting of S, Se, and Te; and
R 1 is independently selected so as to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; or both R 1 groups together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent species such as nitrogen, selenium, tellurium, sulfur or oxygen atoms.
6. The method of claim 3 , wherein the electrically conductive material is a polymer derived from the monomer
wherein:
Q is selected from the group consisting of S, Se, and Te; and
R 7 is the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane, with the proviso that at least one R 7 is not hydrogen, and m is 2 or 3.
7. The method of claim 3 , wherein the electrically conductive material is a polymer derived from the monomer
wherein:
R 1 is independently selected so as to be the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, amidosulfonate, ether carboxylate, ether sulfonate, ester sulfonate, and urethane; or both R 1 groups together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms; and
R 2 is independently selected so as to be the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane.
8. The method of claim 3 , wherein the electrically conductive material is a polymer derived from the monomer
wherein:
a is 0 or an integer from 1 to 4;
b is an integer from 1 to 5, with the proviso that a+b=5; and
R 1 is independently selected so as to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; or both R 1 groups together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur or oxygen atoms.
9. The method of claim 3 , wherein the electrically conductive material is a polymer derived from a monomer selected from the group consisting of monomer A and monomer B as defined below:
wherein:
a is 0 or an integer from 1 to 4;
b is an integer from 1 to 5, with the proviso that a+b=5; and
R 1 is independently selected so as to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; or both R 1 groups together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur or oxygen atoms.
10. The method of claim 3 , wherein the electrically conductive material is a polymer derived from the monomer
wherein:
Q is S, Se, Te, or NR 6 ;
R 6 is hydrogen or alkyl;
R 8 , R 9 , R 10 , and R 11 are independently selected so as to be the same or different at each occurrence and are selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkyl sulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; and
at least one of R 8 and R 9 , R 9 and R 10 , and R 10 and R 11 together form an alkenylene chain completing a 5 or 6-membered aromatic ring, which ring may optionally include one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms.
11. The method of claim 3 , wherein the electrically conductive material is a polymer derived from a monomer selected from the group consisting of monomers A, B, C, D, E, F and G as defined below:
wherein:
Q is S, Se, Te, or NH;
T is the same or different at each occurrence and is selected from S, NR 6 , 0, SiR 6 2 , Se, Te, and PR 6 ; and
R 6 is hydrogen or alkyl.
12. The method of claim 1 , wherein the inspection tool is an optical inspection tool, wherein the contrasting agent is a dye, and wherein the contrast is optical contrast.
13. The method of claim 12 , wherein the contrasting agent is a fluorescent dye.
14. The method of claim 13 , wherein the optical inspection tool utilizes a wavelength of actinic radiation, and wherein the fluorescent dye fluoresces at the wavelength of actinic radiation utilized by the inspection tool.
15. The method of claim 13 , wherein the fluorescent dye is disposed in the planarizing layer.
16. The method of claim 13 , wherein the dye is selected from the group consisting of anthracene dyes, fluoranone dyes and cyanine dyes.
17. The method of claim 13 , wherein the dye is selected from the group consisting of methaniminium chloride, N,N,N′,N′-tetramethylacridine-3,6-diamine, benzanthrenone, 9,10-Bis(2-phenylethynyl)anthracene, 5,12-Bis(phenylethynyl)naphthacene, calcein, 2-chloro-9,10-bis(2-phenylethynyl)anthracene, 2-chromenone, 2-(4-amidinophenyl)-1H-indole-6-carboxamidine, 3,8-Diamino-5-ethyl-6-phenylphenanthridinium bromide, fluorescein, 2-(4-amidinophenyl)-1H -indole-6-carboxamidine, euxanthic acid, luciferins, perylene, phycoerythrobilin, phycourobilin, propidium iodide, trisodium 8-hydroxypyrene-1,3,6-trisulfonate, rhodamine 6G, rhodamine B, SYBR Green I, trans-1,2-diphenylethylene, sulforhodamine 101, sulforhodamine 101 acid chloride, 6-Methoxy-(8-p-toluenesulfonamido)quinoline (TSQ), and 7-hydroxycoumarin.
18. The method of claim 1 , wherein the difference in absorption between the first and second layers of the actinic radiation utilized by the inspection tool is at least 5%.
19. The method of claim 1 , wherein the difference in indices of refraction between the first and second layer is at least 0.05 along at least one axis.
20. The method of claim 1 wherein, if the inspection tool is an optical inspection tool, the contrast is a difference in adsorption of the actinic radiation, and if the inspection tool is an e-beam inspection tool, the contrast is a difference in dielectric constant.
21. The method of claim 3 , wherein the contrasting agent is in the first layer, and wherein the first layer is a planarizing layer.
22. The method of claim 1 , wherein the substrate is a semiconductor wafer.
23. The method of claim 1 , further comprising using the patterned second layer as an etch mask in an etching process to transfer the pattern from the second layer to the first layer, and wherein the etching process occurs after the patterned second layer is inspected.