Process environment for inorganic resist patterning
The processing of radiation patternable organometallic coatings is shown to be improved through the appropriate selection of post processing conditions between coating and development of the pattern. In particular, a coated wafer can be subjected to process delays to allow aging of the coating at various process points, in particular following irradiation. Process delays can be combined and interspersed with heating steps. The atmosphere above the coated wafer at various process steps can be adjusted to obtain desired improvements in the development of the pattern. Reactive gases can be beneficial with respect to improvement of coating properties.
1 . A method for improving the processing of a radiation patternable organo tin-based coating comprising organo tin oxide hydroxide having Sn—C bonds, wherein the organo tin oxide hydroxide coating has a thickness from about 1 nm to about 500 nm, the method comprising:
contacting the wafer with the organo tin oxide hydroxide coating, following irradiation and development to form a developed pattern, to an atmosphere comprising a reactive gas to alter the tin-bound ligands in the developed pattern, wherein the reactive gas comprises SO 2 , H 2 S, an alkyl mercaptan, CO, COS, HOOH, NH 3 , H 2 , O 3 , nitrogen oxide, PH 3 , SiH 4 , Si 2 H 6 , CH 4 , ethylene oxide or a combination thereof, wherein the concentration of the reactive gas is greater than in ambient air.
2 . The method of claim 1 wherein the developed pattern comprises a negative tone pattern.
3 . The method of claim 1 wherein the organo tin oxide hydroxide coating comprises a composition represented by the formula RSnO (1.5-(x/2) (OH) x where 0<x≤3,
wherein R is an organic ligand with 1-31 carbon atoms, with a carbon atom bonded to Sn and with one or more carbon atoms optionally substituted with one or more heteroatom functional groups.
4 . The method of claim 1 wherein the contacting step is performed at a temperature from about 100° C. to about 500° C.
5 . The method of claim 1 wherein the contacting step is performed at a temperature of about 45° C. to about 150° C. for at least about 20 minutes.
6 . The method of claim 1 wherein the contacting step results in an increase in critical dimension in a developed structure for a given exposure dose relative to a corresponding wafer not contacted with the reactive gas, wherein the exposure dose comprises EUV radiation.
7 . The method of claim 1 wherein the contacting step results in an increase in critical dimension in a developed structure of at least about 0.25 nm.
8 . The method of claim 1 wherein the atmosphere comprises reactive gas at a concentration from about 100 ppm by mole to about 10 mole percent.
9 . The method of claim 1 wherein the atmosphere comprises reactive gas at a concentration from about 500 ppm by mole to about 5 mole percent and the pressure of the atmosphere is at least about 600 Torr.
10 . The method of claim 1 wherein the pressure of the atmosphere is above atmospheric pressure.
11 . The method of claim 1 wherein the pressure of the atmosphere is from about 800 Torr to about 1200 Torr.
12 . The method of claim 8 wherein the remaining atmosphere is air with a relative humidity from 40% to 60%.
13 . The method of claim 8 wherein the remaining atmosphere is an inert gas.
14 . The method of claim 13 wherein the atmosphere further comprises water vapor at a concentration of no more than 10 ppm.
15 . The method of claim 8 wherein the remaining atmosphere is nitrogen.
16 . The method of claim 1 wherein the atmosphere has a relative humidity that varies by no more than about 10%.
17 . The method of claim 1 wherein the reactive gas comprises SO 2 , H 2 S, CH 3 SH, COS, PH 3 , SiH 4 , Si 2 H 6 , CH 4 , ethylene oxide or a combination thereof.
18 . The method of claim 1 further comprising, prior to contacting, irradiating the organo tin oxide hydroxide coating and developing the irradiated coating to form the developed pattern.
19 . A method for improving the processing of a radiation patternable organo tin-based coating comprising organo tin oxide hydroxide having Sn—C bonds, wherein the organo tin oxide hydroxide coating has a thickness from about 1 nm to about 500 nm, the method comprising:
contacting the wafer with the organo tin oxide hydroxide coating, following irradiation, to an atmosphere comprising a reactive gas to alter the tin-bound ligands in the irradiated regions, wherein the reactive gas comprises SO 2 , H 2 S, an alkyl mercaptan, COS, PH 3 , SiH 4 , Si 2 H 6 , CH 4 , ethylene oxide or a combination thereof.
20 . The method of claim 19 wherein the reactive gas comprises SO 2 , H 2 S, CH 3 SH, COS or a combination thereof.
21 . The method of claim 19 wherein the contacting step is performed at a temperature from about 45° C. to about 250° C. after irradiating and prior to development.
22 . The method of claim 19 wherein the contacting step is performed at a temperature less than about 100° C. after irradiating and prior to development.
23 . A method for improving the processing of a radiation patternable organo tin-based coating comprising organo tin oxide hydroxide having Sn—C bonds, wherein the organo tin oxide hydroxide coating has a thickness from about 1 nm to about 500 nm, the method comprising:
contacting the wafer with the organo tin oxide hydroxide coating, following irradiation, to an atmosphere comprising a reactive gas to alter the tin-bound ligands in the irradiated regions, wherein the reactive gas comprises SO 2 , H 2 S, an alkyl mercaptan, CO, COS, HOOH, H 2 , O 3 , nitrogen oxide, PH 3 , SiH 4 , Si 2 H 6 , CH 4 , ethylene oxide or a combination thereof, wherein the atmosphere comprises reactive gas at a concentration from about 100 ppm by mole to about 10 mole percent, wherein the concentration of the reactive gas is greater than in ambient air.
24 . The method of claim 19 wherein the organo tin oxide hydroxide coating comprises a composition represented by the formula RSnO (1.5-(x/2) (OH) x where 0<x≤3,
wherein R is an organic ligand with 1-31 carbon atoms, with a carbon atom bonded to Sn and with one or more carbon atoms optionally substituted with one or more heteroatom functional groups.
25 . The method of claim 23 wherein the organo tin oxide hydroxide coating comprises a composition represented by the formula RSnO (1.5-(x/2) (OH) x where 0<x≤3,
wherein R is an organic ligand with 1-31 carbon atoms, with a carbon atom bonded to Sn and with one or more carbon atoms optionally substituted with one or more heteroatom functional groups.
26 . The method of claim 23 wherein the reactive gas comprises SO 2 , H 2 S, CH 3 SH, COS or a combination thereof.
27 . The method of claim 23 wherein the reactive gas further comprises NH 3 .
28 . The method of claim 23 wherein the contacting step is performed at a temperature from about 45° C. to about 250° C. after irradiating and prior to development.
29 . The method of claim 23 wherein the contacting step is performed at a temperature less than about 100° C. after irradiating and prior to development.
30 . The method of claim 23 wherein the atmosphere comprises reactive gas at a concentration from about 500 ppm by mole to about 5 mole percent and the pressure of the atmosphere is at least about 600 Torr.