Gas-based development of organometallic resist in an oxidizing halogen-donating environment
A method provides for performing a dry development of an organotin composition patterned with radiation and having a latent image. The method comprises developing a structure with a gas comprising a halogen based developer and an oxygen source compound, wherein the structure comprises a substrate with layer of composition with a latent image with regions with at least partially condensed tin oxide-hydroxide and separate regions with an organotin composition having carbon-tin bonds, and wherein the developing results in at least partial removal of the organotin composition having carbon-tin bonds. Contact with an oxidizing environment can be performed as a separate step followed by the halogen based thermal development. Suitable apparatuses provide for the desired processing.
1 . A method for performing a dry development of an organotin composition patterned with radiation and having a latent image, the method comprising:
developing a structure with a gas comprising a halogen based developer and an oxygen source compound, wherein the structure comprises a substrate with layer of composition with a latent image with regions with at least partially condensed tin oxide-hydroxide and separate regions with an organotin composition having carbon-tin bonds, and wherein the developing results in at least partial removal of the organotin composition having carbon-tin bonds.
2 . The method of claim 1 wherein the halogen based developer comprises HF, HCl, HBr, HI, an acyl halide (COX 2 ), a carbonyl halide (RCOX), or a mixture thereof, wherein X is F, Cl, Br or I and R is an alkyl group with 1 to 5 carbon atoms.
3 . The method of claim 1 wherein the halogen based developer comprises HF, HCl, HBr, HI, or a mixture thereof.
4 . The method of claim 1 wherein the oxygen source compound comprises O 2 , O 3 , H 2 O, H 2 O 2 , NO 2 , NO or mixtures thereof.
5 . The method of claim 1 wherein the organotin composition having carbon-tin bonds comprises a composition represented by the formula RSnO 1.5-x/2 (OH) x wherein 0<x<3, and R forms a carbon-tin bond and is a hydrocarbyl group having from 1 to 31 carbon atoms with 3 to 31 carbon atoms for the group with a secondary-bonded carbon atom and 4 to 31 carbon atoms for the group with a tertiary-bonded carbon atom, optionally with unsaturated or aromatic carbon bonds.
6 . The method of claim 5 wherein the at least partially condensed tin oxide-hydroxide composition is formed from the composition represented by the formula RSnO 1.5-x/2 (OH) x wherein carbon-tin bonds are cleaved by radiation.
7 . The method of claim 1 wherein the development is a thermal process with the developing step performed at a temperature from about −25° C. to about 250° C.
8 . The method of claim 1 wherein the development is a thermal process with the developing step performed at a temperature from about 0° C. to about 150° C.
9 . The method of claim 8 wherein the processing is performed in a chamber at a pressure of at least 5 Torr.
10 . The method of claim 1 wherein the halogen based developer is provided at a flow rate from about to about 50 sccm to about 5000 sccm.
11 . The method of claim 1 wherein the gas comprises at least 50 mole % oxygen source compound excluding inert gases.
12 . The method of claim 1 wherein the gas comprises air.
13 . The method of claim 12 wherein the water content of the air is adjusted to achieve a desired water partial pressure.
14 . The method of claim 1 wherein the gas comprises from about 1 mol % to about 10 mol % dihalides excluding inert gas contributions.
15 . The method of claim 1 wherein the regions with at least partially condensed tin oxide-hydroxide correspond to irradiated regions and have a lower concentration of carbon-tin bonds than the separate regions.
16 . The method of claim 1 further comprising performing a post-exposure bake (PEB) step prior to the developing step, comprising heating the structure to a temperature from about 60° C. to about 250° C. for from about 0.1 minutes to about 5 minutes under a pressure of at least 200 Torr.
17 . The method of claim 16 wherein the atmosphere during PEB comprises O 2 , O 3 , H 2 O, H 2 O 2 , CO 2 , or combinations thereof.
18 . The method of claim 16 wherein the atmosphere during PEB comprises air.
19 . The method of claim 16 wherein the developing step is performed without purging the PEB atmosphere.
20 . The method of claim 1 further comprising performing a plasma descumming after completing the developing to at least partial removal of the organotin composition having carbon-tin bonds.
21 . A development chamber comprising:
an enclosure configured for achieving a controlled pressure through operation of a pump and suitable pressure sensors;
a substrate support within the enclosure;
a development energy source comprising a heater, a cooler, and/or a plasma source configured to deliver energy to a substrate mounted on the substrate support;
a halide developer source configured to deliver a gas of halide developer into the enclosure from a reservoir through a flow regulator; and
an oxygen compound source configured to deliver a vapor of an oxygen comprising compound into the enclosure from a reservoir through a flow regulator.