Organotin oxide hydroxide patterning compositions, precursors, and patterning
Organometallic precursors are described for the formation of high resolution lithography patterning coatings based on metal oxide hydroxide chemistry. The precursor compositions generally comprise ligands readily hydrolysable by water vapor or other OH source composition under modest conditions. The organometallic precursors generally comprise a radiation sensitive organo ligand to tin that can result in a coating that can be effective for high resolution patterning at relatively low radiation doses and is particularly useful for EUV patterning. The precursors compositions are readily processable under commercially suitable conditions. Solution phase processing with in situ hydrolysis or vapor based deposition can be used to form the coatings.
1. A method for forming a radiation patternable organometallic film on a substrate, the method comprising:
inputting into a deposition chamber closed from the ambient atmosphere a first precursor vapor comprising an organotin composition having at least one Sn—C bond and having at least one ligand having a hydrolysable bond with Sn; and
forming the radiation patternable organometallic film on the substrate, wherein the radiation patternable organometallic film comprises C—Sn bonds and has an average film thickness from about 1 nm to about 50 nm, and wherein the radiation patternable organometallic film comprises an oxo-hydroxo network.
2. The method of claim 1 wherein the organotin composition is represented by the formula R n SnX 4-n wherein R is an organic ligand with 1-31 carbon atoms bound to Sn with a metal-carbon bond, n=1-3 and X is a ligand having a hydrolysable bond with Sn.
3. The method of claim 2 wherein R can be linear, branched or cyclic hydrocarbyl moieties bound to the Sn at a primary, secondary, or tertiary carbon, and may optionally comprise aryl, alkenyl, alkynyl groups and/or heteroatom functional groups.
4. The method of claim 2 wherein R is a methyl, ethyl, i-propyl, n-butyl, s-butyl, t-butyl or t-amyl group.
5. The method of claim 2 wherein X is alkylamido or dialkylamido (—NR 1 R 2 , where R 1 and R 2 are independently hydrocarbon groups with 1-10 carbon atoms or hydrogen), siloxo (—OSiR 1 R 2 R 3 , where R 1 , R 2 , are independently hydrocarbon groups with 1-10 carbon atoms), silylamido (—N(SiR 1 3 )(R 2 ), where R 1 and R 2 are independently hydrocarbon groups with 1-10 carbon atoms), disilylamido (—N(SiR 1 3 )(SiR 2 3 ) where R 1 and R 2 are independently hydrocarbon groups with 1-10 carbon atoms), alkoxo and aryloxo (—OR, where R is an alkyl or aryl group with 1-10 carbon atoms), azido (—N 3 ), alkynido (—C≡CR, where R is a hydrocarbon group with 1-9 carbon atoms), amidato (—NR 1 (COR 2 ) where R 1 and R 2 are independently hydrocarbon groups with 1-7 carbon atoms or hydrogen), amidinato (—NR 1 C(NR 2 )R 3 ) where R 1 and R 2 are independently hydrocarbon groups with 1-8 carbon atoms or hydrogen), imido (—N(COR 1 )(COR 2 ), where R 1 and R 2 are independently hydrocarbon groups with 1-8 carbon atoms or hydrogen), or fluorinated analogues thereof, or combinations thereof.
6. The method of claim 2 wherein X is alkylamido or dialkylamido (—NR 1 R 2 , where R 1 and R 2 are independently hydrocarbon groups with 1-10 carbon atoms or hydrogen).
7. The method of claim 1 wherein forming the radiation patternable organometallic film on the substrate further comprises:
inputting into the deposition chamber a second precursor vapor comprising an oxygen-containing compound capable of reacting with a film of the organotin composition of the first precursor vapor on the substrate-under conditions in the deposition chamber to form a second composition comprising a non-volatile component and a volatile component, the volatile component comprising a reaction product with the at least one ligand having a hydrolysable bond with Sn, and the non-volatile component forms the radiation patternable organometallic film on the surface of the substrate.
8. The method of claim 7 wherein the oxygen-containing compound is water.
9. The method of claim 1 wherein the oxo-hydroxo network comprises metal cations having organic ligands and metal oxygen bonds.
10. The method of claim 7 wherein the inputting of the first precursor vapor and the inputting of the second precursor vapor are repeated at least once to have a second cycle of deposition.
11. The method of claim 7 further including a step of inputting an inert purge gas between each cycle of inputting precursor vapors.
12. The method of claim 1 further comprising:
inputting a second precursor vapor into the reaction chamber simultaneously with inputting the first precursor vapor, the second precursor vapor comprising an oxygen-containing compound capable of reacting with the organotin composition of the first precursor vapor under conditions in the deposition chamber to form a second composition comprising a non-volatile component and a volatile component, the volatile component comprising a reaction product with the at least one ligand having a hydrolysable bond with Sn, and the non-volatile component deposits on a surface of the substrate as the radiation patternable organometallic film.
13. The method of claim 12 wherein the oxygen containing compound comprises water vapor, hydrogen peroxide, ozone, oxygen, an alcohol, or combinations thereof.
14. The method of claim 12 wherein the oxygen-containing compound is water.
15. The method of claim 1 wherein the inputting of the first precursor vapor comprises generating a vapor flow of the organotin composition of the first precursor vapor, generating an aerosol from a liquid comprising the organotin composition of the first precursor vapor, injecting a liquid comprising the organotin composition of the first precursor vapor into a vaporization chamber, flash evaporating the organotin composition of the first precursor vapor, and/or bubbling an inert carrier gas through a liquid comprising the organotin composition of the first precursor vapor wherein the first precursor vapor is formed.
16. The method of claim 1 wherein a third precursor vapor is inputted to the chamber.
17. The method of claim 16 wherein the third precursor vapor comprises an organotin composition represented by the formula R′ n SnX′ 4-n wherein R′ is an organic ligand with 1-31 carbon atoms bound to Sn with a metal-carbon bond, n=1-3 and X′ is a ligand having a hydrolysable bond with Sn.
18. The method of claim 16 wherein the third precursor vapor comprises SnX 4 .
19. The method of claim 1 wherein the deposition chamber has a pressure from about 0.01 Torr to about 25 Torr and wherein the composition of the first precursor vapor has a vapor pressure of at least 0.05 Torr at temperatures in the range of about 50° C. to about 120° C.
20. The method of claim 1 further comprising modulating the pressure in the deposition chamber.
21. The method of claim 1 wherein the deposition chamber, the precursor vapor, and/or the substrate has a temperature from about 40° C. to about 200° C.
22. The method of claim 1 wherein the substrate comprises a semiconductor wafer, wherein the average film thickness is from about 2 nm to about 40 nm and the film thickness variation is no more than about +/−50% from the average film thickness.
23. The method of claim 1 wherein the composition of the first precursor vapor has a vapor pressure of at least 0.05 Torr at temperatures in the range of about 50° C. to about 120° C.
24. The method of claim 1 further comprising an exposing step, wherein the radiation patternable organometallic film is irradiated with a pattern of EUV radiation.
25. The method of claim 24 wherein the radiation has a dose from about 1 mJ/cm 2 to about 150 mJ/cm 2 .
26. The method of claim 24 further comprising baking after the exposing step at from about 45° C. to about 250° C. for about 0.5 minutes to about 30 minutes.
27. The method of claim 24 further comprising developing the irradiated film to selectively remove un-irradiated film material or irradiated film material.
28. The method of claim 24 further comprising forming a pattern on the substrate, wherein the pattern has a pitch of no more than 60 nm, features of no more than 25 nm wide and/or a line width roughness of no more than 5 nm.
29. The method of claim 1 wherein the deposition chamber comprises atmospheric moisture.
30. The method of claim 1 wherein the organotin composition is represented by the formula RSnX 3 , wherein R is an organic ligand with 1-31 carbon atoms bound to Sn with the at least one Sn—C bond and X is the at least one ligand having a hydrolysable bond with Sn.
31. The method of claim 1 wherein the organotin composition is capable of reacting with an oxygen-containing compound under conditions in the deposition chamber to form a non-volatile organometallic component and a volatile component comprising a reaction product with the at least one ligand having a hydrolysable bond with Sn.