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 comprising an oxo-hydroxo network with metal cations having organic ligands with metal carbon bonds and metal oxygen bonds, the method comprising:
inputting into a deposition chamber closed from the ambient atmosphere a first precursor vapor comprising a first 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; and
inputting into the deposition chamber a second precursor vapor comprising a second organotin composition represented by the formula R′ m SnX′ 4-m wherein R′ is an organic ligand with 1-31 carbon atoms bound to Sn with a metal-carbon bond and R′ is different from R, m=1-3, and X′ is a ligand having a hydrolysable bond with Sn,
wherein a substrate receives on a surface the non-volatile components of a composition formed from the reaction of the first precursor vapor and the second precursor vapor with a third precursor vapor comprising an oxygen-containing compound that also form a volatile component comprising a reaction product with X and X′ ligands.
2. The method of claim 1 wherein the third precursor vapor comprises ambient water vapor.
3. The method of claim 1 further comprising inputting the third precursor vapor into the deposition chamber, wherein the oxygen containing compound comprises water vapor, hydrogen peroxide, ozone, oxygen, an alcohol, or combinations thereof.
4. The method of claim 3 wherein the third precursor vapor comprises water vapor.
5. The method of claim 1 wherein the deposition chamber has a pressure from about 0.01 Torr to about 25 Torr and/or wherein the deposition chamber has a temperature from about 40° C. to about 175° C.
6. The method of claim 1 further comprising modulating the pressure in the deposition chamber.
7. The method of claim 1 wherein the first precursor vapor and the second precursor vapor are separately inputted to the chamber.
8. The method of claim 1 wherein the inputting of the first precursor vapor and the inputting of the second precursor vapor is sequential or at the same time.
9. The method of claim 7 wherein the first precursor vapor and the second precursor vapor comprise a blended composition.
10. The method of claim 9 wherein the blended composition comprises at least about 5 mole percent of each organotin composition.
11. The method of claim 9 wherein the blended composition comprises at least about 20 mole percent of each organotin composition.
12. The method of claim 3 wherein the inputting of the first precursor vapor and the second precursor vapor and the inputting of the third precursor vapor are repeated at least once to have a second cycle of deposition.
13. The method of claim 12 further including a step of inputting an inert purge gas between each cycle of inputting precursor vapors.
14. The method of claim 13 wherein the inert purge gas is nitrogen or argon.
15. The method of claim 1 wherein the inputting of the first precursor vapor comprises generating a flow of the first precursor vapor, generating an aerosol from a liquid comprising the first precursor composition, injecting a liquid into a vaporization chamber, flash evaporating the composition of the first precursor vapor, and/or bubbling an inert carrier gas through a liquid comprising the composition of the first precursor vapor wherein the first precursor vapor is formed, and wherein the radiation patternable organometallic film is formed following the input steps by a CVD process.
16. The method of claim 1 wherein the inputting of the second precursor vapor comprises generating a flow of the second precursor vapor, generating an aerosol from a liquid comprising the first precursor composition, injecting a liquid into a vaporization chamber, flash evaporating the composition of the first precursor vapor, and/or bubbling an inert carrier gas through a liquid comprising the composition of the first precursor vapor wherein the first precursor vapor is formed, and wherein the radiation patternable organometallic film is formed following the input steps by a CVD process.
17. The method of claim 1 wherein a fourth precursor vapor is inputted to the chamber, the precursor comprising ML v , where v is 2≤v≤6 and L is an oxidizable ligand or a ligand having a hydrolysable M-L bond or a combination thereof, and M is a metal selected from groups 2-16 of the periodic table or a compound represented by the formula R″ p SnX “ 4-p , wherein R” is bound to Sn with a metal-carbon bond, p=1-3, and X, X′, and X″ are independently a ligand having a hydrolysable bond with Sn.
18. The method of claim 17 wherein the inputting of the fourth precursor vapor comprises generating a flow of the first precursor vapor, generating an aerosol from a liquid comprising the first precursor composition, injecting a liquid into a vaporization chamber, flash evaporating the composition of the first precursor vapor, and/or bubbling an inert carrier gas through a liquid comprising the composition of the first precursor vapor wherein the first precursor vapor is formed, and wherein the radiation patternable organometallic film is formed following the input steps by a CVD process.
19. The method of claim 17 wherein the fourth precursor vapor comprises SnL 4 .
20. The method of claim 1 wherein R and/or R′ is a methyl, ethyl, i-propyl, n-butyl, s-butyl or t-butyl group.
21. The method of claim 1 wherein X and/or 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.
22. The method of claim 1 wherein X and X′ are the same.
23. The method of claim 1 wherein the radiation patternable organometallic film is formed following the input steps, and the method further comprises an exposing step, wherein the radiation patternable organometallic film is irradiated with a pattern of EUV radiation.
24. The method of claim 23 wherein the radiation has a dose from about 1 mJ/cm 2 to about 150 mJ/cm 2 and/or wherein the dose-to-gel is no more than about 5.5 mJ/cm 2 .
25. The method of claim 1 wherein the substrate comprises a silicon wafer and wherein the 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.
26. The method of claim 1 wherein the composition of the first precursor vapor and the second 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.
27. The method of claim 1 further comprising heating the substrate, the walls of the deposition chamber, the first precursor vapor, the second precursor vapor, and/or the third precursor vapor to a temperature independently from about 40° C. to about 200° C.
28. The method of claim 1 further comprising cooling the substrate.