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 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 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 a second precursor vapor comprising an oxygen-containing compound capable of reacting with the composition in the first precursor vapor under conditions in the deposition chamber to form a composition with non-volatile components and a volatile component comprising a reaction product with X ligand or ligands, wherein a substrate is configured with a surface to receive the non-volatile components of the composition.
2. The method of claim 1 wherein the oxygen containing compound comprises water vapor, hydrogen peroxide, ozone, oxygen, an alcohol, or combinations thereof.
3. The method of claim 1 wherein the second precursor vapor comprises water vapor.
4. The method of claim 1 wherein the deposition chamber has a pressure from about 0.01 Torr to about 25 Torr.
5. The method of claim 1 further comprising modulating the pressure in the deposition chamber.
6. The method of claim 1 wherein the deposition chamber has a temperature from about 40° C. to about 175° C.
7. The method of claim 1 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.
8. The method of claim 7 further including a step of inputting an inert purge gas between each cycle of inputting precursor vapors.
9. The method of claim 8 wherein the inert purge gas is nitrogen or argon.
10. 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 film is formed following the input steps by a CVD process.
11. 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 film is formed following the input steps by a CVD process.
12. The method of claim 1 wherein a third 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.
13. The method of claim 12 wherein the inputting of the third 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 film is formed following the input steps by a CVD process.
14. The method of claim 1 wherein R is a methyl, ethyl, i-propyl, n-butyl, s-butyl or t-butyl group.
15. The method of claim 1 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 (—CCR, 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.
16. The method of claim 1 wherein the radiation patternable film is formed following the input steps, and the method further comprises an exposing step, wherein the radiation patternable film is irradiated with a pattern of EUV radiation.
17. The method of claim 16 wherein the radiation has a dose from about 1 mJ/cm 2 to about 150 mJ/cm 2 .
18. The method of claim 16 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.
19. The method of claim 16 , further comprising developing the irradiated film to selectively remove un-irradiated film material or irradiated film material and forming a pattern in the film, 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.
20. The method of claim 16 further comprising developing the irradiated film to selectively remove un-irradiated film material or irradiated film material and forming a pattern in the film, wherein the dose of radiation is from about 8 mJ/cm 2 to about 25 mJ/cm 2 and wherein the pattern has a pitch of no more than a 32 nm, features of no more than 16 nm wide and/or a line width roughness of no more than about 4 nm.
21. The method of claim 16 wherein the dose-to-gel is no more than about 5.5 mJ/cm 2 .
22. 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.
23. The method of claim 12 wherein the third precursor vapor comprises SnL 4 .
24. 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.