Metallic photoresist patterning and defect improvement
View Patent ↗A multilayer structure for lithography patterning is provided. The multilayer structure includes a substrate, a bottom anti-reflective coating (BARC) layer over the substrate, and a photoresist layer over the BARC layer. The BARC layer includes a polymer and a hydrolysis promoting agent. The photoresist layer includes an organometallic dimer obtained by partial hydrolysis of a precursor organometallic compound comprising hydrolysable ligands.
1. A multilayer structure, comprising:
a substrate;
a stack over the substrate for lithographically patterning the substrate, the stack comprising:
a bottom anti-reflective coating (BARC) layer over the substrate, the BARC layer comprising a polymer and a hydrolysis promoting agent selected from the group consisting of toluidine, chlorobenzene and tetrachloroethane; and
a photoresist layer over the BARC layer, the photoresist layer comprising an organometallic dimer obtained by partial hydrolysis of a precursor organometallic compound represented by the following formula:
R n -M-L 4-n ,
wherein:
M is a metal selected from the group consisting of tin (Sn), antimony (Sb) and indium (In);
R is an organic ligand with 1 to 30 carbon atoms bound to M with a metal-carbon bond;
L is a hydrolysable ligand; and
n is an integer of 1 or 2,
wherein the hydrolysis promoting agent is adapted to increase water content in the photoresist layer, thereby causing complete hydrolysis of the organometallic dimer to form an organometallic oxide hydroxide dodecamer cluster through condensation prior to patterning the photoresist layer.
2. The multilayer structure of claim 1 , wherein the hydrolysis promoting agent has a boiling point greater than 180° C.
3. The multilayer structure of claim 2 , wherein the high boiling point solvent is toluidine.
4. The multilayer structure of claim 1 , wherein the BARC layer further comprises a surfactant, a quencher, a thermal acid or thermal base generator or combinations thereof.
5. The multilayer structure of claim 1 , further comprising a planarization layer between the substrate and the BARC layer.
6. The multilayer structure of claim 5 , wherein the planarization layer comprises spin-on carbon, diamond-like carbon, polyarylene ether or polyimide.
7. A multilayer stack for use in a lithography patterning process, comprising:
a bottom material layer over a substrate, the bottom material layer comprising spin-on carbon, diamond-like carbon, polyarylene ether, or polyimide;
a middle material layer over the bottom material layer, the middle material layer comprising a crosslinkable polymer comprising at least one cross-linkable pendant group attached to a polymer backbone and a diffusible molecule for absorbing water from ambient environment, the diffusible molecule represented by the following formula:
R 1 —X,
wherein:
R 1 is an alkyl, cycloalkyl or aryl group; and
X is a polar functional group selected from the group consisting of —I, —Br, —Cl, —SH, —N 3 , imine, aldehyde, sulfone, cyanide and phosphite; and
a photoresist layer over the middle material layer, the photoresist layer comprising an organometallic dimer obtained by partial hydrolysis of a precursor organometallic compound represented by the following formula:
R n -M-L 4-n ,
wherein:
M is a metal selected from the group consisting of tin (Sn), antimony (Sb) and indium (In);
R is an organic ligand with 1 to 30 carbon atoms bound to M with a metal-carbon bond;
L is a hydrolysable ligand; and
n is an integer of 1 or 2,
wherein the hydrolysis promoting agent is adapted to increase water content in the photoresist layer, thereby causing complete hydrolysis of the organometallic dimer to form an organometallic oxide hydroxide dodecamer cluster through condensation prior to patterning the photoresist layer.
8. The multilayer stack of claim 7 , wherein R 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenethyl, naphthyl, phenoxy, methylphenoxy, dimethylphenoxy, ethylphenoxy or phenyloxy methyl.
9. The multilayer stack of claim 7 , wherein the middle material layer further comprises a surfactant, a quencher or a combination thereof.
10. The multilayer stack of claim 7 , wherein the precursor organometallic compound is n-butyltrichlorotin.
11. A multilayer stack for use in a lithography patterning process, comprising:
a planarization layer over a substrate;
a bottom anti-reflective coating (BARC) layer over the planarization layer, the BARC layer comprising a crosslinkable polymer comprising at least one cross-linkable pendant group attached to a polymer backbone, a hydrolysis promoting agent selected from the group consisting of trimethylolpropane and pentaerythritol and an acid generator; and
a photoresist layer over the BARC layer, the photoresist layer comprising an organometallic dimer obtained by partial hydrolysis of a precursor organometallic compound represented by the following formula:
R n -M-L 4-n ,
wherein:
M is a metal selected from the group consisting of tin (Sn), antimony (Sb) and indium (In);
R is an organic ligand with 1 to 30 carbon atoms bound to M with a metal-carbon bond;
L is a hydrolysable ligand; and
n is an integer of 1 or 2,
wherein the hydrolysis promoting agent is adapted to increase water content in the photoresist layer, thereby causing complete hydrolysis of the organometallic dimer to form an organometallic oxide hydroxide dodecamer cluster through condensation prior to patterning the photoresist layer.
12. The multilayer stack of claim 11 , wherein the hydrolysis promoting agent comprises pentaerythritol.
13. The multilayer stack of claim 11 , wherein the acid generator comprises 2,4,4,6-tetrabromocyclohexadienone, 2-hydroxyhexyl p-toluenesulfonate or 2-nitrophenyl tosylate.
14. The multilayer structure of claim 1 , wherein the precursor organometallic compound comprises t-butyltrichlorotin, i-butyltrichlorotin, n-butyltrichlorotin, sec-butyltrichlorotin, ipropyltrichlorotin, n-propyltrichlorotin, t-butyltribomotin, i-butyltribomotin, nbutyltribomotin, sec-butyltribomotin, i-propyltribromotin or n-propyltribromotin.
15. The multilayer structure of claim 1 , wherein the precursor organometallic compound is n-butyltrichlorotin (C 4 H 9 SnCl 3 ).
16. The multilayer structure of claim 1 , wherein the polymer comprises a polymer backbone and a plurality of pendant groups bound to the polymer backbone, the plurality of pendant groups including a first pendant group comprising a crosslinkable functional group for crosslinking the polymer, a second pendant group comprising an aromatic group for absorbing light and a third pendant group comprising a cyclic group for enhancing adhesion of the BARC layer to the photoresist layer.
17. The multilayer structure of claim 16 , wherein the crosslinkable functional group comprises epoxy or alkene.
18. The multilayer stack of claim 9 , wherein the quencher is an organic amine or an organic acid.
19. The multilayer stack of claim 11 , wherein the precursor organometallic compound comprises t-butyltrichlorotin, i-butyltrichlorotin, n-butyltrichlorotin, sec-butyltrichlorotin, ipropyltrichlorotin, n-propyltrichlorotin, t-butyltribomotin, i-butyltribomotin, nbutyltribomotin, sec-butyltribomotin, i-propyltribromotin or n-propyltribromotin.
20. The multilayer stack of claim 11 , wherein the middle layer further comprises an anionic surfactant, a cationic surfactant or a nonionic surfactant.