Photoresist composition

1 . A method of manufacturing a semiconductor device, comprising:

forming a photoresist layer over a substrate;

exposing the photoresist layer to an EUV radiation; and

developing the exposed photoresist layer, wherein the photoresist layer has a composition comprising:

a metal complex comprising a metallic core and at least one ligand bonded to the metallic core, wherein the at least one ligand comprises an alkenyl group, an alkynyl group, or a combination thereof, the at least one ligand comprises a saturated carbon directly bonded to the metallic core, the saturated hydrocarbon is bonded directly to a carbonyl group and bonded to one of an alkyl group and an alkenyl group, the metal complex comprising the metallic core and the at least one ligand comprising the alkenyl group, the alkynyl group, or the combination thereof is selected from the group consisting of following formulae (A1), (A2), (A4), (A7) and (A13):

 wherein A in the formulae (A1), (A2), (A4) and (A7) is the metallic core of the metal complex, and a moiety bonded to A is the at least one ligand of the metal complex.

2 . The method of claim 1 , wherein the at least one metallic core comprises an oxide of Cs, Ba, La, Ce, In, Sn, Ag, or Sb.

3 . The method of claim 1 , wherein the composition of the photoresist layer further comprises:

a solvent, wherein the metal complex is dissolved in the solvent, and the metal complex is at a weight percentage in a range from 0.1 weight % to 10 weight % of a weight of the solvent.

4 . The method of claim 3 , wherein the solvent comprises propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), gamma-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl iobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), or a combination thereof.

5 . The method of claim 1 , wherein the composition of the photoresist layer further comprises at least one additive comprising a radical inhibitor, a thermal radical initiator, or a photo radical initiator.

6 . The method of claim 5 , wherein the at least one additive is at a weight percentage in a range from 0.1 weight % to 30 weight % of a weight of the metallic core.

7 . The method of claim 1 , wherein during exposing the photoresist layer to the EUV radiation, the at least one ligand of the metal complex is cleaved by the EUV radiation.

8 . The method of claim 1 , further comprising:

after exposing the photoresist layer to the EUV radiation, performing a post-exposure baking to the photoresist layer at a temperature in a range from 80° C. to 350° C.

9 . An extreme ultraviolet lithography (EUVL) method, comprising:

turning on a droplet generator to eject a metal droplet toward a zone of excitation in front of a collector;

turning on a laser source to emit a laser toward the zone of excitation, such that the metal droplet is heated by the laser to generate an EUV radiation;

guiding the EUV radiation, by using one or more first optics, toward a reflective mask in an exposure device; and

guiding the EUV radiation, by using one or more second optics, reflected from the reflective mask toward a photoresist coated substrate in the exposure device,

wherein the photoresist has a composition comprising:

a metal complex comprising a metallic core and at least one ligand bonded to the metallic core, wherein the at least one ligand comprises a saturated carbon directly bonded to the metallic core, the saturated hydrocarbon is bonded directly to a carbonyl group and bonded to one of an alkyl group and an alkenyl group, the metal complex comprising the metallic core and the at least one ligand comprising the alkenyl group is selected from the group consisting of following formulae (A1), (A2), (A4) and (A7):

 wherein A in the formulae (A1), (A2), (A4) and (A7) is the metallic core of the metal complex, and a moiety bonded to A is the at least one ligand of the metal complex.

10 . The method of claim 9 , wherein the composition of the photoresist further comprises:

a solvent, wherein the metal complex is dissolved in the solvent, and the metal complex is at a weight percentage in a range from 0.1 weight % to 10 weight % of a weight of the solvent.

11 . The method of claim 9 , wherein the composition of the photoresist further comprises at least one additive comprising a photo acid generator (PAG), a photo decomposable base (PDB), a quencher, or a thermal acid generator (TAG).

12 . The method of claim 11 , wherein the quencher comprises a formula (K1):

13 . The method of claim 9 , wherein the at least one metallic core comprises an oxide of Cs, Ba, La, Ce, In, Sn, Ag, or Sb.

14 . A photoresist, having a composition comprising:

a metal complex configured to be used in extreme ultraviolet (EUV) radiation lithography and comprising a metallic core and at least one ligand bonded to the metallic core, wherein the metal complex is selected from the group consisting of following formulae (A1), (A2), (A4), (A5), (A7), (A8), (A13), (A14) and (A17):

 A is the metallic core of the metal complex, and a moiety bonded to A is the at least one ligand of the metal complex, the at least one ligand comprises a saturated hydrocarbon directly bonded to the metallic core, the saturated hydrocarbon is bonded to one of an alkyl group and an alkenyl group and directly bonded to a carbonyl group.

15 . The photoresist of claim 14 , wherein the composition of the photoresist further comprises a radical inhibitor selected from the group consisting of:

phenothiazine, 2-tert-butyl-1,4-benzoquinone, 1,4-benzoquinone, hydroquinone, 4-tert-butylpyrocatechol, 2,6-di-tert-butylphenol, p-phenylenediamine, hydroxylamine, diethylhydroxylamine, 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 1,1-diphenyl-2-picrylhydrazyl free radical, copper (II) dibutyldithiocarbamate, tert-butylhydroquinone, 6-tert-butyl-2,4-xylenol, 2,6-di-tert-butyl-p-cresol, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy-TEMPO, 97%), 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,6-di-tert-butyl-4-methylphenol (BHT, (99%), tert-butyl hydroquinone (TBHQ, 97%), 2,6-di-tert-butyl-4-methoxyphenol (DTBMP, 98%), and 4-methoxyphenol.

16 . The photoresist of claim 14 , wherein the composition of the photoresist further comprises a thermal radical initiator selected from the group consisting of:

azobisisobutyronitrile (AIBN), 2,2′-azobis(2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4 dimethylvaleronitrile) (ADVN), 4,4′-azobis(4-cyanovaleric acid) (ACVA), dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2-methylpropionamidine) dihydrochloride (AAPH), 2,2′-azobis[2-(2-imidazolin-2-yl)-propane] dihydrochloride, tert-butyl hydroperoxide (TBHP), cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide (BPO), dicyandiamide, cyclohexyl tosylate, diphenyl(methyl)sulfonium tetrafluoroborate, benzyl(4-hydroxyphenyl)-methylsulfonium hexafluoroantimonate, and (4-hydroxyphenyl)methyl-(2-methylbenzyl)sulfonium hexafluoroantimonate.

17 . The photoresist of claim 14 , wherein the composition of the photoresist further comprises a photo radical initiator selected from the group consisting of:

camphorquinone, acetophenone, 3-acetophenol, 4-acetophenol, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 3-hydroxybenzophenone, 3,4-dimethylbenzophenone, 4-hydroxybenzophenone, 4-benzoylbenzoic acid, 2-benzoylbenzoic acid, methyl 2-benzoylbenzoate, 4,4′-dihydroxybenzophenone, 4-(dimethylamino)-benzophenone, 4,4′-bis(dimethylamino)-benzophenone, 4,4′-bis(diethylamino)-benzophenone, 4,4′-dichlorobenzophenone, 4-(p-tolylthio)benzophenone, 4-phenylbenzophenone, 1,4-dibenzoylbenzene, benzil, 4,4′-dimethylbenzil, p-anisil, 2-benzoyl-2-propanol, 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone, 1-benzoylcyclohexanol, benzoin, anisoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, O-tosylbenzoin, 2,2-diethoxyacetophenone, benzil dimethylketal, 2-methyl-4′-(methylthio)-2-morpholinopropiophenone, 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone, 2-isonitrosopropiophenone, anthraquinone, 2-ethylanthraquinone, sodium anthraquinone-2-sulfonate monohydrate, 9,10 phenanthrenequinone, dibenzosuberenone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthen-9-one, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, bis(4-tert-butylphenyl)-iodonium triflate, Bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, [4-[(2-hydroxytetradecyl)-oxy]phenyl]phenyliodonium hexafluoroantimonate, bis[4-(tert-butyl)phenyl]-iodonium tetra(nonafluorotert-butoxy)aluminate, cyclopropyldiphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium triflate, tri-p-tolylsulfonium hexafluorophosphate, 4-nitrobenzenediazonium tetrafluoroborate, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl) vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methylfuran-2-yl) vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(9-oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene 1,5-Salt, 2-(9-oxoxanthen-2-yl) propionic acid diazabicyclo[4.3.0]non-5-ene salt, 2-(9-oxoxanthen-2-yl) propionic acid 1,8-diazabicyclo[5.4.0]-undec-7-ene salt, acetophenone o-benzoyloxime, 2-nitrobenzyl cyclohexylcarbamate, and 1,2-bis(4-methoxyphenyl)-2-oxoethyl cyclohexylcarbamate.

18 . The photoresist of claim 14 , wherein the composition of the photoresist further comprises a solvent, the metal complex is at a weight percentage in a range from 0.1 weight % to 10 weight % of a weight of the solvent.

19 . The photoresist of claim 14 , wherein the additive is at a weight percentage in a range from 0.1 weight % to 30 weight % of a weight of the metallic core.

20 . The method of claim 14 , wherein the at least one metallic core comprises an oxide of Cs, Ba, La, Ce, In, Sn, Ag, or Sb.