Daniel A. Freedman

Ruthenium-arene complexes of curcumin: X-ray and density functional theory structure, synthesis, and spectroscopic characterization, in vitro antitumor activity, and DNA docking studies of (p-cymene)Ru(curcuminato)chloro.

The in vitro antiproliferative activity of the title compound on five tumor cell lines shows preference for the colon-rectal tumor HCT116, IC(50) = 13.98 μM, followed by breast MCF7 (19.58 μM) and ovarian A2780 (23.38 μM) cell lines; human glioblastoma U-87 and lung carcinoma A549 are less sensitive. A commercial curcumin reagent, also containing demethoxy and bis-demethoxy curcumin, was used to synthesize the title compound, and so (p-cymene)Ru(demethoxy-curcuminato)chloro was also isolated and chemically characterized. The crystal structure of the title compound shows (1) the chlorine atom linking two neighboring complexes through H-bonds with two O(hydroxyl), forming an infinite two-step network; (2) significant twist in the curcuminato, 20° between the planes of the two phenyl rings. This was also seen in the docking of the Ru-complex onto a rich guanine B-DNA decamer, where a Ru-N7(guanine) interaction is detected. This Ru-N7(guanine) interaction is also seen with ESI-MS on a Ru-complex-guanosine derivative.

EUV Resists based on Tin-Oxo Clusters

We have studied the photolysis of tin clusters of the type [(RSn)12O14(OH)6] X2 using extreme ultraviolet (EUV, 13.5 nm) light, and developed these clusters into novel high-resolution photoresists. A thin film of [(BuSn)12O14(OH)6][p-toluenesulfonate]2 (1) was prepared by spin coating a solution of (1) in 2-butanone onto a silicon wafer. Exposure to EUV light caused the compound (1) to be converted into a substance that was markedly less soluble in aqueous isopropanol. To optimize the EUV lithographic performance of resists using tin-oxo clusters, and to gain insight into the mechanism of their photochemical reactions, we prepared several compounds based on [(RSn)12O14(OH)6] X2. The sensitivity of tin-oxide films to EUV light were studied as a function of variations in the structure of the counter-anions (X, primarily carboxylates) and organic ligands bound to tin (R). Correlations were sought between the EUV sensitivity of these complexes vs. the strength of the carbon-carboxylate bonds in the counteranions and vs. the strength of the carbon-tin bonds. No correlation was observed between the strength of the carboncarboxylate bonds in the counter-anions (X) and the EUV photosensitivity. However, the EUV sensitivity of the tinoxide films appears to be well-correlated with the strength of the carbon-tin bonds. We hypothesize this correlation indicates a mechanism of carbon-tin bond homolysis during exposure. Using these tin clusters, 18-nm lines were printed showcasing the high resolution capabilities of these materials as photoresists for EUV lithography.

Fluorinated Acid Amplifiers for EUV Lithography

Five new compounds were synthesized for use as acid amplifiers in EUV (13.5 nm) photoresists. Four compounds act as acid amplifiers and decompose by autocatalytic kinetics to generate fluorinated sulfonic acids, essential for the simultaneous improvement of resolution, sensitivity, and line edge roughness (LER) in EUV photoresists. The decomposition rates were studied using (19)F NMR in the presence and absence of 1.2 equiv of tri-tert-butylpyridine. Three acid amplifiers decomposed 490, 1360, and 1430 times faster without base than with base. Preliminary lithographic evaluations show that cis-1-methyl-2-(4-(trifluoromethyl)phenylsulfonyloxy)cyclohexyl acetate simultaneously improves the resolution, LER, and sensitivity of an EUV photoresist.

Platinum and palladium oxalates: positive-tone extreme ultraviolet resists

Abstract. Here, we present platinum and palladium mononuclear complexes with EUV photosensitivity and lithographic performance. Many platinum and palladium complexes show little or no EUV sensitivity; however, we have found that metal carbonates and metal oxalates (L2M(CO3) and L2M(C2O4); M=Pt or Pd) are sensitive to EUV. The metal carbonates give negative-tone behavior. The most interesting result is that the metal oxalates give the first positive-tone EUV resists based on mononuclear organometallic compounds. In particular, (dppm)Pd(C2O4) (dppm=1,1-bis(diphenylphosphino)methane) (23) prints 30-nm dense lines with Esize of 50  mJ/cm2. Derivatives of (23) were synthesized to explore the relationship between the core metal and the resist sensitivity. The study showed that palladium-based resists are more sensitive than platinum-based resists. The photoreaction has been investigated for two of our most promising resists, (dppm)Pd(C2O4) (23) and (Ph2EtP)2PdC2O4 (27). Our experiments suggest the loss of CO2 and the formation of a zerovalent L4Pd complex upon exposure to light. We have identified dppm2Pd(δ(P)23.6) as the main photoproduct for (23) and (Ph2EtP)4Pd (δ(P)32.7) as the main photoproduct for (27).

High-sensitivity molecular organometallic resist for EUV (MORE)

We have developed organometallic carboxylate compounds [RnM(O2CR’)2] capable of acting as negativetone EUV resists. Overall, the best and fastest resists contain antimony, are pentavalent and the carboxylate group contains a polymerizable olefin (e.g. acrylate, methacrylate or styrenecarboxylate). Evidence suggests that high sensitivity is achieved through the polymerization of olefins in the exposed region. We have performed a systematic sensitivity study of molecules of the type RnM(O2CR’)2 where we have studied seven R groups, four main group metals (M), and three polymerizable carboxylate groups (O2CR’). We found that the greatest predictor of sensitivity of the RnSb(O2CR’)2 resists is their level of polymerizable olefins. We mathematically define the polymerizable olefin loading (POL) as the ratio of the number of olefins vs. the number of non-hydrogen atoms. Linear and log plots of Emax vs. POL for a variety of molecules of the type R3Sb(O2CR’)2 lend insight into the behaviour of these resists.

Low-line edge roughness extreme ultraviolet photoresists of organotin carboxylates

Abstract. Pure thin films of organotin compounds have been lithographically evaluated using extreme ultraviolet lithography (EUVL, 13.5 nm). Twenty compounds of the type R2Sn(O2CR′)2 were spin-coated from solutions in toluene, exposed to EUV light, and developed in organic solvents. Exposures produced negative-tone contrast curves and dense-line patterns using interference lithography. Contrast-curve studies indicated that the photosensitivity is linearly related to the molecular weight of the carboxylate group bound to tin. Additionally, photosensitivity was found to be linearly related to free radical stability of the hydrocarbon group bound directly to tin (R=phenyl, butyl, and benzyl). Dense-line patterning capabilities varied, but two resists in particular show exceptionally good line edge roughness (LER). A resist composed of an amorphous film of (C6H5CH2)2Sn(O2CC(CH3)3)2 (1) achieved 1.4 nm LER at 22-nm half-pitch patterning and a resist composed of (C6H5CH2)2Sn(O2CC6H5)2 (2) achieved 1.1 nm LER at 35-nm half-pitch at high exposure doses (600  mJ/cm2). Two photoresists that use olefin-based carboxylates, (C6H5CH2)2Sn(O2CCH⏧CH2)2 (3) and (C6H5CH2)2Sn(O2CC(CH3)⏧CH2)2 (4), demonstrated better photospeeds (5  mJ/cm2 and 27  mJ/cm2) but worse LER.

Metal–coumarin complexes: synthesis and characterization of 7-isocyanocoumarin ligands and Mo(CO)4(7-isocyanocoumarin)2 complexes. X-ray crystal structure of Mo(CO)4(7-isocyano-4-trifluoromethylcoumarin)2

Abstract The preparation and characterization of four different 7-isocyanocoumarin ligands is described. The four ligands are 3,4-dimethyl-7-isocyanocoumarin (Dmic), 7-isocyano-4-methylcoumarin (Mic), 3-chloro-7-isocyano-4-methylcoumarin (Cmic) and 7-isocyano-4-trifluoromethylcoumarin (Tic). Reaction of the four 7-isocyanocoumarin ligands with Mo(CO)4(pip)2 (pip=piperidine) gave the Mo(CO)4L2 complexes. IR and UV–vis spectra of the complexes indicate that the 7-isocyanocoumarin ligands are significantly stronger π-acids than simple aromatic isocyanide ligands. An intense visible absorption band, assigned to a metal-to-ligand charge transfer (MLCT) transition, is present in the UV–vis spectra of the four Mo(CO)4L2 complexes. Excitation into the MLCT band of the Mic, Cmic, and Dmic complexes gave yellow–orange emission at room temperature in methylene chloride solution. Photolysis of Mo(CO)4(Mic)2 with P(Ph)3 in THF solution produced Mo(CO)3(PPh3)(Mic)2.

Low-LER tin carboxylate photoresists using EUV

Pure thin films of organotin compounds have been lithographically evaluated using extreme ultraviolet lithography (EUVL, 13.5 nm). Twenty-one compounds of the type R2Sn(O2CR’)2 were spin-coated from solutions in toluene, exposed to EUV light, and developed in organic solvents. Exposures produced negative-tone contrast curves and dense-line patterns using interference lithography. Contrast-curve studies indicated that the Emax values were linearly related to molecular weight when plotted separately depending upon the hydrocarbon group bound directly to tin (R = butyl, phenyl and benzyl). Additionally, Emax was found to be linearly related to free radical stability of the hydrocarbon group bound directly to tin. Dense-line patterning capabilities varied, but two resists in particular show exceptionally good line edge roughness (LER). A resist composed of an amorphous film of (C6H5CH2)2Sn(O2CC(CH3)3)2 (13) achieved 1.4 nm LER at 22 nm half-pitch patterning and a resist composed of (C6H5CH2)2Sn(O2CC6H5)2 (14) achieved 1.1 nm LER at 35 nm half-pitch at high exposure doses (600 mJ/cm2). Two photoresists that use olefin-based carboxylates, (C6H5CH2)2Sn(O2CCH=CH2)2 (11) and (C6H5CH2)2Sn(O2CC(CH3)=CH2)2 (12), demonstrated much improved photospeeds (5 mJ/ cm2 and 27 mJ/cm2) but with worse LER.

EUV resists comprised of main group organometallic oligomeric materials

We present the synthesis and preliminary lithographic evaluation of Molecular Organometallic Resists for EUV (MORE) that contain post transition metals. These post transition metal nuclei have high EUV optical density so they can utilize a high fraction of the incident photons. We will describe two technical approaches for EUV resist platforms that contain bismuth. Approach 1: Combination of organometallic compounds with photoacid generators. Approach 2: Combination of high-oxidation state metal-center oligomers that utilize carboxylate anions bound to the metal centers.

Advanced development techniques for metal-based EUV resists

Pure thin-films of unimolecular organometallic photoresists were lithographically evaluated using extreme ultraviolet light (EUV, λ = 13.5 nm) and developed using solutions containing carboxylic acids. Optimization of development solutions used with a cobalt-oxalate EUV resist (NP1, 2) led to a switch in lithographic tone from negative to positive. Additional optimization led to an improvement in top loss (35 to 7%) with development in cyclohexanone and 2-butanone, respectively. We saw a drastic improvement in photo-speed (Emax = 5 mJ/cm2) and contrast of the negative-tone imaging with development in certain acidic solutions. Additionally, carboxylic acid solutions provide excellent development conditions for resists that we, in the past, have been unable to successfully develop.