Top-Surface Imaging Using Selective Electroless Metallization of

Chapter 14

Top-Surface Imaging Using Selective Electroless Metallization of Patterned Monolayer Films 1

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J. M . Calvert , W. J. Dressick , C. S. Dulcey , M . S. Chen , J. H . Georger , D. A. Stenger , T. S. Koloski , and G. S. Calabrese 2

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Downloaded by FUDAN UNIV on December 16, 2016 | http://pubs.acs.org Publication Date: November 23, 1993 | doi: 10.1021/bk-1994-0537.ch014

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Code 6900, Naval Research Laboratory, Washington, DC 20375-5320 Geo-Centers, Inc., Fort Washington, MD 20744 Shipley Company, Marlborough, MA 01752 2

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A top surface imaging microlithographic process that involves selective elec troless (EL) metallization of surfaces modified with ligating organosilane ultrathinfilms(UTFs) is described. Fabrication of metal features with 0.4 μm linewidths using 193 nm exposure is shown. Metal-ligand complexation chem istry is used for covalent attachment of a Pd(II) catalyst to the UTF-treated surface. The molecular nature of the UTF layer is shown to control the adhesive strength of the EL metal deposit; values of > 500 psi on single crystal Si wafers have been obtained. The ligand-based UTF process is a promising approach for a range of microelectronic applications where high resolution, adherent, selective metallization is required.

The great majority of useful resist systems for microlithographic applications involve irradiation of a thick (~ 0.5-2 fim) polymer film (1, 2). Exposure takes place throughout the entire bulk of the film and changes the characteristics of the polymer in the irradiated regions by a variety of mechanisms (chain scission, crosslinking, destruction of a dissolution inhibitor, etc.) (2-3). Surface imaging approaches, in which some property of only the outer layer of the resist is modified, were developed (4, 5) to alleviate some of the problems in the thick film approach. For optical lithography, especially with deep U V ( "R-Si-O-(substrate)" + 3HX 3

X = -C1, - O C H , - O C H


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Films containing pyridyl (PYR), ethylenediamine (EDA), and diethylenetriamine (DETA), and ethylenediaminetriacetic acid (EDTA) ligands have been prepared in this manner. Surface-bound bipyridyl (BPY) and quinolinyl (QUIN) ligands were prepared using chemical coupling reactions, in which amide or sulfonamide bond formation served to graft the ligand onto an aminosilane treated substrate. Chemical structures of various ligand silanes are shown in Figure 1. Ligand UTFs were characterized by a variety of techniques, including U V spectroscopy, contact angle goniometry, x-ray photoelectron spectroscopy (XPS), and ellipsometry (20, 21, 25). U V spectra of ligand films such as PYR, BPY, PEDA, and QUIN on fused silica exhibit absorptions characteristic of the aromatic chromophores in the molecules; U V spectra of EDA, DETA, and E D T A films are too weak to be useful as diagnostics of film quality. Water contact angles of the films were 10 ° for freshly made films of D E T A and EDTA, 20 ° for BPY, 35 ° for EDA, - 45-50 ° for PYR, 60-65 ° for P E D A and - 55-60 ° for QUIN. XPS spectra of ligand films on non-Si substrates (e.g., Pt) showed the presence of both N and Si. Ellipsometry of PYR, EDA, and PEDA films on Si native oxide substrates gave typical thicknesses of ~5-10 A , indicative of essentially monolayer coverage. UTF Patterning and Selective Metallization In our original process, metallization was obtained by the adsorption of a Pd/Sn catalyst (26) to a U T F coated surface. The interaction between the catalyst and the film was relatively non-specific. Polar, hydrophilic surfaces (e.g., treated with aliphatic or aromatic amines) could be metallized as well as non-polar hydrophobic surfaces (e.g., treated with aliphatic or aromatic hydrocarbons). However, the Pd/Sn catalyst was found not to adsorb to clean, smooth silica or silicon surfaces, which have a high density of silanol (Si-OH) groups (6, 16, 17). Patterned metallization could therefore be obtained on U T F treated surfaces only by photochemically removing the entire organic functionality of the film, leaving a pattern of silanol groups to which the Pd/Sn catalyst did not adsorb. As a consequence, the molecular design of UTF materials for practical lithographic applications was constrained by the necessity to have high absorbance at the patterning wavelengths and efficient photocleavage to generate a surface silanol. Metallization of substrates using any of the ligand UTFs shown in Fig. 1 was obtained by treating the surface with an aqueous catalyst solution based on P d a " (20). Binding of Pd(II) by the surface ligands was confirmed by U V and surface spectroscopic techniques. Films of PYR treated with Pd(II)-containing 2

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Thompson et al.; Polymers for Microelectronics ACS Symposium Series; American Chemical Society: Washington, DC, 1993.

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Electroless Metallization of Patterned Monolayer Films


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solutions have been shown to exhibit increased U V absorption at ~235 nm, consistent with formation of a Pd(II)-pyridine complex (22). Rutherford backscattering spectrometry of ligand UTFs treated with the Pd(II) catalyst gives Pd surface concentrations of ~1 X 10 atoms/cm . Immersion of a Pd(II)catalyzed UTF surface directly into an E L plating bath results in homogeneous metallization of the substrate. The ligand-based process is highly selective. For example, surfaces that are treated with non-ligating UTFs (e.g., phenethyltrichlorosilane, which is structurally analogous to P Y R without the N atom) cannot be metallized using this approach (27). The ligand process is also simpler than the Pd/Sn catalyst system because no intermediate "acceleration" step is required to prepare the catalyst for metal deposition. Pattern formation with the ligand U T F approach has been achieved by exposing the films to masked deep U V radiation from ArF (193 nm) and KrF (248 nm) excimer lasers, and from H g / X e lamp-based sources (25). Irradiation destroys the ligating ability of the film, creating regions of intact and modified ligand binding sites. Upon treating the surface with the catalyst solution, Pd(II) is covalently bound only in the regions that have intact ligating sites. After rinsing, the surface is immersed in an E L plating bath, and metal is deposited selectively at the catalytic sites. The ligand-based selective metallization process is shown schematically in Figure 2. A variety of techniques have been used to characterize the ligating film following photochemical modification. PYR films on fused silica substrates were exposed to either ~1.5 J / c m of 193 nm radiation or ~4.5 J / c m of 248 nm radiation. The U V absorptions between 190-260 nm, characteristic of the pyridyl chromophore, were greatly reduced at these doses (22). A concomitant decrease in hydrophobicity of the P Y R surface (water contact angle changes from 45 ° to < 10 °) was observed upon exposure. Laser desorption Fourier transform mass spectrometry showed that the ethylpyridyl group was removed from the surface upon irradiation at 193 nm. XPS analysis of Pt substrates treated with P Y R showed that Si remained on the surface after exposure of the ligand film. These observations suggest a photochemical mechanism in which the P Y R molecule is cleaved at the Si-C bond, eliminating both the pyridine ligand and ethyl spacer, and leaving Si-OH residues at the surface. Selective binding of the Pd(II) catalyst to patterned P Y R films was demonstrated by scanning Auger microscopy, which indicated the presence of Pd only in the unexposed regions of the surface. Immersion of the catalyzed surface in E L Co or N i plating baths resulted in patterned metal deposition, yielding an overall positive tone image. Figure 3 is a combination scanning electron micrograph (SEM) and Auger analysis, which shows ~20 wide E L Ni lines and superimposed line scans for Si and Ni (29). A SEM showing ~0.4 fjum Ni lines produced by 193 nm contact printing with the P Y R film is shown in Figure 4. The photochemistry and selective metallization of other ligand UTFs has also been investigated. The E D A silane, consistent with its weak absorption at 193 nm, has been reported to have a photochemical dose (elimination of the N signal by XPS analysis) of -13-15 J / c m (23, 30). However, the P E D A silane which has a large absorption at 195 nm due to the phenyl chromophore, exhibits a dose for selective metallization of -300 mJ/cm at 193 nm on a Si thermal oxide substrate.


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LIGATING UTF

Figure 2. Schematic of ligand-based selective metallization process. The goalpost structures represent ligating groups of the UTF layer. Removal of the goalpost indicates loss of ligating ability, and not necessarily complete removal of the ligand or organofunctional groups in the film.

Figure 3. Overlay of SEM photo and Auger line scans of patterned E L N i plated wafer. A Si native oxide wafer was coated with the P Y R film, exposed to - 4 J / c m of 193 nm radiation ( 2 9 ) (Questek Model 2000 A r F laser; - 4 mJ/cm /pulse) through a low resolution fused silica mask in hard contact with the wafer. The wafer was treated with the Pd(II) solution for 30 min, rinsed with DI water, and metallized with Shipley NIPOSIT* 468 electroless N i bath (10% strength) for 20 min. A PHI Model 660 Auger spectrometer was used to analyze the sample. The trace that is low in the dark regions and high in the bright regions is the N i element scan; the other trace is the Si scan. 2

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Figure 4. SEM photo of E L N i patterns produced using a high resolution grating mask. The experimental conditions for producing the patterned wafer were as described in the caption of Fig. 3. The micrograph was obtained using a Cambridge Model S200 electron microscope.


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Controlled Adhesion of E L Metal Deposits In addition to selectivity, another attribute of the ligand-based metallization process is that the strength of the catalyst binding to the surface should be "tunable" by virtue of the formation constant, K , of the Pd-ligand complexation reaction (20). K is known to be affected by factors such as the type of ligand donor atoms (N-, S-, P-, O-, etc.) and the number of binding sites (denticity) (32). We have observed that monodentate ligands, such as films of PYR, exhibit lower adhesion than that observed with films of corresponding bi- or tridentate ligands (22). For example, -400 A thick E L Co films can be deposited without flaking on a silicon substrate using the ligand-based metallization process with films of PYR. However, > 70% of the metal film is removed during a tape peel test. In contrast, Co films in excess of 2500 A can be deposited without flaking onto the same Si surface using the BPY silane as the ligating film. Peel tests show that no Co metal is removed from BPY-treated surfaces. A similar trend has been observed with E L Ni plated Si wafer surfaces: the PYR film exhibits only partial metal adhesion during a Scotch tape peel test, whereas all of the metallized biand tridentate ligand films in Fig. 1 pass the test completely. Average stud pull values of -100 psi and - 300 psi have been measured for the adhesive strength of Ni plated P Y R and BPY surfaces, respectively; however, individual metallized BPY samples have yielded pull strengths in excess of 500 psi (22). f


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CONCLUSIONS The U T F ligand-based chemistry offers several unique features compared to conventional photoimaging processes for IC fabrication. It is one of the few true top surface, as opposed to near surface, imaging processes currently under development. As such, it is particularly well suited for exposure systems such as 193 nm, projection x-ray, and low voltage electron and ion beams that can best take advantage of a surface imaging resist (25). The use of Ni instead of a silicon oxide as the etch mask considerably diminishes the required thickness of the layer and should provide increased latitude in pattern transfer processing. The ultimate resolution of the ligand-based UTF process will likely be limited by the graininess or lateral spread of the catalyst/EL metal, rather than by the latent image created by exposure of the UTF. Further research along these lines should also lead to fundamental insights about the detailed mechanism of the initiation of E L deposition at surfaces. The use of patterned ligand surfaces as a reactivity template for the selective attachment of a variety of species other than Pd catalysts and E L metals is currently under investigation. The ligand-based chemistry also has several attractive features for use as an advanced metallization process where high throughput, adhesive, selective metallization on a variety of substrates is crucial (33). The versatility of the process with regard to surface attachment of UTFs to most key technological materials such as polymers, plastics, and diamond has already been demonstrated (20, 21, 34). The elimination of an "acceleration" step simplifies and reduces the overall cost of the E L metallization process; also, the selective metal deposition is


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additive in nature, so that metal is deposited only where it is required. The ability to manipulate the macroscopic adhesive strength of the E L metal deposit by "tuning" the molecular metal-ligand binding strength parameters is potentially of considerable significance in the fabrication of high density interconnects for P C / P W B and multi-chip module applications, especially where surface roughening is undesirable.


ACKNOWLEDGMENTS Funding for this work was provided by the Manufacturing Technology Office of the Assistant Secretary of the Navy, Shipley Co., and the Office of Naval Research. Experimental assistance from H . Stever and M . Thomas (both of National Semiconductor Co.) for adhesion measurements and C. Gossett and C. Cotell for RBS measurements is gratefully acknowleged, as well as helpful discussions with M . Peckerar. TSK acknowleges the Office of Naval Technology for a postdoctoral fellowship at the Naval Research Laboratory. REFERENCES 1. W. Moreau, Semiconductor Lithography, Plenum Press, NY, 1988. 2. Polymers in Microlithography, E . Reichmanis, S.A. MacDonald and T. Iwayanagi, eds., ACS Symposium Series No. 412, ACS Press, Washington, DC, 1989. 3. R. Dammel Proc. PMSE 1992, 66, 1841. 4. G.N. Taylor, L . Stillwagon, and T. Venkatesan J. Electrochem Soc., 1984, 131, 1658. 5. O. Nalamasu, F.A. Baiocchi and G.N. Taylor, in Polymers in Microlithography, E . Reichmanis, S.A. MacDonald and T. Iwayanagi, eds., ACS Symposium Series No. 412, ACS Press, Washington, DC, 1989, p.189-209. 6. J.M. Calvert, et. al. Solid State Technology 1991, 34(10), 77. 7. J.M. Calvert, et. al. J. Electrochem. Soc. 1992, 139, 1677. 8. G.N. Taylor, R.S. Hutton, and D.L. Windt Proc. SPIE 1990, 1343, 258. 9. H.I. Smith and M.L. Schattenburg in Semiconductor Materials and Processing Technologies, J.M. Poate, ed., Kluwer Academic Publishers, Dordrecht, The Netherlands, 1992, p. 1-14. 10. S.W. Kuan, et. al. J. Vac. Sci. Tech. 1989, B7, 1745. 11. F. Coopmans and B. Roland Proc. SPIE 1986, 631, 34. 12. J.W. Thackeray, et. al. Proc. SPIE 1990, 1185, 2. 13. S.A. MacDonald Proc. PMSE 1992, 66, 97. 14. G.S. Calabrese, et. al. Proc. SPIE 1991, 1466, 528. 15. K. Radigan and S. Liddicoat Proc. SPIE, 1992, 1672, 394. 16. J.M. Schnur, et. al. U.S. Patent 5,077,085. 17. J.M. Calvert, et. al. Thin Solid Films 1992, 210 / 211, 359. 18) J.M. Calvert, et. al. J. Vac. Sci. Technol. B 1991, 9(6), 3447. 19. C.S. Dulcey, et. al. Science 1991, 252, 551. 20. J.M. Calvert, W.J. Dressick, G.S. Calabrese, and M . Gulla U.S. Patent Application 07/691,565, pending. 21. W.J. Dressick, et. al. Proc. MRS, 1992, 260, 659. 22. 2-(trimethoxysilyl)ethyl-2-pyridine (PYR) (21), N-(2-aminoethyl)-3Thompson et al.; Polymers for Microelectronics ACS Symposium Series; American Chemical Society: Washington, DC, 1993.

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aminopropyltrimethoxysilane (EDA) (23), trimethoxysilylpropyldiethylenetriamine (DETA), and N-[(3-trimethoxysilyl)propyl]ethylenediamine triacetic acid (EDTA) UTFs were prepared by treating a clean substrate with a 1% solution of the appropriate organosilane in acidic aqueous methanol for 20 min. Film treated surfaces were then baked at 120 °C for 5 min. BPY and QUIN UTFs were prepared by treating a propylamine silane-modified substrate with an acetonitrile solution of 2,2'-bipyridine-4,4'-carbonyl chloride or 8-quinolinylsulfonyl chloride in the presence of triethylamine (20). The reaction of trimethoxyorganosilanes with a hydroxylated surface typically involves formation of at least one siloxane-surface bond per molecule of coupling agent. The other coordination sites of Si may be involved in intermolecular siloxane bonding, or exist as free Si-OH groups (24). B. Arkles in Huls Silicon Compounds Register and Review, 5th Edition, R . Anderson, G.L. Larson, and C. Smith, eds., Huls America, Piscataway, NJ, 1991; p. 59. J.H. Georger, et. al. Thin Solid Films 1992, 210/211, 716. The Pd/Sn catalyst is these studies was obtained from Shipley Co. It should be noted that Pd/Sn catalysts from other manufacturers may have different surface chemical characteristics, and results from these experiments may not be generalizable to all Pd/Sn formulations. Ligand-modified surfaces are also amenable to E L metallization using the conventional Pd/Sn catalyst. With the ligand-based metallization process, pattern formation should be achievable by any photochemical or beam process that is capable of spatially modifying the ability of the film to perform its usual function, e.g., binding metal ions. Patterning of U T F ligand films using alternative radiation sources, including focussed ion beams, projection x-ray, and STM is currently under investigation. For experiments in which patterned metal surfaces were to be analyzed by electron beam techniques, Si native oxide was used as the substrate to minimize charging effects. However, a higher U V dose was required for native oxide in comparison to a fused silica or Si thermal oxide substrates (~ 1.5 J / c m for the latter). The necessity of increased U V dose on the less insulating substrate has been observed previously for non-ligating UTFs (19) and may be related to more efficient excitation energy relaxation into the substrate. D.A. Stenger, et. al J. Am. Chem. Soc 1992, 114, 8435. A . E . Martell and R . M . Smith Critical Stability Constants, Plenum Press, NY, 1975. Other U T F materials, which utilize the ligand-based metallization chemistry but incorporate a different photochemical reaction mechanism, have recently exhibited selective metallization at doses of

Top-Surface Imaging Using Selective Electroless Metallization of

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