Communications film, resulting in terraces of bilayer steps. The regions of arachidic acid in the mixed LB film can be removed by washing in ethanol to leave behind islands of cadmium arachidate molecules. ExperimentalLangmuir-Blodgett films of arachidic acidicadmium arachidate were prepared using a constant-perimeter barrier trough (purpose-built) located in a Class 10000 microelectronics clean room. The subphase was ultrapure water obtained from a commercial reverse osmosisideionizationiUV sterilization system. The arachidic acid (eicosanoic acid) was obtained from Sigma (99 % purity). For salt formation, CdCIp (BDH, Analar Grade) was added to the suhphase to give an overall concentration of 2.5 x lo4 M. The pH was adjusted to 5.7i0.1 by the addition of HCI (BDH, Aristar Grade) or ammonia solution (BDH, Aristar Grade). Transfer of the floating monolayers onto hydrophilic silicon wafers ((100) orientation) was undertaken at a suhphase temperature of 19i1 "C and a deposition pressure of 30 mN m-'. The dipping speed was 2 mm m i d . Transfer ratios for all the monolayers deposited were 1.0oi0.05.A Digital Instruments Nanoscope Ill atomic force microscope was used to examine the topographical nature of the arachidic acidicadmium arachidate LB film surface following dipping and after washing in ethanol (to remove the free acid). All of the high resolution AFM images were acquired in air at room temperature using the contact mode and a 1 pm x 1 pm piezoelectric scan head. A 200 pm narrow-legged silicon nitride cantilever with a small spring-constant ( k = 0.06 Nm-') was used to minimize film damage due to high contact forces. The lower resolution images were acquired in air using the tapping mode in conjunction with a 10 ym x 10 Fm piezoelectric scan head. This technique employs a stiff silicon cantilever oscillating at a large amplitude near its resonance frequency (several hundred kilohertz) which is detected by an optical beam system. AFM images are presented as unfiltered data in gray-scale and were found to be stable and unchanged over long periods of observation.

Deep ultraviolet (UV) irradiation is shown to modify organosilane self-assembled monolayer (SAM) films by a photocleavage mechanism, which renders the surface amenable to further SAM modification. Patterned UV exposure creates alternating regions of intact SAM film and hydrophilic, reactive sites. The exposed regions can undergo a second chemisorption reaction to produce an assembly of SAMs in the same molecular plane with similar substrate attachment chemistry. The UV-patterned films are used as a template for selective buildup of fluorophores, metals, and biological cells.

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The photochemistry of organosilanes was used to (1) create mixed monolayers having continuously adjustable surface free energies and (2) affect high resolution adhesion and spatial orientation of biological cells on silica substrates. Monolayers were formed from two materials, an aminoalkylsilane, NH2(CH2)2NH(CH2)3Si(OCH3)3 (EDA), and a perfluorinated alkylsilane, CF3(CF2)s(CH2)2Si(CH3)zC1 (1 3F), and were characterized by ellipsometry and water contact angle measurements. Deep UV (193 nm) radiation was used to induce photochemical changes in the cell-adhesive EDA monolayers. X-ray photoelectron spectroscopy indicated that the amine groups of EDA were removed by the exposure, leaving only Si-OH or alkyl fragments having 5 3 carbons. The exposed substrates were then reacted with 13F to form mixed monolayers or hydrophobic monolayers that inhibited cell adhesion in the irradiated regions. The degree of 13F reactivity with EDA in the unirradiated regions was observed to be solvent-dependent, suggesting that conformational states of the surface amine groups lead to a reduction in their accessibility. The selective photochemistry was exploited to produce high resolution molecular patterns, defined using patterned irradiation, that were mapped with scanning Auger electron spectroscopy. The patterns were used to spatially control the adhesion and direct the outgrowth of rat hippocampal neurons and porcine aortic endothelial cells in vitro. Patterns of controlled geometry may provide new approaches to the study of surface-directed growth, intercellular communication, and organogenesis or be used to control the alignment of individual cells with transducer elements in biosensors and implants. IntroductionRecent reports have indicated that monolayer systems can be targeted for a variety of applications, including cell adhesion and patterning.',2 Several techniques have been introduced in the past few years for the production of patterned self-assembled monolayers (SAMs) of organic functionalitie~.~~~ One approach utilizes conventional photoresist methodology to produce high resolution patterns for the adhesion and growth of cells.2 A fundamentally new technique involves direct modification of SAMs by patterned deep UV e x p o s~r e .~~~ Molecules in the exposed regions of a SAM absorb the radiation and undergo photocleavage to yield surface residues. These residues can then be modified with a second type of functionality. This technique offers several

A new approach for the selective electroless (EL) metallization of surfaces is described. Surfaces are modified with a chemisorbed ligand-bearing organosilane film, and then catalyzed with an aqueous Pd(II) catalyst solution. The catalyzed substrate is then immersed in an EL metal deposition bath to complete the metallization process. The ligating surfaces are produced by molecular self-assembly of 2-(trimethoxysilyl)ethyl-2-pyridine (PYR) on silicon or silica substrates. The catalyst consists of chloride-containing aqueous Pd(II) solutions buffered at pH 5.0 to 6.4; oligomeric chloro and/or hydroxo-bridged Pd(II) complexes act as the catalytic species at the surface. The activity of the catalyst has been characterized and modeled as a function of solution pH, [C1-], and time from preparation. Adhesion of the Pd(II) EL catalyst to the substrate involves covalent bond formation with the surface ligand. An average minimum Pd(II) level on the surface of -10 '~ Pd atom cm 2 is shown to be necessary to initiate EL metallization of the substrate with an EL Co bath. This process involves fewer steps and displays improved selectivity compared to processes that involve a conventional Pd/Sn catalyst. Fabrication of high resolution metal patterns using the new metallization chemistry in conjunction with deep UV patterning of PYR films is demonstrated.

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This paper presents an approach for fabricating surfaces with precise positional control of chemical functionalities at submicron resolutions using direct patterning of organosilane self-assembled monolayer films (SAFs) with lithographic exposure tools. Although the process is of general applicability, microelectronics applications are emphasized here. The suitability of monolayer SAFs for high resolution patterning is discussed and deep UV photochemical mechanisms for several classes of SAFs are presented. Selective electroless metallization of patterned SAFs provides sufficient plasma etch resistance and compatibility with current microelectronics processing technologies to allow fabrication of functioning Si MOSFET test structures. Unique features of the process, including an ability to utilize a variety of substrates and control metal film adhesion by judicious choice of the SAF, are discussed.

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