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New resists are needed to advance EUV lithography. Tailored design of efficient photoresist is impossible without fundamental understanding of EUV induced chemistry. Resists incorporating high cross-section elements efficiently utilize EUV photons via radiation absorption by core-level electrons, resulting in emission of primary electrons. However, this is only an initial step in the process. Auger emission, molecular fragmentation, and subsequent electron-resist interactions are also critical. Understanding all these steps is crucial to harness all the deposited energy for improved patterning results.
In this work, we present recent results of multimodal experimental approaches to study photoresist materials. To build our grasp of EUV photochemistry from the ground up we aim for understanding the whole variety of processes happening after absorption of an EUV photon by a single building block of resist material – a resist molecule. Model photoresist constituent molecules functionalized with halogen atoms, are isolated in the gas phase and exposed to tunable EUV radiation from the Advanced Light Source, Berkeley Lab and the direct processes are investigated by photoelectron spectroscopy and photoionization mass spectrometry. We quantify the performance of several candidate molecules in terms of photoemission cross-sections and electron yield per primary photoionization event. We demonstrate that some prototype resist molecules can emit several (photo- and Auger) electrons after single EUV photon absorption. Following the electron emission, the atomic relaxation leads to the molecule fragmentation, which also depends on the halogen functionalization. Secondary electron-driven reactions are studied by tunable electron impact ionization and dissociative electron attachment mass spectrometry. We demonstrate that even very low kinetic energy electrons may lead to the molecule dissociation.
While gas-phase studies do provide insight into the primary EUV photon or electron induced events in the individual resist molecules, we seek to understand these processes in the condensed phase as this is where industrially relevant processes will occur. We discuss techniques allowing for generation of resist nanoparticles of different morphology, representing either condensed resist or a substrate coated by a resist film. The same techniques, as applied to investigate resist’s building blocks, are used to study the condensed resist material, connecting our understanding of the fundamental phenomena from each isolated molecule to the solid state system.
This work presents the low temperature plasma-enhanced atomic layer deposition (PE-ALD) of TiN, a promising plasmonic synthetic metal. The plasmonics community has immediate needs for alternatives to traditional plasmonic materials (e.g. Ag and Au), which lack chemical, thermal, and mechanical stability. Plasmonic alloys and synthetic metals have significantly improved stability, but their growth can require high-temperatures (>400 °C), and it is difficult to control the thickness and directionality of the resulting film, especially on technologically important substrates. Such issues prevent the application of alternative plasmonic materials for both fundamental studies and large-scale industrial applications. Alternatively, PE-ALD allows for conformal deposition on a variety of substrates with consistent material properties. This conformal coating will allow the creation of exotic three-dimensional structures, and low-temperature deposition techniques will provide unrestricted usage across a variety of platforms. The characterization of this new plasmonic material was performed with in-situ spectroscopic ellipsometry as well as Auger electron spectroscopy for analysis of TiN film sensitivity to oxide cross-contamination. Plasmonic TiN films were fabricated, and a chlorine plasma etch was found to pattern two dimensional gratings as a test structure. Optical measurements of 900 nm period gratings showed reasonable agreement with theoretical modeling of the fabricated structures, indicating that ellipsometry models of the TiN were indeed accurate.
KEYWORDS: Electron beam lithography, Scanning electron microscopy, Scanning probe microscopy, Chemistry, Calibration, Line scan image sensors, Electron beams, Atomic force microscopy, Lithography, Line edge roughness
One of the key challenges to high resolution resist patterning is probing the resist properties at length scales commensurate with the pattern size. Using a new scanning probe microscopy (SPM), Peak Force™ tapping, we map exposure dependent nanoscale modulus of the exposed/developed resist patterns with sub-10 nm resolution. By innovative electron beam exposure pattern design, the SPM technique reveals that resist modulus follows the height contrast profile, but with a shift to higher exposure doses. SEM image analysis of patterned resist structures confirm that the best line-space patterns are achieved at exposure dose where modulus reaches its maximum and shows how modulus can be used to probe patternability of resist systems.
Numerous studies report the importance of nanoscale metallic features to increase the sensitivity of gas sensors, biodetectors, and for the fabrication of the new-generation plasmonic devices. So far, nanoimprint lithography has not shown the capability to pattern a metallic structure that would both be sub-15 nm and sufficiently thick to ensure electrical conductance. To overcome these limitations, we report a step and repeat nanoimprint lithography (SR-NIL) on a pre-spin-coated layer stack. This work reports the fabrication of sub-15-nm lines that are 15-nm thick and have a 50-nm-half-pitch grating with 35-nm-thick metal, which represents the new state of the art for SR-NIL.
One of the key challenges to high resolution resist patterning is pattern collapse. Using a new scanning probe microscopy (SPM), Peak ForceTM tapping, we map nano-mechanical properties-- modulus, adhesion, and dissipation-- of the exposed/developed resist structures with sub-10 nm resolution. Properties are compared across a carbon based negative resist with and without cross-linking. The SPM technique reveals that cross-linking significantly enhances the mechanical properties to give a champion resolution of sub 20 nm half-pitch in a chemically amplified negative resist system. Beyond mechanical properties, surface morphology and redistribution kinetics were examined using complementary techniques and reveal additional benefits with cross-linking.
Here, we report the highest recorded resolution for a negative-tone, carbon-based, chemically amplified (CA) resist of 20 nm half-pitch (HP) using both E-beam and EUV exposure systems. The new chemistry incorporates variable amounts of oxetane (0, 5, 10 and 20%) cross-linker into a base of Noria-MAd (methyl-admantane) molecular resist. Cross-linkable resists showed simultaneous improvements in surface energy, structural integrity, and swelling to ensure collapse free 20nm HP patterns and line-edge roughness (LER) down to 2.3 nm. EUV exposed Noria-Ox (5%) cross-linked resist patterns demonstrated 5 times improvement in Z-factor (for 24 nm HP) over Noria-MAd alone.
This paper will review the top down technique of ICP etching for the formation of nanometer scale structures. The increased difficulties of nanoscale etching will be described. However it will be shown and discussed that inductively coupled plasma (ICP) technology is well able to cope with the higher end of the nanoscale: features from 100nm down to about 40nm are relatively easy with current ICP technology. It is the ability of ICP to operate at low pressure yet with high plasma density and low (controllable) DC bias that helps greatly compared to simple reactive ion etching (RIE) and, though continual feature size reduction is increasingly challenging, improvements to ICP technology as well as improvements in masking are enabling sub-10nm features to be reached. Nanoscale ICP etching results will be illustrated in a range of materials and technologies. Techniques to facilitate etching (such as the use of cryogenic temperatures) and techniques to improve the mask performance will be described and illustrated.
David Carlton, Brian Lambson, Zheng Gu, Scott Dhuey, Li Gao, Brian Hughes, Deirdre Olynick, Charles Rettner, Andreas Scholl, Brian Youngblood, Anthony Young, Ilya Krivorotov, Stuart Parkin, Jeffrey Bokor
As conventional Silicon-based transistors reach their scaling limits, novel devices for performing computations have
emerged as alternatives to continue the improvements in information technology that have benefited society over the
past 40 years. One candidate that has shown great promise recently is a device that performs logical computations using
dipole coupled nanomagnets. In this paper, we discuss recent advances that have led to a greater understanding of signal
propagation in nanomagnet arrays. In particular, we highlight recent experimental work towards the imaging of a
propagating magnetic cascade.
Scanning probe-based methods for surface modification and lithography are an emerging method of
producing sub 20-nm features for nanoelectronic applications. In this study, we have demonstrated the nanoscale lithography based on patterning of 10 to 50-nm-thick calix[4]arene by electric-field-induced electrostatic scanning probe lithography. The features size control is obtained using electrostatic interactions and depends on the applied bias and speed of the AFM tip. The width of the obtained lines and dots varies from 10 to 60 nm depending on tip-sharpness, tip-substrate separation and tip-bias voltage.
Plasma etching is an enabling technology in nano optic, nanoelectronic devices, nano electro mechanical systems
(NEMS) and nanoresolution templates for nano imprint lithography (NIL). With shrinkage, one must overcome
significant challenges to meet the stringent profile and CD goals necessary for nanoscale applications. Using the
example of Si nanoimprint template fabrication, we show how ion/sidewall/mask interactions can dominate feature
profile evolution at the nanoscale and what to look for successful pattern transfer. Gas chopping or multiplexed etching,
generally used for deep silicon etching, is often avoided at the nanoscale due to unacceptable undercut and sidewall
scalloping. We demonstrate a multiplexed etching process in silicon with sub-5 nm amplitude scallops which is well
suited for NEMS and nano optics applications and which reduces the deleterious role of ion/sidewall/mask interactions at
the nanoscale.
One of the many technology decisions facing the semiconductor industry for the 45 nm node (and beyond) is the selection of the best critical dimension (CD) metrology equipment to meet the needs of process equipment suppliers and semiconductor manufacturers. In an effort to address this need we fabricated advanced metrology structures using the Nanowriter e-beam writing tool at the Center for X-Ray Optics (CXRO) at Lawrence Berkeley National Laboratory. The structures include lines and holes both in resist and etched into substrates. The smallest isolated CDs are 16 nm, while the smallest holes are less than 50nm. We used these samples to characterize a variety of metrology technologies. In this paper we discuss the capability of those technologies to measure structures having dimensions representative of the 45 nm and 32 nm nodes.
We have utilized the nanoimprint lithography process described this paper to fabricate a rewritable, nonvolatile memory cell with an equivalent density of 6.4 Gbits/cm2. The architecture of the circuit was based on an 8x8 crossbar structure with an active molecular layer sandwiched between the top and bottom electrodes. A liftoff process was utilized to produce the top and bottom electrodes, made of Pt/Ti bilayers. The active molecular layer was deposited by the Languir-Blodgett technique. We proposed the use of a new class of nanoimprint resist formulated by dissolving a polymer in its monomer, such as poly(benzyl methacrylate) dissolved in benzyl methacrylate (~8%/92% wt). The new resist enabled us to achieve Pt /Ti lines of 40 nm in width and 130 nm in pitch, as described in this paper. Our overall nanofabrication process has the advantages of relatively low temperature (~70°C) and pressure (~500 psi or 4.5 MPa), both of which are critical to preserving the integrity of the molecular layer.
While interferometry is routinely used for the characterization and alignment of lithographic optics, the ultimate measure of performance for these optical systems is the transfer of an image or pattern into photoresist. Simple yet flexible exposure systems play an important role in this task because they allow complex system-dependent effects to be isolated from the printing results. This enables the most direct lithography evalaution of the optical system under investigation. To address tehse issues for commercial-class EUV optics, a synchrotron-based programmable illuminator exposrue station has been implemented at Lawrence Berkeley National Laboratory (the Advanced Light Source). As previously presented, this static microfield exposure system has been used to lithography characterize a 4-mirror optical system designed for the EUV Engineering Test Stand (ETS) prototype stepper. Based on the lithographic characterization, here we present a detailed performance analysis of the 0.1-NA ETS Set-2 optic. Operation of the static printing system with the Set-2 optic yielded approximately 330 exposed wafers, where each wafer contains one or more focus-exposure matrices. A wide variety of parameters were studied includign, among others, illumination conditions, resist thickness, and mask tone. Here we present a subset of this data in terms of process-window results. The resutls demonstrate a depth of focus (DOF) approximately 2μm for isolated 70-nm line features, 1 μm for nested 70-nm line features, and 0.5μm for 70-nm contacts on 270-nm pitch.
While interferometry is routinely used for the characterization and alignment of lithographic optics, the ultimate performance metric for these optics is printing in photoresist. The comparison of lithographic imaging with that predicted from wavefront performance is also useful for verifying and improving the predictive power of wavefront metrology. To address these issues, static, small-field printing capabilities have been added to the EUV phase- shifting point diffraction interferometry implemented at the Advanced Light Source at Lawrence Berkeley National Laboratory. The combined system remains extremely flexible in that switching between interferometry and imaging modes can be accomplished in approximately two weeks.
The soft x-ray, full-field microscope XM-1 at Lawrence Berkeley National Laboratory's (LBNL) Advanced Light Source has already demonstrated its capability to resolve 25-nm features. The soft x-ray, full-field microscope XM-1 at Lawrence Berkeley National Laboratory's (LBNL) Advanced Light Source has already demonstrated its capability to resolve 25-nm features. This was accomplished using a micro zone plate (MZP) with an outer zone width of 25 nm. Limited by the aspect ratio of the resist used in the fabrication, the gold-plating thickness of that zone plate is around 40 nm. However, some applications, in particular, biological imaging, prefer improved efficiency, which can be achieved by high-aspect-ratio zone plates. We accomplish this by using a bilayer-resist process in the zone plate fabrication. As our first attempt, a 40-nm-outer-zone-width MZP with a nickel-plating thickness of 150 nm (aspect ratio of 4:1) was successfully fabricated. Relative to the 25-nm MZP, this zone plate is ten times more efficient. Using this high-efficiency MZP, a line test pattern with half period of 30 nm is resolved by the microscope at photon energy of 500 eV. Furthermore, with a new multilayer mirror, the XM-1 can now perform imaging up to 1.8 keV. An image of a line test pattern with half period of 40 nm has a measured modulation of 90%. The image was taken at 1.77 keV with the high-efficiency MZP with an outer zone width of 35 nm and a nickel-plating thickness of 180 nm (aspect ratio of 5:1). XM-1 provides a gateway to high-resolution imaging at high energy. To measure frequency response of the XM-1, a partially annealed gold island pattern was chosen as a test object. After comparison with the SEM image of the pattern, the microscope has the measured cutoff of 19 nm, close to the theoretical one of 17 nm. The normalized frequency response, which is the ratio of the power density of the soft x-ray image to that of the SEM image, is shown in this paper.
The XM-1 is a soft x-ray full-field microscope that uses zone plates for the condenser and objective lenses. One of the main features of XM-1 is the high spatial resolution, which is made possible by the fine features of the objective zone plate. At present, the microscope uses a zone plate with an outer zone width of 25 nm. Several test patterns containing periodic lines and spaces were fabricated to measure the resolution of the microscope. Experimental data shows that the microscope can resolved 25 nm features. As simulations indicate that good contrast can be observed with even smaller features, test patterns with finer features are being fabricated to actually determine the resolution limit of the microscope.
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