A novel chemically amplified resist (CAR) was synthesized incorporating a photoacid generating (PAG) moiety, etch resistant nanoparticle, and various acrylated monomers. The addition of acrylated monomers was found to promote good film formation and to improve film adhesion. Directly tethering the nanoparticle into the polymer increases the etch performance of the resist and helps avoid any potential issues with phase separation of components in the resist film. The PAG in these materials is also directly incorporated into the resist backbone. It has been shown that these materials display enhanced sensitivity and contrast using LVEBL. This paper will discuss the material characteristics and lithographic performance of these materials using 2 keV, 10 KeV, and 20 KeV electron beam (EB) exposure. For example, these materials have demonstrated an extremely high sensitivity of only 0.6 μC/cm2 at 2 KeV. Contrast and sensitivity data along with preliminary imaging results will be presented for these materials. Initial imaging results at 20 keV are promising. Achieving similar resolution at low keV also appears to be possible with this material. The trade-off between sensitivity and resolution will also be presented for different electron beam accelerating potentials. Etch resistance and selectivity of this material will also be studied and compared to PHOST and novolac based resists. It will be demonstrated that such materials show great promise for advanced resist applications in a variety of next generation lithography (NGL) applications including electron beam lithography.
Current resist materials used for electron beam lithography applications, such as mask making, have relatively low contrasts as compared to modern optical resists. Recently, our group has been investigating two component, polsulfone-novolac (SNS) resists which offer high sensitivities and moderate contrasts for electron beam lithography. Surface inhibition, which can help to reduce top surface loss in unexposed and partially exposed regions of the resist, is a very desirable property in such resists in order increase resist contrast. The main phenomenon being investigated in this work is the effect of soft bake temperature on surface inhibition in SNS resists. It was found that surface inhibition decreases dramatically in this resist system as a function of increasing bake temperature above 90°C. Results from this study indicate that there is a segregation of the polar polysulfone inhibitor away from the resist-air interface at bake temperatures above 90°C. Results from studies using various techniques including X-ray photoelectron spectroscopy and contact angle measurements to investigate this phenomenon are reported. Methods to enhance surface inhibition, and hence improve resist contrast, such as using surfactant loaded developers were also investigated in this work.
Dissolution rate monitors (DRMs) and related techniques have been used for a number of years to study the dissolution behavior of photoresist materials in detail. Due to the relative difficulty in obtaining commercial DRM instruments, crude methods for measuring dissolution rates such as the (formula availble in paper) have been developed. In this method, the resist-coated substrate is immersed in a developer solution for a fixed development time, removed and dried, and the remaining film thickness is measured. The dissolution rate information for the resist is then calculated from the slope of the resist thickness versus development time data. This method is simple and can easily be used in a fab environment, but it suffers from a number of limitations. For example, this method is very inaccurate for resists that develop very quickly (< 20 seconds) such as many modern chemically amplified resists. Such quick development times are often crucial in exploring the full behavior of a resist. A much better method for measuring the dissolution behavior of photoresist films is to use interferometric methods such as those suggested originally by Dill and coworkers. In this work, an extremely flexible and simple instrument based on inexpensive, commercially available, PC card spectrometers will be presented that can be used quite robustly in both fab and laboratory environments for measuring the dissolution behavior of photoresist films. The hardware required in order to construct such a simple apparatus will be discussed along with various experimental configurations that are appropriate for different measurement tasks. Thin film thickness estimation using the DRM can be done using either single wavelength versus time interferometry data (plot of reflected light intensity versus development time) or the complete multiwavelength spectra obtained from a spectroscopic reflectometry system. Film thickness estimation using single wavelength data analysis is good for films that: develop completely to the substrate, do not swell during the development process, and do not develop very fast (i.e., > 100 nm/s). Hence for films that either have very long development times (typically very thick films of the order of ~ 5μm), films that have very short development times (usually with dissolution rates exceeding 100 nm/s), or films that swell during development, film thickness determination using the multiwavelength reflectance spectra is the best solution. With this motivation, a multiwavelength interferometric data analysis software (MIDAS) has been developed in this work that can robustly perform both single and multiwavelength DRM data analysis. It has been found to be very useful in analyzing thin film dissolution data with dissolution rates exceeding 400 nm/s. Another useful application has been to measure swelling in the processing of photoresists and other polymer thin films. For example, such resist swelling appears to be an issue in the case of resists or other polymers developed or cleaned using high pressure CO2. The basic approaches and algorithms used for thin film thickness/rate determination in MIDAS will be discussed. The advantages and disadvantages of this method will be compared with quartz crystal microbalance techniques as well. It will also be shown that these two methods can be coupled for demanding applications. Results from the use of the MIDAS software in various applications will be presented.
The goal of this work was to develop a resist material for high-keV (>=10 keV) electron beam patterning with: (1) high sensitivity (~10 (mu) C/cm2 50 keV), (2) high contrast, and (3) etch resistance comparable to current optical resists. In this work, an approach was desired that used multi-component resist design to (1) decouple sensitivity from etch performance and to improve resist contrast but (2) avoided environmental stability problems. Therefore, a resist design first proposed by researchers at IBM in the late 1980s that uses an electron beam sensitive polymeric dissolution inhibitor (poly (2-methyl-1-pentene co 2-ethoxyethyl-methallyl ether sulfone)) in conjunction with novolac resins was explored in this work. Significant advancements have been made in high performance novolac resins used for advanced I-line resist materials since the original work performed at IBM. Thus, one of the primary reasons for reinvestigating this resist design is to evaluate the performance of resists formulated using polysulfone dissolution inhibitors in conjunction with such advanced novolac resins. In this work, the basic lithographic performance of sulfone-novolac system (SNS) resists formulated using modern novolac resins was evaluated and optimized by varying the resist film preparation and development conditions.
The goal of this work was to develop a resist material for high-keV (>=10 keV) electron beam patterning with: (1) high sensitivity (~10 (mu) C/cm2 50 keV), (2) high contrast, and (3) etch resistance comparable to current optical resists. In this work, an approach was desired that (1) used multi-component resist design to decouple sensitivity and etch performance and improve contrast but (2) avoided environmental stability problems. Therefore, a resist design first proposed by researchers at IBM in the late 1980s that uses an electron beam sensitive polymeric dissolution inhibitor (poly (2-methyl-1-pentene co 2-ethoxyethyl-methallyl ether sulfone)) in conjunction with novolac resins was explored in this work. In this paper, the fundamental behavior of the polysulfone dissolution inhibitor upon exposure to e-beam and heat was studied. This behavior establishes the processing window for the polysulfone dissolution inhibitor. The thermal stability of polysulfone was studied using TGA, FTIR, and mass spectrometry. The results show that accelerated decomposition of polysulfone occurs above 150 degree(s)C. Polysulfone decomposition upon exposure to e-beam was studied using (1) ellipsometry, (2) quartz crystal microbalance methods, and (3) FTIR. The results of this study show that polysulfone is highly sensitive to electron beam exposure and most of it decomposes at a very low nominal e-beam dose.
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