Patternable materials for next-generation lithography

One of the salient truths facing the microelectronics industry today is that photolithography tools are unable to meet the resolution requirements for manufacturing next-generation devices. In the past, circuit feature sizes have been minimized by reducing the exposure wavelength used for patterning. However, this strategy failed with the worldwide dereliction of 157 nm lithography in 2003. Extreme ultraviolet (EUV) lithography still faces many technical challenges and is not ready for high volume manufacturing. How will the microelectronics industry continue to innovate without regular advances in photopatterning technology? Regardless of which paradigm is adopted, new materials will probably be required to meet the specific challenges of scaling down feature sizes and satisfying the economic ultimatum of Moore’s Law. In the search for higher resolution patterning tools, device manufacturers have identified block copolymer (BCP) lithography as a possible technique for next-generation nanofabrication. BCP self-assembly offers access to sub-5 nm features in thin films, well beyond the resolution limits of photolithography. However, BCP materials must be carefully designed, synthesized, and processed to create lithographically interesting features with good etch resistance for pattern transfer. In this dissertation, we describe a pattern transfer process for 5 nm BCP lamellae and a directed self-assembly (DSA) process for aligning 5 nm structures in thin films. To achieve defect-free alignment, the interfacial interactions between the BCP and pre-patterned substrate must be precisely controlled. We also discuss a new process for selectively modifying oxidized chromium films using polymer brushes, which could further improve the aforesaid DSA process. To facilitate better pattern transfer of BCP structures, several new BCPs with “self-developing” blocks were synthesized and tested. These materials depolymerize and evaporate in strongly acidic environments, leading to developed BCP features without the need for etching or solvent. “Self-developing” polymers may also be useful materials for traditional photolithography. Chemically amplified resists used in manufacturing today are fundamentally limited by a trade-off between sensitivity and pattern quality. To overcome this problem, we present a new type of photoresist that relies on depolymerization, rather than catalysis, to achieve amplification without producing significant roughness or bias in the final patternChemical Engineerin

Catalysis and materials development for photolithography

textIn recent years the microelectronics industry as found itself at an impasse. The tradition pathway towards smaller transistors at lower costs has hit a roadblock with the failure of 157 nm lithography and the continued delays in 13.5 nm extreme ultra violet light sources. While photolithography has been able to keep pace with Moore’s law over the past four decades, alternative patterning technologies are now required to keep up with market demand. The first section of this dissertation discusses the new resolution enhancement technique develop in the Willson lab termed pitchdivision. Through the incorporation of specifically tailored photobase generators (PBGs) into commercially available resists, the resolution of current 193 tools may be doubled. Special two-stage PBGs were designed and synthesized to increase the image fidelity of pitchdivision patterns. The next project deals with the design, synthesis, and evaluation of resists that find amplification through unzipping polymers. An aromatizing polyester polymer that acts as dissolution inhibitor in novolac and is inherently sensitive to 13.5 nm exposure is discussed. Initial results show excellent sensitivity and promise towards a new class of EUV resists.Chemistr

Photocrosslinkable nonlinear optical polymers and directly-patternable polyimide dielectrics

textThe development of high-efficiency nonlinear optical (NLO) polymers has opened up many opportunities in the field of electro-optics. However, current NLO polymers do not meet stability requirements for semiconductor integration. In an effort to improve this, we examined the effects of crosslinking following electric field poling. A series of photocrosslinkable polymers bearing side chain chromophores was synthesized, poled and evaluated on the basis of the thermal stability of Second Harmonic Generation. Photoinitiation allowed for control of the onset of curing. Crosslinking was monitored by FTIR and optimal conversion was achieved by applying a slow temperature ramp during exposure. The ultimate stability of the poled polymers was directly related to the number of crosslinking substituents attached to the chromophore pendant group. With two reactive groups per chromophore significant SHG was retained at temperatures beyond the polymer Tg. In integrated circuit packaging there is a need for directly-patternable polymers of low dielectric constant. Bridging the gap between the high-value silicon chip and circuit board is a substrate comprising alternating layers of metal conductor and polymer dielectric. PMDA-ODA, an aromatic polyimide, meets many of the requirements for integration and can be patterned using a photobase generator (PBG). Due to absorbance by the PMDA-ODA precursor, this PBG must have activity at visible wavelengths. Several oxime urethanes were synthesized and evaluated as candidate long wavelength PBG. These compounds exhibit clean photochemistry and high visible light sensitivity. Unfortunately, carbamate thermal stability is insufficient for patterning PMDA-ODA. For improved material properties, PMDA-TFMB, a fluorinated polyimide, was also evaluated. Importantly, the polymer precursor is sufficiently transparent to employ thermally-stable near-UV photobases. With photobase, 2.5 micron features were resolved in PMDA-TFMB. An ancillary benefit of this methodology is reduced cure temperature (~200 °C), a traditional drawback of polyimides. This material demonstrates a dielectric constant near 3 and a thermal expansion coefficient (CTE) of approximately 6 ppm/°C in-plane. Through-plane thermal expansion is somewhat problematic, with a CTE of approximately 160 ppm/°C, and will likely require a nanoparticle composite strategy. However, this combination of material and lithographic properties make PMDA-TFMB a promising candidate for this application.Chemistr

Photo-definable dielectrics with improved lithographic, mechanical, and electrical properties

Permanent dielectric materials are integral to the fabrication of microelectronic devices and packaging. Dielectrics are used throughout devices to electrically and mechanically isolate conductive components. As such, they are required to have low electrical permittivity and robust mechanical properties. For packaging applications, dielectrics can be directly photo-definable. Dielectrics need to have excellent lithographic properties. These properties are pivotal for enabling high yield and low cost fabrication of reliable, energy efficient devices. The aim of this work was to develop new positive tone dielectrics which have improved or application-specific lithographic, mechanical, and electrical properties. To this end, several new dielectric polymers and chemistries were evaluated and characterized. Initially, it was desired to develop a positive tone, polynorbornene (PNB) dielectric that utilizes diazonaphthoquinone (DNQ) photochemistry. Cross-linking was achieved with epoxy cross-linkers during a thermal cure. Several DNQ-containing compounds were evaluated, but only one had good miscibility with PNB. The dissolution characteristics of PNB were measured with respect to polymer composition, DNQ loading, and cross-linker loading. PNB films exhibited unique dissolution properties, and these measurements allowed for an optimum formulation to be developed. A formulation with 20 pphr DNQ and 10 pphr epoxy cross-linker had sufficient inhibition in unexposed regions and fast dissolution in exposed regions. The resulting dielectric was the first positive tone, DNQ-based PNB dielectric. After achieving photo-definability, the cross-linking of the cured dielectric was evaluated by characterizing the mechanical properties. It was discovered that DNQ acted as a cross-linker in these films, and this insight was key to achieving good curing of the dielectric. Several experiments were performed to support this conclusions, and the reaction kinetics of this cross-linking reaction were evaluated. This effort produced a functional, positive tone dielectric with a sensitivity of 408 mJ cm-2 and contrast of 2.3. The modulus was 2.0 to 2.6 GPa and the dielectric constant of 3.7 to 3.9, depending on the curing conditions. The DNQ cross-linking results led to the investigation of other cross-linking chemistries for positive tone dielectrics. A chemically amplified (CA) photochemistry was utilized along with a Fischer esterification cross-linking reaction. Patterning and cross-linking were demonstrated with a methacrylate polymer. Successful positive tone lithography was demonstrated at a high sensitivity of 32.4 mJ cm-2 and contrast of 5.2. Cross-linking was achieved at 120°C as shown by residual stress and solubility measurements. The CA photochemistry and Fischer esterification cross-linking were also demonstrated using a PNB dielectric, which was shown to have improved lithographic properties: a sensitivity of 8.09 mJ cm-2 and contrast of ≥ 14.2. Work was performed to evaluate the effect of the polymer composition on the mechanical and electrical properties. A polymer with 60 mol% hexafluoroisopropanol norbornene and 40 mol% tert-butyl ester norbornene exhibited a dielectric constant of 2.78, which is lower than existing positive tone dielectrics. It also outperformed existing dielectrics in several other categories, including dark erosion, volume change, cure temperature, and in-plane coefficient of thermal expansion. However, a limitation of this dielectric was cracking in thick films. The final study was to improve the mechanical properties of this CA PNB dielectric specifically to enable 5 µm thick films. First, a terpolymer was tested that included a non-functional third monomer. The dielectric constant increased to 3.48 with 24 mol% of the third monomer. Second, low molecular weight additives were used to lower the modulus. Only one of the five tested additives enabled high quality, thick films. This additive did not significantly affect the dielectric constant at low loadings. An optimized formulation was made, and processing parameters were studied. The additive decreased the lithographic properties, lowering the sensitivity to 175 mJ cm-2 and lowering the contrast to 4.36. In all, this work produced three functional dielectrics with positive tone photo-definability and good lithographic properties. Each dielectric can serve a variety of purposes in microelectronics packaging.Ph.D

CHEMICALLY AMPLIFIED RESISTS FOR ELECTRON BEAM LITHOGRAPHY

This thesis describes the development of chemically amplified resists for electron beam lithography. The techniques and concepts oflithography are discussed and the motivations for the development of chemically amplified resists are examined. The experimental techniques used in this work are then described. Two groups of resists, derivatives of fullerene and derivatives of triphenylene, were tested for chemical amplification and the results obtained from the research are presented. A systematic study of the response of several methanofullerenes and polysubstituted triphenylene derivatives before and after chemical amplification is presented. Films of the compounds were prepared by dissolving the resists in solvents such as chloroform and adding to the solution various concentrations of certain photoacid generators and crosslinkers, and spin coating the mixture on hydrogen terminated silicon wafers. The films were irradiated using 20 keY electrons. Post exposure bakes between 90 to 120 'C for 30 to 180 s were applied to the resists before development with non-polar solvents such as monochlorobenzene. Most of the chemically amplified resists showed sensitivity enhancement compared to their pure counterparts. Fullerene derivative, 3' H-cyclopropa [I, 9, 5, 6] fullerene-C60-Ih - 3', 3'- carboxylic [ 2-2-(2-hydroxyethoxy) ethoxyl ethyl] ester (a mixture of adducts) demonstrated the highest sensitivity enhancement with the incorporation of an epoxy novolac crosslinker and bis[4-di(phenylsulfonio) phenyl]sulfide bis(hexafluorophoshate) as photoacid generator with a sensitivity of -8 ~Clem' and a resolution of -24 nm. The polysubstituted triphenylene derivative, 2,6,10-trihydroxy-3,7,11- tri(pentyloxy) triphenylene, showed a sensitivity of -5 ~Clem' when the crosslinker hexamethoxymethylmelamine and the photoacid generator triphenylsulfonium triflate were added to the compound. However, fine patterning in the resist was not very successful due to acid diffusion. An alternative triphenylene derivative similar to 2,6, 1 0-trihydroxy-3,7, 11- tri(pentyloxy) triphenylene, with epoxides incorporated into the structure showed better results with the photoinitiator bis[ 4-di(pheny lsulfonio) phenyl]sulfide bis(hexa fluorophoshate). The chemically amplified C51epoxide demonstrated a sensitivity of ~9 f..!C/cm2 and a resolution of 40 nm. The etch durabilities of these chemically amplified resists for dry plasma etching with SF6 are reasonably high, comparable to a conventional high durability novolac resist

Novel resists for next generation lithography

With progress in the semiconductor industry, transistor density on a single computer chip has increased dramatically. This has resulted in a continuous shrinkage of the minimum feature size printed through microlithography technology. Resist, as the pattern recording medium of such printing, has been extensively studied to achieve higher resolution, higher sensitivity and lower line edge roughness. For decades this has been realized through chemical amplification. With the feature size continuously shrinking and the energy of exposure source therefore exceeding the resist ionization threshold, the performance of conventional chemically amplified resists is approaching the limits. Novel high-performance chemically amplified resists or non-chemically amplified resists are urgently needed to meet the requirement of next generation lithography. In this work a negative tone chemically amplified resist system based on a novel method to control the catalytic chain reaction is presented. The method to control the catalytic chain reaction is demonstrated using two model polymer resists. This method is then applied to a fullerene-based molecular resist system and a combination of good industrial compatibility, high resolution and good sensitivity has been achieved in this resist. Through a chromatographic separation, another chemically amplified molecular resist was also developed with further improved performance. An alternative route to sensitivity improvement other than chemical amplification is then introduced and a family of fullerene-based metal containing materials is presented. Lithographic performance is compared between the fullerene-metal resists and their control materials without metal. Using an aberration corrected scanning transmission electron microscope, the distribution of metal in the resist film and its behavior during the lithography process is evaluated and discussed