Thermally curable hybrid high refractive index polymer solutions have been developed. These solutions are stable up to 6 months under room temperature storage conditions and can be easily spin-coated onto a desired substrate. When cured at elevated temperature, the hybrid polymer coating decomposes to form a metal oxide-rich film that has a high refractive index. The resulting films have refractive indices higher than 1.90 in the entire visible region and achieve film thicknesses of 300-900 nm depending on the level of metal oxide loading, cure temperature being used, and number of coatings. The formed films show greater than 90% internal transmission in the visible wavelength (400-700 nm). These hybrid high refractive index films are mechanically robust, are stable upon exposure to both heat and UV radiation, and are currently being investigated for microlithographic patterning potential.
The performance of optoelectronic devices can be increased by incorporating a high refractive index layer into the system. This paper describes several potential high refractive index resin candidates. Our materials include the added advantages over other systems because the new materials are cationically photocurable and free flowing, have low shrinkage upon cure, have no (or little) volatile organic components, are applicable by a variety of methods (dip coating, roller coating, injection molding, or film casting), can be applied in a variety of thicknesses (10-100 m), are fast-curing, and possess robust physical properties. Particular attention focuses on the refractive index in the visible spectrum, light transmission, and formulation viscosity.
A series of soluble, fully aromatic polyetherimides were prepared as candidate materials for optical coating applications. Most of the new polymer coatings possessed high transparency in the optical and near-infrared spectral regions at thicknesses ranging from 1 to 10 microns. The refractive indices obtained ranged from 1.60 to 1.80 at visible wavelengths, with the highest values generally being obtained near 400 nm followed by a gentle decline as wavelength increased to 700 nm and beyond. The refractive index values could be controlled by varying the dianhydride and diamine composition. All of the polyimides showed good thermal stability to 400°C and displayed glass transition temperatures above 220°C, making them excellent candidates for device applications where increased refractive index and high optical clarity are desired. The paper will discuss the preparation and physical and optical properties of the polymers and compare them to other high index coating systems.
The performance of many solid-state devices including emissive displays, optical sensors, integrated optical circuits, and light-emitting diodes can be improved by applying a transparent high refractive index coating (≥ 1.65) onto the light-emitting or light-sensing portion of the device. Ideally, the coating should combine the excellent durability and easy deposition of a spin-applied polymer coating with the high refractive index and optical clarity of a vacuum deposited metal oxide coating such as titanium dioxide or zirconium oxide. While some success has been achieved in combining these very dissimilar materials to form transparent hybrid coating systems, for example, using sol-gel or nanoparticle dispersion techniques, the resulting coating systems often require complicated manufacturing schemes and have limited storage stability and reliability.
We have demonstrated two new approaches to development of high refractive index polymer coatings. In the first approach, an organometallic polymer and a conventional organic polymer are combined to form a compatible coating. When cured at elevated temperatures, the organometallic polymer decomposes to form a highly dispersed metal oxide phase that imparts high index properties to the final hybrid coating. The new coatings are transparent and have
refractive indices ranging from 1.6 to as high as 1.9 depending on the metal oxide content.
The second approach utilizes our discovery that polyimide materials possess naturally high refractive indices in comparison to most polymer materials. Through careful molecular design, we have developed a new class of polyimide materials having refractive indices ranging from 1.60 to 1.78 at visible wavelengths and exhibiting excellent optical clarity. The new polyimides can be spin-applied to a layer thickness of more than 10 microns in a single coating step and form thermally stable films with good mechanical strength and adhesion to device substrates.
Microelectromechanical systems (MEMS) device manufacturers today are faced with the challenge of protecting electronic circuitry and other sensitive device structures during deep silicon wet-etch processes. Etch processes of this nature require prolonged exposure of the device to harsh corrosive mixtures of aqueous acids and bases at higher than ambient temperatures. A need exists for a spin-applied polymeric coating to prevent the exposure of such circuitry against the corrosive etchants. The challenge exists in developing protective coatings that will not decompose or dissolve in the etchants during the etch process. Such coatings require superior adhesion to the substrate without destroying the sensitive features below. Brewer Science, Inc., has developed a multilayer coating system for basic etchants which is compatible with a variety of semiconductor materials and offers protection against concentrated potassium hydroxide (KOH) etchants at prolonged exposure times of more than 8 hours. In addition, a second multilayer coating system is being developed for use with strong hydrofluoric and other various mixed acid etchants (MAEs) for exposures of 30 minutes or longer. These materials are specifically designed to protect circuitry subjected to concentrated MAEs during the wafer thinning processes used by MEMS device manufacturers.
This paper highlights the performance of new materials that have been developed for use in 193-nm trilayer microlithography. The products are embedded etch masking layers (EMLs) and bottom antireflective coatings (BARCs). Both coatings are spin applied from organic solvent(s) and then thermoset during a hot plate bake. The EMLs (middle layers) are imaging compatible with JSR, Sumitomo, and TOK 193-nm photoresists. Best-case trilayer film stacks have given 100-nm dense and semi-dense L/S. Plasma etching, selectivities and solution compatibility performance of the EMLs meet or exceed proposed product targets. In addition, the EMLs exhibit both solution and plasma etching properties that should lead to successful rework processes for photoresists. The multiplayer BARCs offer good thick film coating quality and contribute to excellent images when used in trilayer applications. Combining the EMLs, which are nearly optically transparent (k=0.04) at 193-nm, with the new trilayer BARCs results in outstanding Prolith simulated reflectance control. In one modeling example, reflectance is a flat line at 0.5% on five different substrates for BARC thicknesses between 300 and 700-nm.
We are developing a set of dyed red, green, and blue color filter coatings for the fabrication of high resolution CCD and CMOS image sensor arrays. The resists contain photosensitive polymer binders and various curing agents, soluble organic dyes, and solvents. The new dyed photoresists are sensitive to i-line radiation, primarily at 365 nm, and are negative-working, requiring less than 500 mJ of exposure energy for patterning. The coatings are developed in standard Tetramethylammonium Hydroxide (TMAH) developers. Many dyes were examined in order to achieve the desired spectral properties as well as the meet the solvent solubility and thermal stability requirements. Computer modeling was utilized to determine the correct proportions of dye(s) in each resist, after which the modeling results were verified by actual formulation and testing. Thermal stability of the dyes was determined using isothermal. Thermogravimetric Analysis (TGA) at 200°C for 30 minutes. The dyes were evaluated in both traditional (free radical) and novel polymer systems to see if adequate sensitivity, resolution, and feature quality could be obtained. The studies showed that traditional free radical-based photochemistries are marginal at best for high resolution (1-2 micron) applications. To overcome this limitation, a new polymer system having photodimerizable functional units and acid functional groups was developed to impart photosensitivity and developer solubility, respectively. This system, which does not use free radical-initiated photopolymerization as a mechanism for patterning, shows low exposure dose requirements and is capable of resolving features less than 2 micron in size.
A need exists for spin-applied polymeric coatings to protect electronic circuitry and other sensitive structures on MEMS devices during deep silicon wet etching processes involving corrosive mixtures of aqueous acids and bases. The challenge exists in developing protective coatings that do not decompose or dissolve in the harsh etchants and, more importantly, that maintain good adhesion to the substrate during the sometimes long etching processes. We have developed a multilayer coating system that is stable and adheres well to silicon nitride and other semiconductor materials and affords chemical protection for at least eight hours in hot potassium hydroxide etchant. The same coating system is also compatible with concentrated hydrofluoric acid etchants, which can diffuse rapidly through many polymeric materials to attack the device substrate.
We report here the development of a fast-etching i-line bottom anti-reflective coating (BARC): EXP97002B. The new BARC is applied from a safe solvent system, exhibits wide spin bowl compatibility with photoresists, and may be processed with common edge bead removal solvents. The optical density of the new BARC is 6.15/micrometer at 365 nm (n equals 1.71, k equals 0.39). We have demonstrated plasma etch rates for the new coating in excess of 1.5 - 2.0 times that of conventional i- line photoresists. The coating system planarizes substrate topography, reducing resist film thickness variations and, thereby, resist swing. Feature coverage is still excellent, as evidenced by the ability of the new BARC to coat 0.7 micrometer vertical topography. The practical issues for implementing the new BARC in a manufacturing environment is also discussed.
Preliminary studies with Brewer Science CD9 ARC have shown that high-intensity ultraviolet exposure results in significant changes in film properties, including thickness, plasma etch resistance, and develop rate. This process has been studied over a range of temperatures and exposure conditions, and their results are interpreted in terms of competing polymer main chain scission and crosslinking reactions. The process represents a path to improved etch performance, and the possibility exists for use of Brewer ARC in a bi-layer portable conformable mask resist scheme.
In this paper, we describe the results of experiments performed using wafers having either phosphorous (POCl3) doped polysilicon, LPCVD silicon nitride, LPCVD silicon dioxide, LPCVD silicon dioxide over POCl3 doped polysilicon, evaporated aluminum, or CVD tungsten thin films, patterned with and without the use of deep UV anti-reflective coatings. The parameters of reflectance control, critical dimension control, focus/exposure latitude, and resist profiles were studied for line/space gratings and contacts. Incorporation of anti-reflective coatings was shown to be very beneficial for reducing the impact of highly reflective substrates, grainy surfaces, and topographical features encountered during deep UV imaging. The ARC process is independent of the substrate's reflectivity, allowing the same exposure dose for all substrates studied. Without ARC the optimum exposure dose for the same substrates varied over a 35% range. ARC also provides slightly increased exposure and focus windows for some substrates, and was shown to significantly improve linewidth control on rough substrates such as POCl3 doped polysilicon and tungsten. The grainy surface of the tungsten wafers was nearly impossible to pattern without the use of an anti-reflective coating; without ARC, there was virtually no process window (approximately 2 mJ/cm2) for retention of 0.50 micrometers features.
This paper discusses issues concerning the use of a thin absorbing organic anti-reflective (AR) coating for 0.5 micrometers excimer laser lithography. Linewidth profiles, CD control, substrate dependence and etching are all affected by the presence of the AR coating. The advantages of implementing highly absorbing organic AR coatings are that CD control with resist thickness (swing curve) is improved, substrate reflectivity effects becomes negligible, adhesion is improved and reflective notching is decreased, leading to better CD control over topography. For example, the swing curve was reduced from 0.18 micrometers to 0.04 micrometers by using an absorbing AR film. Exposure/focus latitudes were modeled using Obelisk software. This gave an exposure dose of 26 mJ/cm2 for printing 0.5 micrometers dense lines on aluminum, poly- silicon, oxide, nitride and tungsten. In addition, the exposure latitudes for these substrates was found to be +/- 10% when the total depth of focus was 1.2 micrometers . Statistically designed experiments were used to optimize resist profiles of the SNR248 resist images on AR coating. Issues relating to implementing organic AR coatings under a 1300 angstrom absorbing AR coating reduced reflectivity variation on poly-silicon from 38% to 6% over a resist thickness range of 350 angstrom. By using the AR coating the swing curve variation was reduced from 0.18 micrometers to 0.04 micrometers .
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