Yuqiang Tu

Wavelength-Invariant Resist Composed of Bimetallic Layers

Two layer co-sputtered Bi over In thin films (40 nm/layer) act as a microfabrication resist with many potential applications. Their physical, chemical and optical characteristics change after laser exposures that produce a rapid thermal anneal in selected areas. Unlike organic photoresists, Bi/In is a bimetallic thermal resist whose sensitivity shows a near wavelength invariance for wavelengths from Near IR to UV. The laser-induced patterns are developed by an etch that selectively removes unexposed areas and retains converted ones. The optical density (OD) of 40 nm thick Bi/In films on quartz substrates, for example, changes from 3.3 OD to 0.37 OD in the annealed area. This has enabled the creation of direct-write photomasks for standard photoresist exposures. In this paper, the composition, morphology, and nanostructure of the resist before and after laser processing were studied in order to determine the mechanism of the laser-induced material conversion. AFM, XRD, and TEM show that the as-deposited films are polycrystalline, continuous, but with a rough, island morphology. Furnace anneals in air above the eutectic temperature (150-250°C, 3 hours) result in the formation of the tetragonal phase BiIn with a small degree of oxidation. The island morphology is maintained but there is evidence of melting and recrystallization. Transparency is much lower than after laser annealing. RBS and NRA depth profile analysis show that Bi/In films exposed to laser annealing in air contain a large fraction of oxygen and suggest that the converted film may be a BiIn0.6O6 /Bi0.3InO6 bilayer.

Bi/In as patterning and masking layers for alkaline-based Si anisotropic etching

A new resist for alkaline-based silicon anisotropic etching process has been developed. Bismuth over Indium films, 30 nm to 90 nm thick for each layer, were DC-sputtered on silicon substrates, and were used as a thermally activated photoresist on which patterns were generated using focused Argon laser beam. Both physical and chemical properties of the bimetallic film changed after the laser exposure. Unlike normal organic photoresist, Bi/In is laser wavelength invariant as it is a thermal processes. The laser exposed patterns were developed in diluted RCA2 solution that selectively removed the unexposed area and retained the exposed. The developed Bi/In patterns acted as an etching mask for the subsequent alkaline-based silicon anisotropic etch at 85°C. It was found that the developed Bi/In has a lower etch rate than that of SiO2 in the etching solutions, making it a potential masking material for silicon bulk micromachining process. Solar cells with V-groove surface textures were manufactured to show the compatibility of Bi/In with conventional processes.

Creating precise 3D microstructures using laser direct-write bimetallic thermal resist grayscale photomasks

Previous research demonstrated Sn/In and Bi/In bimetallic thermal resists are promising new materials for direct-write analogue grayscale photomask processes. These materials turn transparent with increased laser exposure power and their optical density changes smoothly from 3 OD when unexposed to less than 0.22 OD when fully exposed. The transparency is the result of an oxidation process that is controllable with exposure to generate the grayscale levels in the photomask. In order to produce precise 3D structures in regular photoresists, the steps involved in microlithography must be quantified and examined. The lithographic process includes drawing 8-bit grayscale bitmap patterns, computer-aided laser writing photomasks on bimetallic films, and regular photoresist exposure using a mask-aligner. Compensation during the mask-writing process was necessary since the relationship between the optical density of the exposed bimetallic films and the laser writing power was not completely linear. In addition, the response of the photoresists to the mask exposure time was also a non-linear relationship. To investigate the resolution limit for Bi/In and Sn/In bimetallic thermal resists as a masking material, we used a modified form of interference lithography to expose and develop structures in Bi/In resists with widths that are less than 200 nm. As a result of the lithography, we were able to create structures in the Bi/In films that are up to 20 times smaller than previously obtained using the direct-write method.

Bi/In thermal resist for both Si anisotropic wet etching and Si/SiO2 plasma etching

Bi/In thermal resist is a bilayer structure of Bi over In films which can be exposed by laser with a wide range of wavelengths and can be developed by diluted RCA2 solutions. Current research shows bimetallic resist can work as etch masking layer for both dry plasma etching and wet anisotropic etching. It can act as both patterning and masking layers for Si and SiO2 with plasma “dry” etch using CF4/CHF3. The etching condition is CF4 flow rate 50 sccm, pressure 150 mTorr, and RF power 100 - 600W. The profile of etched structures can be tuned by adding CHF3 and other gases such as Ar, and by changing the CF4/CHF3 ratio. Depending on the fluorocarbon plasma etching recipe the etch rate of laser exposed Bi/In can be as low as 0.1 nm/min, 500 times lower than organic photoresists. O2 plasma ashing has little etching effect on exposed Bi/In. Bi/In also creates etch masking layers for alkaline-based (KOH, TMAH and EDP) “wet” anisotropic bulk Si etch without the need of SiO2 masking steps. The laser exposed Bi/In etches two times more slowly than SiO2. Experiment result shows that single metal Indium film exhibits thermal resist characteristics but at twice the exposure levels. It can be developed in diluted RCA2 solution and used as an etch mask layer for Si anisotropic etch. X-ray diffraction analysis shows that laser exposure causes both Bi and In single film to oxidize. In film may become amorphous when exposed to high laser power.

Expanding grayscale capability of direct-write grayscale photomask by using modified Bi/In compositions

Bimetallic thin films have been proven to be effective in creating analog direct write grayscale photomasks. DC-sputtered Bi/In or Sn/In oxidizes under laser writing exposure. The optical density decreases from >3OD as deposited to a transparency of <0.22OD at 365 nm with increasing laser power. The bimetallic film has a response curve that is nearly linear for much of the curve, but non-linear at maximum absorption and transmission. In order to create more accurate gray levels, a more gradual OD change versus laser writing power is desired. In this research a new reactive sputtered, oxygenated Bi/In film was created that has an 8-bits grayscale level sensitivity of 1.1 gray levels/mV, compared with the previous Bi/In of 3.2 gray levels/mV and Sn/In of 2.8 gray levels/mV. This modified Bi/In film provides more than twice the laser writing power range for controlling the same OD range, as compared to our original Bi/In or Sn/In films. This wider power range provides easier and more accurate laser power-to-grayscale calibration, because each grayscale can now be spaced more evenly over the increased laser writing power range. In addition, the surface of modified Bi/In is found to be much smoother than the original Bi/In and Sn/In films, thus increasing the overall quality of grayscale photomask. Finally grayscale uniformity of the laser writing process has been investigated and techniques such as laser beam shaping and defocusing have been used successfully to eliminate the variations.

Adding grayscale layer to chrome photomasks

Recent work has shown that bimetallic films, such as Bi/In and Sn/In, can create laser direct-write grayscale photomasks. Using a laser-induced oxidation process; bimetallic films turn transparent with variations in optical transparency that are a function of the laser power. The films exhibit transmittances <0.1% when unexposed and >60% when full laser exposed. A novel grayscale photolithography technique is presented that utilizes conventional chrome photomasks as the high resolution pattern-defining layer with a bimetallic thin film layer deposited on top as the grayscale-defining layer. Having the grayscale layer on top of the chrome, grayscale patterns can be aligned to the underlying chrome patterns. Laser power and bimetallic thin film thickness are carefully calibrated such that no chrome ablation or conversion occurs. The calibration ensures that during laser scanning, the bottom chrome layer defines the fine features of the underlying patterns and remains unchanged, while the bimetallic thin film layer is converted to provide grayscale tones. To further investigate the optical density (OD) properties of this type of mask, we measured the transient time response for pure chrome mask and Bi/In coated chrome mask to help fine tune the laser writing parameters. Using bimetallic Bi/In/Cr photomasks, we have successfully created continuous tone 3D structures with superimposed binary structures in SU-8 photoresist. By introducing this novel combined chrome-bimetallic mask, the fine detail features found in binary lithography may be combined with smoothly-varying 3D microstructures best suited to grayscale methods.

Laser-induced oxidation of Zn and Zn alloy films for direct-write grayscale photomasks

Previous research showed that bimetallic Bi/In and Sn/In films exhibit good grayscale levels after laser exposure due to controlled film oxidation. While giving a large alteration in optical density (OD) from 3.0OD to 0.22OD at 365 nm, Bi/In and Sn/In films show a very nonlinear OD change with laser power, making fine control of grayscale writing difficult at some gray levels. This paper studies Zn and Zn alloy films as possible candidates for improved direct-write grayscale photomask applications. Zn and Zn alloys laser oxidation have been reported previously, but without grayscale optical measurements and applications. In this paper Zn films (50 nm ~ 240 nm), Sn/Zn (100 nm), Al/Zn (100 nm), Bi/Zn (100 nm) and In/Zn (100 nm) were DC- and RF-sputtered onto glass slides and then were scanned by argon ion CW laser (488 nm). Among these films, the highest OD change, 3OD (from 3.2OD before exposure to 0.2OD after laser exposure) at 365 nm, was found in the In/Zn (25/75 nm or 84at% Zn) film. The characterization of grayscale level to laser power modulation in Zn and Zn alloy films with various thickness or composition ratios were investigated. The Zn OD change versus laser power curve is more linear than those of Sn/In and Bi/In films. In/Zn films have better characterization of grayscale level versus laser writing power than pure Zn film. Among these four Zn alloy films, Zn/Al shows most linear relation of OD at 365 nm to laser power modulation.

Enhanced inorganic bimetallic thermal resists transparency and resolution for photomask fabrication

Bimetallic films have been found to be promising direct write binary and grayscale photomask materials, as they turn transparent after laser exposure. Current structural analysis shows that the laser exposure is an oxidation process. The amount of the oxidized metal created during the laser writing process is related to the laser power, which in turn, determines the gray level (OD) of the exposed film. New exposure conditions have greatly increased the transparency of exposed films (down to 0.18 OD at 365 nm). Furthermore, this extended to deeper UV (300 nm). As the transparency of exposed area changes with the laser exposure power, grayscale photomasks can be created with the bimetallic films, and 3D structures can be produced in the substrate. Interference lithography has been used to investigate the bimetallic films resolution limit, which can generate much finer structures. Lines of 100-180 nm wide were successfully created on silicon and silicon dioxide. Aluminum thin films were found to turn transparent (0.28 OD) after laser exposure with high power, indicating that Al can also be a potential direct-write photomask material.

Creating 3D Structures with A Direct-Write Gray-scale Photomask Made from Sn/In Bimetallic Films

Bilayer thermal resist Sn/In films have been found to be promising analogue direct-write photomask materials. The bimetallic films turn to be more transparent after a laser exposure which raises the films above the eutectic temperature. Laser converted layers are oxidized to a controlled extent, depending on the laser exposure energy. The exposure causes a change of absorption at 365nm from 3OD to 0.22OD. The thermal resist shows near wavelength invariance from IR to UV. The Sn/In films, each layer ~40 nm thick, were DC-sputtered onto glass slides or quartz substrates. To make grayscale photomasks the samples are placed on a computer-controlled high accuracy X-Y table. The computer takes a bitmap gray-scale pattern as the input and modulates an optical shutter, which in turn, controls the actual power of a CW Argon laser (514 nm) beam applied to the thermal resist according to the gray-scale value. Sn/In photomasks have been used together with a standard mask aligner to successfully make 3D patterns on Shipley SPR2FX-1.3 photoresist. CF4/O2 plasma etching has been used to transfer the 3D patterns to SiO2 substrates. XRD analysis shows that laser power determines the extent of oxidation of the metal films.

Real-time optical characterization of laser oxidation process in bimetallic direct write gray scale photomasks

DC-sputtered Sn/In and Bi/In bimetallic thin films oxidize and turn transparent under laser exposure. The films transparency, or optical density (OD), changes smoothly with increasing laser power, from ~3.0OD (unexposed) to <0.22OD (fully exposed). Laser-induced oxidation of bimetallic films can be used to produce direct-write binary and analogue grayscale photomasks. In order to create high quality grayscale photomask and to improve our current laser writing process, requires real time measurement of OD values, and a greater understanding of the laser-induced oxidation process of the bimetallic thin films. An OD measurement system has been developed capable of providing real time optical density and exposure power changes for the bimetallic thin films. Three silicon-based PIN photodiodes were used to monitor the incident and transmitted beams powers, allowing us to measure the OD change as the film oxidizes, giving us a real time measure of the optical density changes of the bimetallic thin film. With this OD measurement system, real time OD data can be used to adjust the laser power to compensate any variations in laser output power, film characteristics and other variations in the laser writing system. Furthermore, with the incident beam focused, we can precisely measure OD level in areas as small as the laser spot size. Exposed Bi/In/O films show an immediate rapid -2OD/ms change in the first 0.5 ms of exposure. However, In/Sn and Zn films show an initial time delay before OD begins to change, and then a less rapid change of -0.56OD/ms or -0.32OD/ms respectively.