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.
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.
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.
A laser direct write process has been developed for turning patterned bimetallic Sn/In film into a indium tin oxide layer. Sn over In films (15-120nm thick) with a 1:10 thickness ratio were deposited by DC sputtering. An argon laser beam (0.1 - 0.9 W, spot size: 2 micron, scan speed: 1 cm/s) exposes the film into patterns. These Sn/In films' optical absorption changed from 3 OD at deposition to 0.24 OD after exposure (at 356 nm). XRD, SEM, EDX, and Auger have been used to investigate the film's microstructure and composition suggesting ITO like characteristics. XRD indicated a preferred In2O3 (222) orientation which is similar to ITO films deposited by other methods. Four-point probe tests showed a converted film resistivity of 0.26x10-3 to 9.7x10-3 ohm-cm depending on the laser power and Sn concentration. Hall tests indicated that the bulk carrier concentration was in the range of 1018 to 1020 cm-3. Developed in a wet HCl: H2O2: H2O =1:1:48 solution removes unexposed Sn/In leaving patterned ITO films created at much lower laser power levels than needed for ablative patterning of ITO. Developed films are also resistant to KOH anisotropic etching at a 1:700 ratio producing <111> trenches in Si (100). The large change in optical density means Sn/In films can be used as a material of the direct write photomasks.
Bimetallic thin films were previously shown to create laser direct write binary and analog gray scale photomasks. DC-sputtered Sn/In (5at.% Sn, 80 nm) oxidize under laser exposure, modifying the optical density at 365 nm from >3OD to <0.22OD. Bimetallic Sn/In thin film grayscale photomasks have been successfully used to create concave and convex 3D structures using mask aligners with Shipley photoresists. To produce precise 3D structures in the organic photoresists, every mask making step was studied. Compensations during the mask making process were necessary because that the relationship between the optical density of the exposed bimetallic films and the laser writing power is not accurately linear, and also that the response of the photoresists is not linear to the exposure. V-grooves with straight slope profile were produced with calibrations taken into account. X-ray diffraction analysis indicates that structure of laser exposed Sn/In bimetallic films is similar to that of ITO films, suggesting new directions for improvement of bimetallic film optical properties, and that the theoretical maximum transmission should approach pure ITO’s ~0.05OD in the visible wavelength.
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.
Bimetallic thin films containing indium and with low eutectic points, such as Bi/In, have been found to form highly sensitive thermal resists. They can be exposed by lasers with a wide range of wavelengths and be developed by diluted RCA2 solutions. The exposed bimetallic resist Bi/In can work as an etch masking layer for alkaline-based (KOH, TMAH and EDP) “wet” Si anisotropic etching. Current research shows that it can also act as a patterning and masking layer for Si and SiO2 plasma “dry” etch using CF4/CHF3. 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 0.1nm/min, 500 times lower than organic photoresists. O2 plasma ashing has little etching effect on exposed Bi/In, indicating that laser exposure is an oxidation process. Experiment result shows that single metal Indium film and bilayer Sn/In exhibit thermal resist characteristics but at higher exposure levels. They can be developed in diluted RCA2 solution and used as etch mask layers for Si anisotropic etch and plasma etch.
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.
New types of analog gray-scale laser direct-write masks have been created using bimetallic thermal resists and a direct- write laser process. Bimetallic resists consist of two layers of thin films, eg. Bi over In or Sn over In, which react to form a low temperature alloy when a laser raises the films above the eutectic temperature. Depending on the exposure energy, resulting alloyed layers appear to become oxides, causing a change of absorption at 365nm from >3OD to <0.3OD. The thermal resists show 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 gray-scale photomasks the samples were placed on a computer-controlled high accuracy X-Y table. A bitmap gray-scale pattern was raster-scanned with a CW Argon laser (514 nm) beam. An optical shutter controlled the actual laser power applied onto the thermal resist film according to the gray-scale value. When exposed to a laser beam greater than 0.6 W, the Sn/In film became nearly transparent (0.22OD) at I-line (365nm) wavelength. Sn/In and Bi/In photomasks have been used together with a standard mask aligner to successfully pattern Shipley SPR2FX-1.3 photoresist. CF4/O2 plasma etching has been used to transfer the three-dimensional pattern to SiO2 and Si substrates. Also a 160 beam laser diode thermal imaging tool was used to create BiIn direct-write binary masks.
Bilayer Bi/In thin film thermal resists are Bi and In films which form an etch resistant material at ~7 mJ/cm2 laser exposures with near wavelength invariance from visible to EUV. New simulations predicted that Bi/In film of 15/15nm absorbs substantially at 1 nm, which projects single pulse exposure sensitivity of ~16 mJ/cm2, hence suggesting good sensitivity to X-ray range. Thermal modeling has confirmed the exposure time/optical energy requirements for Bi/In. Exposed and developed Bi/In resist etches slower than silicon dioxide in alkaline-based silicon etchants TMAH, KOH, and EDP, making it a better masking layer for anisotropic Si etching. Also Bi/In has been used to create a direct-write photomask as its optical transmission changes from OD>2.9 before laser exposure to OD<0.26 after exposure. Both Bi/In anisotropic etching and direct write masks have been combined to successfully build test photocells with V-groove surface textures by using Bi/In masked silicon anisotropic etching and the other layers created using regular lithography but with Bi/In masks. These devices showed no operational differences from those created with regular resist processes. Investigation of resist interactions with Silicon after laser exposure and strip were done with Auger surface analysis which showed no detectable Bi or In contamination on substrates and no substrate sheet resistance change. X-ray diffraction and Rutherford back scattering tests suggest that the converted Bi/In may involve oxides.
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