The E-ReticleTM system was used to assess the electrostatic risks from mask manufacturing equipment
and processes. Test results showed that some mechanical operations of the equipment examined may
cause electrostatic potential differences in a production reticle higher than the ITRS recommended
specifications, which may bring electrostatic risks to the reticle.
E-ReticleTM data also indicated that the
processes play an important role in controlling electrostatic potentials in the reticle. The E-ReticleTM
system can be used as an in-situ equipment assessment tool, as well as a process optimization device.
Experimental results of tool-to-tool polarization comparison at hyper numerical aperture with POLARISTM PSM
Polarimetry (Polarization Affected Resist Image Sensor) are presented. Measurements of tool-to-tool variation of the
Intensity in the Preferred Polarization State (IPS) are shown with two modes of operation: 1) measurement of relative
IPS difference between tools, which does not require calibration with on-board metrology and 2) estimate of actual IPS
measurement, which requires calibration with on-board technique. Relative tool-to-tool variation is generally more
important, as it, rather than actual IPS values, determines any induced tool-to-tool CD variation. Monitoring single tool
stability has been shown in previous work to remain stable to within a fraction of 1%. Tool-to-tool monitoring has
additional sources of variation. The example shown illustrates matching with on-board metrology generally within 2%,
but up to 4% at a maximum. Some causes of these potential variations are discussed as well as strategies to improve
accuracy. The impact of metrology-induced resist burning is assessed and believed to cause uncertainty in the
measurement less than 1%. Finally, a set of measurements comparing azimuthal and horizontal-vertical polarization
states are shown, illustrating the capability of POLARISTM to report the polarization behavior at arbitrary locations
within the pupil. Although pupil-averaged IPS values match to the on-board technique within 1.2%, the angular resolved measurements do not necessarily match theoretical values and vary by up to 10%.
E-Reticle system is an electrostatic field test device, which has the form factor of a conventional six
inch quartz production reticle. The E-Reticle was used to assess the ESD damage risks in a mask cleaning
tool. Test results indicate that a reticle may see higher than ITRS recommended electrostatic potential
specifications when mechanical operations and cold DIW rinse start and in progress, hence seeing
increased probability of electrostatic induced damages.
Experimental verification of Phase Shift Mask (PSM) Polarimetry is provided at numerical apertures up to 1.35.
Promising initial results of periodic monitoring of a few polarized illuminators are illustrated and track with a scanner
on-board technique to within a fraction of a percent. Earlier publications have introduced the concept and provided
experimental validation up to 0.93NA. This paper discusses a variety of design improvements to improve the usability,
flexibility and robustness of this technique at NAs up to 1.35. The specialized test reticle, which consists of a large
number of polarization-sensitive chromeless phase shifting patterns, was successfully fabricated using a commercial
mask shop. Polarization sensitivity has improved by up to 7x when compared to two earlier generation reticles, helping
to minimize the impact of experimental noise. Various use models, the experimental flow, and details on the
experimental procedure are provided. It is concluded that this resist-based method can serve as a highly sensitive
polarization monitoring system for all hyper-NA applications.
A third generation phase shift polarization monitor reticle is reported with improved resolution within the
pupil and across the slit. The polarization state of illumination can be measured for lithography systems
with NA up to 1.45. A double-reticle concept is proposed to expose both polarization test patterns and
SEM alignment marks and polarimeter coordinates in the resist to optimize exposure for each
independently. Both SEM imaging and polarization calculation is improved with the double reticle
scheme. The single-exposure approach previously employed which can only measure three polarization
states (X, Y and unpolarized) has been enhanced by a novel reciprocal exposure technique. The new
exposure approach allows lithography engineers to vary effective polarization and measure at multiple
custom polarization settings. Experimental results show that the sensitivity of the new reticle to
polarization has more than doubled compared to the previous generation.
This paper will provide experimental results of Phase-Shift Mask (PSM) Polarimetry, a previously introduced resistbased
polarization monitoring technique that employs a specialized chromeless phase-shifting test reticle. The patterns
derived from high-NA proximity effects have proven to be 2 to 3 times more sensitive to polarization than a previously
reported generation of patterns. Example results in this paper show that for a numerical aperture (NA) of 0.93, this
technique is likely capable of measuring the intensity in the preferred polarization state (IPS) to within about 3%. Data
from a follow-on reticle for NAs up to 1.35 is expected soon and promises to measure IPS to within about 1.5%. This is
expected to suffice for monitoring polarization at the 22nm node for water-based immersion tools over time or from tool
to tool. This technique is extendable and likely offers even greater sensitivity for high-index immersion lithography,
should NAs greater than 1.35 become available. Advantages and disadvantages of this technique will be addressed.
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.
Bimetallic Bi/In films demonstrate grayscale levels after exposed with different laser powers due to controlled film oxidation. Although large optical density (OD) change from 3.0 OD to 0.22 OD at 365 nm was observed, these films show a rapid and nonlinear OD change with laser power, which is not desirable for fine control of grayscale levels. This paper aims to explore and evaluate some new metal films as possible candidates for direct-write grayscale photomask applications. Sn/In, Al/Zn, Bi/In/O and Al/In films were DC-sputtered onto glass slides and then were raster-scanned by argon CW laser. Among these films, the highest OD change at 365nm was found in Sn/In film, Al/Zn shows the most linear relation of OD to laser power modulation, and Bi/In/O has the best over-all performance as a potential grayscale mask material. A grayscale test photomask of 16×16, 20μm squares over the full OD range was made using Bi/In/O and a test exposure created squares of different heights on regular photoresist. Interference lithography using 266nm DUV has been utilized to investigate the resolution limit of these bimetallic films, which can generate much finer structures. The true resolution limit of Bi/In should be at least less than 50nm.
DC-sputtered Sn/In and Bi/In bimetallic thin films oxidize and turn transparent under laser exposure. The film's 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.
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 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.
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.
A new single step direct-write photomask process has been proposed by using Bi/In bimetallic thermal resist which turns almost transparent with high energy laser exposure. The Bi over In metallic films, each layer approximately 40 nm thick, were DC-sputtered onto quartz mask plate substrates in a single pump-down chamber. Before laser exposure the Bi/In had 2.91 Optical Density. Bi/In is a bimetallic thermal resist and hence shows near wavelength invariance exposure sensitivity from Near IR to UV light. For Bi/In exposure, up to 0.9 W Argon laser (514 nm) beam was focused by an f = 50 mm lens to a 10 micron spot. When writing a mask the Bi/In coated sample was placed on a computer-controlled high accuracy X-Y table and the pattern was raster-scanned by the laser at 10 mm/sec. After exposure the Bi/In film became nearly transparent (0.26 OD) at I-line (365 nm) wavelength, and remained conductive. Bi/In photomasks have been used together with a standard mask aligner to pattern the oxide and Al layer during the manufacturing of test solar cell devices in the lab. Experiments also showed that annealing the as-deposited films at 90°C before laser exposure increase the Bi/In transparency.
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.
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.
Bilayer Bi/In thin films form thermal resists with many new microfabrication and micromachining applications due to their changed physical, chemical and optical characteristics after the laser exposures. Wavelength invariance has been shown from the results of both experiment and Airy Summation optical modeling. The modeling projects bimetallic resist sensitivity to be nearly constant at about ~7 mJ/cm2 from 248 to 13.4 nm and is still very sensitive at 1 nm in X-ray range. Two kinds of acid solutions were effective in developing the exposed films by removing the unexposed area. Both nitric acid mixture (HNO3:CH3COOH:H2O=1:3:6) and hydrochloride acid mixture (HCl:H2O2:H2O=1:1:48) give etching selectivity of exposed to unexposed area of larger than 60:1. The etch rate of unexposed area is about 2.6 nm/sec. The Bi/In resist can be stripped away by an RCA2 clean. Bi/In resist was successfully used as a mask layer for KOH anisotropic silicon etching process. Due to the unusual conductive property of its exposed and developed films, Bi/In has demonstrated that it can be used as a direct laser write electroplating resist material. Copper and nickel plating was carried out on developed Bi/In layers on various substrates such as Si wafers, glass slides, wet-oxidized wafers. Large optical transmission changes (OD>3.5 before exposure and OD<0.3 after exposure at I-line) indicate that Bi/In can be used as a direct-write photomask material.
Bimetallic thermal resist Bi/In has shown many applications in the areas of microfabrication, photomasks and data storage. Optical modeling shows that this class of thermal resist is wavelength invariant, and Bi/In can perform even better at 13.4 nm than at 248 nm due to the increase of absorption and the reduction of reflection. Images were successfully made on Bi/In films with both proximity and projection exposures with Nd:YAG laser running at 2nd harmonic wavelength. A new kind of developing solution used at room temperature was found to be more effective in descumming than nitric acetic acid solution. Both have the etching selectively of unexposed area to exposed areas > 60:1. Developed Bi/In resists shows good conductivity, which can be used as both a metal plating masking and seeding layer, 2 to 10 micrometers wide CU and Ni lines and squares were successfully plated on the developed Bi/In patterns on glass slides and silicon wafers. Shelf test shows that the properties of Bi/In film do not change after being kept in a humid temperature-lifted environment for 10 days. Large optical transmission changes indicate Bi/In can be used for direct-write photomasks and data storage media. Heat- treatment enhances the OD exposed/unexposed OD change.
A class of DC-sputter deposited bimetallic thermal resists (BiIn, SnIn, BiSn) have been investigated with exposure sensitivities (7mj/cm2) near those of current organic photoresists. A prototype resist consists of stacked bismuth on indium layers (30-45nm thick) with thickness ratios matching the eutectic alloy points in BiIn binary phase diagram. Laser exposed areas have significantly different optical characteristics, with lower reflectivity and higher transparency, hence showing the imaged pattern before development, thus confirming correct exposures. Predicted exposure levels are almost wavelength invariant: <5% change between 248 and 157nm. Profilometery results and SEM images showed no signs of ablation in the exposed areas. The BiIn resist was wet developed using a HNO3:CH3COOH:H2O (1:3:6) acid solution which preferentially removed the unexposed areas leaving written patterns of alloyed lines seen both under profilometery and SEM, and stripped in a dilute HCl:H2O2:H2O bath. Shelf tests shows that the BiIn film is stable under 50#C/90% humidity conditions. XRD and TEM show that the film is polycrystalline. Both SnIn and BiSn exhibit similar resist property as BiIn that the exposed area converts to greater transparencies that unexposed areas, indicating these three bimetallic films can be a group of potential inorganic thermal resist.
The Thermal Resist Enhanced Optical Lithography (TREOL) process models an optical system to double device resolution by exploiting non-reciprocal laser activated processes. A possible prototype thermal resist consists of stacked bismuth on indium layers sputter deposited on a glass/quartz substrate with thickness ratios matching the eutectic alloy (Bi 53%). Laser radiation locally melts the metals which alloy upon cooling. BiIn resist is relatively wavelength insensitive because its UV optical characteristics vary modestly. Reflection and energy absorption/cc calculations indicate the best arrangement is a 30-45-nm total thickness bilayer with bismuth on indium. Exposing the highly absorbing BiIn with CW argon (514/488 nm) or 4-ns Nd:YAG pulses at 533 nm (40 mJ/cm2 for 300-nm thick) and 266 nm transforms the resist to a weakly absorbing alloy with a visually identifiable pattern. 30-nm thick converted film transmission changes from 1.0OD to 0.35OD (830-350 nm) until a 350-nm absorption edge. Profilometry and SEM showed no signs of ablation or oxide growth in exposed areas. The resist was developed with HNO3:CH3COOH:H2O etch, preferentially removing unexposed areas, leaving written patterns of alloyed lines seen both in profilometry and SEM images. Thus BiIn forms a complete thermal alloying resist with selectively etched exposed patterns that can be stripped in an HCl:H2O2:H2O bath.
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