The main characteristics of the ENEA Discharge Produced Plasma (DPP) Extreme Ultraviolet (EUV) source are presented together with results of irradiations of various materials. The DPP EUV source, based on a Xe–plasma heated up to a temperature of 30 ÷ 40 eV, emits more than 30 mJ/sr/shot at 10 Hz rep. rate in the 10 ÷ 18 nm wavelength spectral range. The DPP is equipped with a debris mitigation system to protect particularly delicate components needed for patterning applications. The ENEA source has been successfully utilized for sub–micrometer pattern generation on photonic materials and on specifically designed chemically amplified resists. Details down to 100 nm have been replicated on such photoresists by our laboratory–scale apparatus for contact EUV lithography. Preliminary EUV irradiations of graphene films aimed at modifying its properties have been also performed.
Due to its chemical specificity, the near edge X-ray absorption fine structure spectroscopy is an interesting technique to study the changes in hybrid organic-inorganic photoresists. In this work, we analyzed the chemical changes occurring in photoresists synthesized from organically modified precursors and transition metal alkoxides by sol-gel route. These systems are nonchemically amplified resists for ultraviolet, extreme ultraviolet, and electron beam lithography. They are based on Si, Zr, and Ti oxides or a combination of these. The experiments were conducted at the PolLux beamline of the Swiss Light Source, by a scanning transmission X-ray microscopy, which combines the spatially-resolved microscopy and fine structure spectroscopy at once. The absorption spectra were collected in the energy range of the carbon edge (≈ 290 eV) before and after in situ exposure of the photoresists to 500 eV photons. The variations in peak intensity after exposure reveal the changes in the chemical environment of carbon and the chemical configuration of the organic ligands, regardless of the inorganic part. It was found that the photon exposure induced sizable photodegradation or photopolymerization of organic groups (phenyl or methyl methacrylate, respectively). These mechanisms contribute to the foundation for the exposure reaction in negative-tone hybrid photoresists. Interestingly, it was also found that the detachment of the phenyl ligand occurs in a variety of possible pathways to condensation. We believe that our results and approach can provide a better understanding of photochemistry of resists, in particular for extreme ultraviolet lithography.
Engineered organic-inorganic hybrid materials, HyMat, offer new opportunities for the easy, fast and cheap development
of miniaturized functional devices. The integration of inorganic oxide networks, organic functional groups and optically
active molecules or nanoparticles allows to obtain combinations of properties and structures otherwise impossible with
traditional materials.
In particular, a simple and highly versatile synthesis platform enabling preparation of HyMat is presented, which is built
up by a bottom-up sol-gel approach at low processing temperatures. A few types of key building blocks pave the way for
accessing HyMat and make up their formulation, providing a means to synthesize innovative materials enabling to get:
- optically active micro and nanostructures;
- miniaturized sensors for analytes in gaseous or liquid media;
- direct patternability with a range of lithographic techniques;
- variable inorganic and organic compositions, and controlled porosity.
Examples of micro and nanostructures based on these spin-on materials with ceramic (i.e. SiO2, GeO2, Al2O3, ZrO2,
TiO2,) and hybrid compositions will be presented for different applications including plasmonic or fluorescent sensors,
dry-etching masks with outstanding resistance, optically active micro and nanostructured platforms and high resolution
patterns.
We present the design, realization and characterization of active deformable gratings for extreme-ultraviolet monochromators for ultrashort pulses. The core device consists of a bimorph deformable mirror on the top of which a diffraction grating with laminar profile is realized by UV lithography. The curvature radius of the grating substrate can be varied changing the voltage applied to an underlying piezo-actuator. The advantage of this technology is to provide gratings with high optical quality, robust, compatible with any coating deposition and realized with only vacuumcompatible materials. We present the characterization of a time-delay compensated monochromator realized with these devices, showing that the active grating can optimize the beam focusing through its rotation and deformation. Two equal active gratings have been mounted in a compensated configuration to realize a grazing-incidence double-grating monochromator for the spectral selection of ultrashort pulses and the simultaneous compensation of the pulse front-tilt given by the diffraction. The wavelength scanning is performed by the first grating through rotation. The radiation is focused on the intermediate plane, where a slit carries out the spectral selection. Finally, the second grating compensates for the pulse front-tilt given by the first one. The spectral focusing of both gratings is maintained at the different wavelengths through the variation of the radii of curvature. The instrument has been tested with a Ti:Sa laser operated at 800 nm. We have been able to demonstrate that the double-grating configuration with active gratings compensates for the pulse front-tilt, that is reduced from 1 ps at the intermediate plane to 100 fs at the output. The final value is limited by the group delay dispersion of the monochromator within the 10-nm bandwidth of the laser. A configuration for the selection on XUV ultrashort pulses has been theoretically studied and the expected performances presented. Active gratings may be considered as a cheaper and more flexible alternative to standard gratings for the realization of extremeultraviolet monochromators for ultrafast pulses, such as free-electron lasers and high-order laser harmonics.
In the last years inorganic semiconductor (particularly CdSe and CdS) quantum dots (QDs) have received great attention
for their important optical properties. The possibility to tune the emission wavelength, together with their high
fluorescence quantum efficiency and photostability, can be exploited in photonic and optoelectronic technological
applications. The design of DFB devices, based on QDs as active optical material, leads to the realization of compact
laser systems. In this work we explore the use of an inorganic/organic hybrid material composed of CdSe-ZnS
semiconductor quantum dots doped into a zirconia sol-gel matrix for optical gain applications. Through the use of soft
lithography on a sol-gel germania-silica hybrid, large scale distributed feedback gratings can be created. Used in
conjunction with the CdSe-ZnS/ZrO2 hybrids, these gratings can act as microcavities and allow for the realization of true
lasing action. The lasing properties within these devices are characterized in the femtosecond regime by both one- and
two-photon excitation. From experimental data the value of the optical gain of the core-shell quantum dot samples has
been estimated. Moreover, one- and two-photon lasing threshold and stability are reported.
A hybrid organic-inorganic sol-gel material based on 3-(glycidoxypropyl)-trimethoxysilane (GPTMS), an organically modified alkoxide containing an epoxy ring in the organic functional group, and titanium isopropoxide Ti(OPri)4 has been synthesised. The presence of Ti alkoxide is important in order to increase the refractive index and to improve the mechanical and physical properties of the film. A basic catalysis has been used to perform the hydrolysis/condensation reactions of the inorganic network and to preserve the presence of unreacted epoxy rings. The epoxy groups are thus available in the final solid state films for the UV-photopolymerization process. The photopolymerization allows one to increase the refractive index and to pattern the film directly.
The modification of the hybrid sol-gel TiO2 matrix microstructure during the thermal treatment and the interaction with the UV light have been investigated by FT-IR and UV-Vis spectroscopies, DTA and TGA thermal analysis. The sol-gel film thickness and roughness have been analyzed by a profilometer: the films possess high optical quality and well controlled thickness, ranging from 500 nm to 2 μm. The refractive index of sol-gel thin films was measured by m-line spectroscopy and ellipsometry. An increase of the refractive index in the range 0,02÷0,1 was achieved, depending on the UV irradiation dose.
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