TW583412B - Optical lithography and method of inducing transmission in optical lithography preforms - Google Patents

Abstract

The invention provides an ultraviolet lithography method/system. The lithography method and system include providing a below 200 nm radiation source, providing a photolytically improved transmitting fused silica glass lithography optical element, transmitting below 200 nm photons through said photolytically improved transmitting fused silica glass lithography optical element to form a lithography pattern which is reduced and projected onto a radiation sensitive lithography printing medium to form a printed lithography pattern. Providing the photolytically improved transmitting fused silica glass lithography optical element includes providing a photolytically improved transmitting fused silica glass lithography optical element preform body and forming the photolytically improved transmitting fused silica glass lithography optical element preform body into said lithography optical element.

Description

583412 A7 B7 V. Description of the invention (Field of invention: Currently invented lithography silk lithography, _is__wave recording method and light lithographic printing system, for example, outside line lithography using 2 fine lines = ^ = Background of the purple invention in the domain: The Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed a method / system for projecting light flat brushes using material lines with a wavelength below nanometers. The use of materials with a wavelength of 193 nanometers has the power to improve the manufacturing of integrated circuits with smaller part sizes; however: the mass production of integrated circuits with ultraviolet light at 200 nanometers Commercial use and adoption have been slow. The slow progress of the semiconductor industry for UV below 200 nanometers is partly due to the lack of high-quality optical lithographic printing elements with high-quality optical lithography that can be economically manufactured. Stone glass. In order to apply the advantages of ultraviolet lithography in the 193¾ micron region, such as the ArF excimer laser emission spectrum, to the manufacture of integrated circuits, we It requires optical lithographic printing elements, fused silica glass, and optical elements with favorable optical properties, which can be manufactured economically and can be used with UV photons below 200 nanometers. We need to be photolytically In order to improve the lithography optical element's transmission of fused silica glass below 300 nm. We need to pass photolysis to cause the transmission of fused silica glass below 30 nm. We need to cause lithography through photolysis Technical components Hyun Rong Shi Xi Shi glass This paper is scaled to the Chinese National Standard (CMS) A4 specification (2 丨 〇 > < 297 mm) 583412 A7 ----- B1 V. Low description of the invention (2) With a transmission of 300 nanometers, this glass contains non-filled hydrogen. This glass was added to the fused silica glass when the stone spar particles were melted together to form a glass. We need to include SiP fused silica glass Photolytically induced transmission below 300nm and improved quality. We need to include fused silica glass with SiP species and H2 content below 2x1017 molecules / cm3. Photolytically induced transmission of less than 30011111 and improved quality. Important points of the invention: The present invention includes a deep ultraviolet lithography method. The deep ultraviolet lithography method includes: providing lithography with ultraviolet and radiation A fused silica glass lithography optical element that provides photolysis to improve transmission; and passes the generated lithographic photons through this photolysis to improve fused silica glass lithography optical element. This method includes using These photons are used to form a lithography pattern, and this lithography pattern is projected onto a radiation-sensitive lithography printing medium to form a lithography pattern. Making the present invention further includes a method of manufacturing fused silica glass for an optical element. The manufacturing method includes: providing an optical element fused silica glass having an internal transmittance of T (% / cm) below 300 nm; and irradiating the fusion with photolysis using photon irradiation below 300 nm Silica glass in order to provide a fused silica glass with a photodegradation and improved transmission with an internal transmittance of ΙΝ (% / cm) below 300 nm, where ΙΝ-Τ = △ transmittance (% / cm), and △ Transmission -.07. Call 412 A7 —______ B7 —__ 5. Description of the invention (s) Brief description of the drawings: The first figure (Figure 1) shows the UV lithography method and system according to the present invention. The second figure (Figure 2) shows an ultraviolet lithography method and system according to the present invention. The third figure (Figure 3) shows an ultraviolet lithography method and system according to the present invention. The fourth figure (FIG. 4) shows an ultraviolet lithography method and system according to the present invention. The fifth figure (FIG. 5) shows a lithographic printing method according to the present invention. The sixth figure (FIG. 6) shows a lithographic printing method according to the present invention. The seventh figure (FIG. 7) shows a lithographic patterning method according to the present invention. The eighth figure (FIG. 8) shows a lithographic patterning method according to the present invention. The ninth figure (FIG. 9) shows a lithographic patterning method according to the present invention. The tenth figure (Figure 10) shows the method according to the invention and shows the optical elements and preforms of the invention. The eleventh figure (Figure 11) shows the method according to the invention. The twelfth figure (Figure 12) shows the method and system according to the invention. Printed by the Consumers' Cooperative of the Chungli Standards Bureau of the Ministry of Health Figure 12 (Figure 13) shows the method and system according to the present invention. Fourteenth figure (Figure 14) shows the method according to the invention. Figure 15 (Figure 15) shows the method according to the invention. The sixteenth figure (Figure 16) shows the method according to the invention. The seventeenth figure (Figure 17) is for the two output values of fused silica glass, the transmittance (% / cm) at 193 μm (y-axis), relative to the cation impurity paper size of Na depends on Chinese national standards (CNS)) 583412 A7 B7 V. Description of the invention (4) The relationship diagram of the mass content ppb printed by the Consumer Cooperatives of Zhongli Standard Bureau of the Ministry of Carpling. The eighteenth figure (Figure 18) is the resulting 215 nm absorption / cm [-log (T / TO)] (y-axis), relative to the number of pulses of 193 nm (6mJ / cmV pulse) [time (minutes )] (X-axis). Figure 19 (Figure 19) is the resulting 193 nm absorption / cm [-log (T / TO)] (y-axis), relative to the number of pulses (6mJ / cm2 / pulse, 193 nm / card, repeated) Rate (400 Hz) [time (seconds)] (x-axis). The twentieth graph (Figure 20) is the resulting 193 nm absorption / cm [-l0g (T / TO)] (y-axis) relative to the time (seconds) when the 193 nm excimer laser light was irradiated Diagram. The twenty-first figures A and B (Figures 21A-21B) are the relationship diagrams of the internal transmittance of 193 nm with respect to the melting and melting; the depth (in millimeters) of the non-coherent irradiation of the Xe light source by the epsilon glass. The twelfth figure (Figure 22) is a graph of the internal transmittance of 193 nm with respect to the depth (mm) of the fused silica glass irradiating the mercury ultraviolet light source. Description of the symbols of the drawings: "radiation source 20; photon 22; mask 24; printing medium 26; wafer 27; lithographic method / system 28; lithographic optical element 30; mask pattern 32; lithographic pattern 34; excimer Laser 36; fused silica glass optical element preform 40; photon irradiation 42; light less than 300 nm 44; laser 46; wire 48; optical element fusion_Shilai body 5 (), integrated sphere 52; reflection Surface 54; Fused Silica Glass 56; Silica Particles 58; Burner 60; Conversion Point 62; Burning Furnace 64; Burner Flame Refractive Index Stripe Paper China National (Please read the precautions on the back before filling this page) Order 583412 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (f) 68 〇 Detailed description: The present invention includes a UV lithography method. As shown in Figure 丨 this side, including: providing less than 200 nm A-wavelength radiation source 20 to generate photons 22; and provide a fused silica glass lithographic element 30 with photolysis to improve transmission. This method includes passing lithographic photons 22 below 200 nanometers through this photolysis to improve transmission melting Silica glass plate Printing the optical element 30. This method includes using a lithographic photon 22 to form a lithographic pattern and reducing the lithographic pattern, and projecting the lithographic pattern onto a radiation-sensitive lithographic printing medium 26 to form a print As shown in FIG. 2, the lithographic method / system 28 of the present invention preferentially utilizes multiple photolysis to improve the transmission of fused silica glass lithographic optical elements 30. As shown in FIG. 3, this lithographic method / System 28 may contain a large number of fused silica glass lithographic optical elements 30 for photolytically improved transmission to process lithographic photons and lithographic patterns to form a printed lithographic pattern on the printing medium 26 of the wafer 27. Figure 5 The lithographic pattern ic shown on the lithographic mask 24. As shown in FIG. 6, the transmission characteristics of the mask 24 and the pattern 1C, through the lithographic photons below 200 nm, form the lithographic pattern 1C. As shown in Fig. 7, this lithographic pattern 1C is reduced and projected onto the wafer 27. Similarly, the mask pattern 32 of the mask 24 in Fig. 8 Also reduced, and projected onto radiation-sensitive lithographic media 26 in Figure 9 to provide a printed lithographic pattern 34. In a preferred embodiment, such as shown in Figure 4, providing a radiation source 20 includes providing an ArF standard Molecular laser 36, and provide 193 nm lithographic photons. Provide melting for photolysis to improve transmission. Paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling (This page)

583412 A7 V. Description of the invention (t) Silica glass lithographic printing optical element 30 printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs includes a fused silica glass lithographic printing optical element preform object 40 that provides photolysis to improve transmission, and This preform 40 forms a lithographic optical element 30. As shown in FIG. 10, a fused silica glass optical element preform 40 is formed into an optical element lens 30. Forming the optical element 30 preferably includes shaping the preform to provide the optical shape of the element 30 via grinding and polishing. Element 30 can also be coated and mounted in a housing for assembly. Fig. 10 shows a cross section of the preform 40, preferably a dish-shaped cylinder, and a cross section of the optical element 30. Prior to being molded into the optical element 30, this fused silica glass preform object 40 is preferentially subjected to photolysis irradiation in accordance with the present invention in order to improve its transmittance. Fused silica glass lithographic optical element preform object 40 providing photolysis improving transmission includes: providing an unirradiated internal transmittance of T (% / cm) optical element fused silica glass object 50 below 2000 nm; And use less than 300 nanometers photon irradiation and photolytically irradiate this fused silica glass to provide less than 200 nanometers with an increase in internal transmittance of 1N (% / cm). Photolysis improved fused silica glass object , Where IN_τ = Δtransmittance (% / cm), and Δtransmittance- · 07. As shown in FIG. 11, this method includes providing an optical element fused silica glass object 50 having an unirradiated internal transmittance of less than 200 nm (acr / cm); and irradiating 42 to photons with a photon of less than 300 nm Photolysis irradiates fused silica glass preform 50. The preform 50 is exposed to photon irradiation fluence for a period of time, so that the internal transmittance of the preform is increased to an improved internal transmittance IN, which is greater than that of the original preform glass 50 before irradiation. The internal transmittance τ is also at least .07 (〇 / 〇 / cm). As shown in Figure 11, photolysis of this fused silica glass includes the provision of a small paper size suitable for financial management ΓΟ (please read the precautions on the back before filling this page), 11 583412 Μ B7 V. Description of the invention (勹) The Ministry of Economic Affairs, led by Feng's employees, cooperated with the company to print light 44 printed on 300 nanometers onto this fused silica glass. Figures 12-13 show an embodiment using less than 300 nanometers of light 44 to photodissolve the preform 50. The photolytic exposure of the fused silica glass preform 50 preferably includes: optically processing this light of less than 300 nanometers. In FIG. 12, the optical treatment of the irradiation light smaller than 300 nm is to expand the homogeneous laser light beam generated by the laser light 46 smaller than 300 nm. In the preferred embodiment, the laser 46 is an excimer laser. In FIG. 13, less than 300 nanometers of illumination light generated by the light source 48 passes through the integrated sphere 52, and the reflective surface 54 of the internal light of the integrated sphere 52 is less than 300 nanometers for optical processing. In a preferred embodiment of the present invention, providing a fused silica glass having an unirradiated transmittance of T (% / cm) below 300 nm includes providing a fused stone glass that is doped with incomplete rhenium. Preferentially, this hydrogen is inherent to Xuan Rong Shi Xi Shi glass, rather than being input into the glass from the outside, for example, through an infiltration process after glass formation. As shown in Figure 14-15, providing the molten silica glass 50% of the original fused silica glass preform that can be irradiated with νυν% includes: providing a plurality of stone spar particles 58 in the presence of hydrogen, of which Η2 is added Into the fused fused stone glass 56 and the preform 50 into the fused silica glass. As shown in Figs. 14-; 15, hydrogen is preferably added to the ytterbium-purity fused silica glass of the present invention during the glass-forming phase of the direct deposition. Preferentially, this fused silica glass is produced by a single-step flame hydrolysis treatment, in which a supply material for forming silica, such as a supply material containing high-purity si, such as SiCh or 0MCTS (cyclosilyloxy-octamethyl (Cyclosilane) is transferred to the burner 60 in the transfer position 62 in a direct-deposited fused silica glass burner 64 containing heat. Burner flame 66 of this Si supply raw material in flame hydrolysis conversion position 60

Wooden paper scale sword scarf Guanjia County (⑽) Eighty-four Secrets (21 () × 297) U (Please read the precautions on the back before filling out this page} Order. III 12 II. 583412 A7 B7 V. Description of the invention ( g is converted, and the burner 60 is supplied with hydrogen-containing fuels, such as CD4, h2, natural gas, and oxygen. As shown in FIG. 16, the fused silica glass 56 produced in the direct deposition combustion furnace 64 is unirradiated. Source of the original fused silica glass preform 50. The preform 50 is removed from larger mother glass objects by glass removal processes such as cutting and core drilling. Then, the preform 50 is photolyzed to provide Photolytically improved transmission-compatible fused silica glass lithographic optical element preform object 40, and then this preform object 40 is formed into lithographic optical element 30. Direct deposition of molten silica glass object 56 is formed, preferably included in hydrogen The silica particles 58 are formed into a fused silica glass object 56 in the presence of silicon, so that the produced fused silica glass 56 and the preform 50 both contain Sip atomic groups. Members of the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperation, Printing The SiP radicals in the degree of melting have ultraviolet absorption of less than 300 nanometers which can be removed by photolysis. The method of the present invention converts these radicals into less-absorbent glass species by photon irradiation of less than 300 nanometers. See Figure 14 As shown, the fused silica glass formed by this direct deposition forms a refractive index streak 68 of a multilayer structure, and as shown in FIG. 16, this method includes suppressing the removal of streaks formed in glass 56. Any presence in the glass The suppression of streaks is suppressed by avoiding the thermomechanical processing of this glass, such as homogenization and molding of the glass. Do not subject the preform to photolytic irradiation without disturbing other glass structures. In particular, make the glass uniform To make the stripe structure uniform, and the mechanical thermal processing / molding of the glass must be avoided and not used. 50 photolytic irradiation of the glass preform includes prefabricating the glass that has not been homogenized or thermally processed / molded. Piece 50 photolytic irradiation. Provides fused stone glass 56 containing Si | M sub-groups, preferably including a melting content &lt; 2xl017 grams molecule / cubic centimeter. Silica glass%. This paper is suitable for Guancai County (CNS) M specifications (Training / ⑼ 公 发 583412 Α7 Β7) 5. Description of the invention (Η) The present invention further includes a method for manufacturing fused silica glass 40 of optical elements. As shown in FIG. 11, this method includes: providing an optical element fused silica glass 50 having an unirradiated internal transmittance of less than 300 nm τ (% / cm); irradiating with photons less than 300 nm, Fused silica glass uses fused silica glass with photolysis below 300 nm to provide photodegradation to improve the transmission of fused silica glass 40, which improves the internal transmittance to ιν (% / cm), where Ν—τ = △ transmittance (% / Cm), and △ transmittance -.07. The invention also includes the use of this photolysis to improve the transmission of fused silica glass 40 to operate multiple photons with a wavelength of $ 248 nanometers. For example, the glass 40 of FIG. 10 is formed into a lens 30. This lens 30 can be applied as shown in FIG. 4 Lithography system. Provides an optical element fused silica glass 50 having an unirradiated internal transmittance of τ (% / cm) below 300 nm, preferably including providing an unirradiated transmittance T of less than 300 nm of not more than 99.92V The optical element of the centimeter is fused silica glass 50. 98% / cm。 Prior to 50 photolytic irradiation of this glass can preferentially improve the transmittance IN of less than 300 nm at least 99.98% / cm. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. In a preferred embodiment, this method includes photolysing the glass to increase the transmittance of the glass such that Δ transmittance-· 09, and more preferably △ transmittance 16. A method for photolytically irradiating fused silica glass 50 with &lt; 300 nm photons, including providing &lt; 300 nm light, and projecting &lt; 300 nm light 44 on the fused silica glass . As shown in Figures 12-13, this method involves the use of an optical processing system, such as a beam expander, or a reflective integrated sphere to optically process and direct the &lt; 300 nm light. In an embodiment, the method includes providing a laser light source of &lt; 300 nm; providing a laser beam of &lt; 300 nm; expanding the laser beam of &lt; 300 nm; and adapting the paper size China National Standard (CNS) M specification (210X 297 mm) 13 583412 A7 B7 V. Description of the invention (丨 0) The expanded &lt; 300 nm laser beam is projected on the fused silica glass 50. This M-ray beam may be successively generated, such as from a laser, or may be pulsed, such as from an excimer laser. As shown in FIG. 13, an embodiment of the present invention includes a method of: providing a <300 nm non-homogeneous light source 48, such as a discharge light bulb; providing a reflective container 52; arranging fused silica glass 50 in the reflective container 52; and &Lt; 300 nm light 44 is projected onto the fused silica glass in this reflective container. This reflective container 52 is preferably an integrated sphere having a reflective surface 54 of &lt; 300 nm ultraviolet, which preferably seals the glass 50. Printed by the Central Standard of the Ministry of Economic Affairs and Consumer Cooperatives. The method of providing fused silica glass with a non-irradiated transmittance of τ (% / cm) below 300 nm includes providing fused silica glass 50 doped with non-filled hydrogen. The hydrogen contained in this glass 50 is preferentially inherent to the glass, rather than being input into the glass through the enrichment process. Provides melting below 3,000 nanometers with a transmittance of T (% / cm); Mayanite glass, preferably including a plurality of silica particles 58 in the presence of hydrogen, of which Η2 is added to the fused silica In glass 56, as shown in the direct deposition process of FIGS. 14-15, out of which is added during the direct deposition glass formation stage. This method includes providing a precursor supply material of silica; transferring the supply material of the stone sieve to a conversion position burner; using the conversion position burner, converting the supply material of silica into a plurality of silica dust particles 58; Stone dust particles are deposited on the heated fused silica surface of the glass object 56 so that the silicon dust particles are melted into the heated fused silica surface, and hydrogen molecules are added to the fused silica glass 56. With this direct deposition process, the hydrogen in the glass is generated by the switching position, its reaction, the fuel, and the supply materials that are delivered to the burner. Use thorium-containing fuels (such as H2, CH4) and hydrogen-containing paper standards to comply with China National Standards for Standards (CNS) A4 (210X 297 issued) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 583412 A7 B7 V. Inventions Note (丨 丨) The supply of raw materials can provide hydrogen in Na Weaving. In the presence of hydrogen, direct deposition to form molten fused silica preferentially produces fused fused silica glass 56 containing SiH * flippers. At UV ^ absorption below ca nanometers, the Sip species in the glass have photolytic removal, and the SiH * species can be edited by the invention A method is included in which the fused silica glass 56 formed by direct deposition contains the refractive index fringes 68 of the multilayer structure formed, and the method further includes suppressing the removal of the formed fringes, especially before the irradiation step. Inhibition of removal is achieved by avoiding homogenization of the glass and avoiding mechanical thermal processing / plasticization of the glass. Fused silica glass with a non-irradiated transmittance of τ (% / cm) below 300 nm is provided, preferably including fused silica glass with a content of &lt; 2x10ΐ8ΐ2 / cm3. The provision of fused silica glass with a non-irradiated transmittance of T (% / cm) below 300 nanometers preferentially includes the provision of fused silica glass containing uniform impurities, the impurity value being in the glass surface area and inside the glass It is best to be less than 200ppb. The present invention further includes a method in which the provision of fused silica glass 50 is to provide a high-purity fused silica glass component having a large size D &gt; 17 cm and a thickness TH &gt; 7 cm; preferably a diameter &gt; 8 inches. At the same time, the dish is 4 inches thick. High-purity fused silica has high internal transmittance to ultraviolet light, highly uniform refractive index, low birefringence, and can be formed, molded, and polished into optical elements. Because the light source used in modern lithographic step appliances is excimer laser, the resistance to pulses and high-energy light is also an important parameter for the lifetime. The non-reactive molecular hydrogen (¾) existing in the fused silica glass can be adapted to the Chinese national standard (CNS) A4 specification (X 297 mm) according to the paper size 12 (Please read the precautions on the back before filling this page)

583412 A7 A7 _____ B7 V. Description of the invention ((1 Laser radiation · The observation of the reaction time and the content of the recording class is reduced and the resulting recording is not as good as the money. Wei, than the unpaired left of Equation 1 The electronics are much smaller.

= SiO + I / 2H2-) &gt; = Si〇H The central standard fisherman's consumer cooperative print bag A + Equation i of the Ministry of Economy Therefore, in general, the molecule H2 is regarded as a necessary permeate in high-purity molten stone. There are several ways to determine that Hz is added to glass. A simple but time-consuming method is to make the county gas infiltrate the glass under high pressure. This method is quite time consuming, because it must be based on the diffusion constant of Naaishi. For continuous applications, lens blank-sized parts (diameters> 8 inches and thickness about 4 shots) will require 2282 days to load at 35G ° C. When the loading temperature is 800 ° C, this time is reduced to 68 days. It should also be noted that when using a higher loading temperature to penetrate the glass, jj2 will react with the glass to produce SiOH and SiH. As will be demonstrated below, this process and reaction product SiH can be detrimental to the transmission characteristics of this material. Clearly, this is not only a time-consuming process, but also the use of high-temperature and high-pressure Qin gas to infiltrate fused silica glass has also caused considerable problems for actual industrial manufacturing. According to the present invention, the addition of H2 during the true formation of high-purity fused silica glass is a preferred method of providing fused silica glass for optical components. The glass has an unirradiated internal transmittance of less than 300 nm and an inherently non-input non-filled hydrogen. . The preferred method of the present invention is shown in Figs. 14-15. Direct deposition flame hydrolysis is used to produce high-purity fused silica containing intrinsic molecules Qin; this knife Hz is added to the fused silica glass simultaneously during deposition and solidification. Provides high-purity fused silica glass, where the laser is damaged (forms a color center

: SiH

13 (Please read the notes on the back before filling this page)

14 14 583412 Central Standard of the Ministry of Economic Affairs 印 Printed by employees' consumer cooperatives A7 B7 5. The invention description (β)) is minimized and no post-processing of glass is required, such as refractive index homogenization or hydrogen filling, and minimal SiH formation occurs . Through balanced fuel (CH4, H2), oxidant (〇2), and supply gas (SiCk OMCTS cyclosilaneoxy), we can make the inherent concentration of high-purity fused silica glass from &lt; 1016 g HVcc Si〇2 It reached 1018 gram molecules Hz / cc SiO2, which was measured using the Raman spectrum analyzer H2 molecule extension. We have observed that the absorption characteristics of the Raman spectrum at 2260 cnT1 in high-purity molten silica loaded with H2 and then heated are related to the magnitude of the subsequent absorption spike characteristics. This spectral position is close to where SiH vibration (2280 cm-1) was found in photolyzed samples containing silica. We believe that the vibration at 2260 cm_1 is due to the SiH species (we are represented by SiH *) bonded to η, which is formed by the high temperature reaction of H2 with Shi Xishi, and this species is a precursor of photochemical , Can produce Si E, center. The decrease in absorption is thought to be due to the reaction of E 'with Η, that is, the SiH produced by the pairwise recombination in equation c. To explain the decrease in absorption, it is believed that the absorption cross-section of SiH is much smaller than that of SiH *. These reactions are shown in equations A and B, where the precursors regarding the initial absorption spikes are represented as Sip. Equation C is written at the bottom, showing the reaction of E ’center with Η to produce SiH species:

Si-0-Si + H2 + thermal- &gt; SiH * + SiOH * equation (A) SiH * + hv-&gt; [E '+ Η] equation (B) [E, + H]-&gt; SiH equation ( C) We have found that the presence of SiP results in that the transmittance of fused silica glass can be improved by irradiating the glass with photolysis. We found that the absorption of the fused silica glass containing SiH will eventually be lower than the initial absorption measurement, and this paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). 1 (Please read the back first (Notes to fill out this page)

583412 A7 B7 5 11 5 'Invention description (丨 ψ) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs That is, through this irradiation treatment, this glass becomes more transparent. At short lithographic wavelengths below 200¾ microns, such as 193 nm, the absorption due to the species' low-energy tail can be improved by photolytic irradiation, such as photolytic irradiation using a strong excimer light source. It is believed that the absorption cross section of plutonium is much larger than that of SiH. Important practical considerations for SiH * are the effect on the initial transmission of 193 nm, and the removal of Sip can provide fused silica glass with improved induced transmission. According to the present invention, high-purity fused silica glass is measured by a frequency spectrophotometer to provide highly accurate internal transmission measurement. This glass was then irradiated with 193 nm excimer laser radiation and measured again in a spectrophotometer. The data from this spectrophotometer show that the transmission of 193 nm has increased by 0.17%, which is the result of the disappearance of SiP. Photolytically exposing fused silica glass to ultraviolet light at <300 nm in accordance with the present invention results in an increase in the transmittance of the glass at wavelengths below 300 nm. Both excimer radiation and continuous UV light sources have been shown to be effective in this process. According to the present invention, the process of forming fused silica glass under high-temperature environmental conditions of high molecular weight europium 2 has been shown to form Sip species in glass. Within a particular set of experimental or processing conditions, the strength of Sip correlates well with the final H2 gram content of this glass. This species is assumed to have an electron transition at high energy (> 6.4 eV); that is, this low-energy, long-wavelength tail will absorb at 193 nm. The photolysis of SiH * reduces its degree by breaking Si—H * bonds. The recombination of silicon and listeners produces a related SiH species, which is different from the original wood atom group. According to this issue (please read the precautions on the back before filling out this page) Order 16587412 A7 V. Description of the invention (\ 〇 Employees' cooperation agreement of the Central Bureau of Standards of the Ministry of Economic Affairs ^ indicates that the type of SiH produced is more than SiH * Small absorption cross section, so the shape of this surface depends on 193 nanometers of transmissibility. Through prior irradiation, Sl_ is converted to SlH through photolysis process. This is the process of the present invention to increase the transmission below 300 nanometers. In this example, in terms of industrial manufacturing considerations, the irradiation of large prefabricated pieces (diffuse ride) is a baffle to produce excimer laser beams to provide excimer beams. For light bulb irradiation It is large enough inside a reflective container, such as an integrated sphere, to preform parts of the Rongqi stone to determine uniform illumination. We observed (Figure 17) that the relatively high H2 in the glass and the relatively low 193 nm Transmission correlation. Shown are two types of H2 values that are lean at a fixed impurity concentration. In this case, the transmittance is measured by a spectrum photometer (Hitachi UV spectrometer) with a low-power illumination source. Figure 18 display Graph of the relationship between the absorption of 215 nm / cm caused by each fused silica glass and the number of pulses of 193 nm exposure, one of which is made by flame hydrolysis treatment, and the other glass is filled with pressure / High temperature glass is formed after processing. When the glass is exposed to 193 nm excimer laser radiation (6mj / cm2 / pulse), the absorption can be seen to increase very rapidly (because the center of 215 is at 193 nm, there will be Significant absorption. This measurement is taken as a measure of change in transmission at 193 nm). This absorption then decreases to a lower value over time. The Raman spectrum of the glass treated at high pressure Hz / high temperature conditions shows the presence of specific hydrogen The absorption of the bond type is called SiP (Si〇2 + H2-> SiH * + HOSi). The intensity of this absorption is well related to the value of the absorption peak. Read the notes on the reverse side and fill in this page) This paper size applies to China National Standard (CNS) A4 (210X 297 mm) \ C1 583412 A7 B7 5. The description of the invention (丨 b) is related. As shown here Trace The presence of SiH * indicates that high-purity fused silica glass such as directly deposited (; 0171 丨? Inc.rporate (1 HPFSR fused silica glass has a relatively low transmittance, because the Qin content is increased The photolysis of the center will cause it to decrease, and increase the transmission of 193 nm. This transient absorption is related to the processing of glass, especially the processing conditions of high H2 concentration and a certain temperature time. Figure 19 shows Graph of 193 nm absorption / cm2 vs. pulses caused by glass, this glass is made by direct deposition flame hydrolysis, and also uses 193 nm light for a short period of time, but uses much lower irradiation (&lt; 1 mJ / cm2 / pulse with a repetition rate of 400 Hz). 1 mJ / cm2 / pulse and less exposure are expected by the lithographic optical element method of the present invention. This figure shows that after about 800,000 pulses at a lower fluence, the glass appears to `` cause transmission, '' meaning that the provided fused silica glass becomes more transparent to irradiation. This fused silica glass is more transmissive (negative absorption) at 193 nm after an exposure time of 2000 seconds. Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs Figure 20 is for two glasses with different H2 content The measurement of the 193 nanometer transmittance (called the internal transmittance) is made. The "initial" transmittance is the transmission measured using a spectrum analyzer when the original fused silica glass was made. One million pulses of 193 nm excimer laser light were irradiated with this molten silica glass by photolysis, and the amount of irradiation was 丨 pulse. "The final π transmission is measured after the processing, using a spectrometer to measure the molten silica. Glass increases transmission by 193 nm. We noticed that the transmittance increased by 0.12 to 0.17% / cm. We further observed that in higher samples, higher transmission increases can be measured. This —10g (17T〇) zero line shows that the paper size is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) 7,0 583412 A7 V. Description of the invention (ΐΠ) 8 Photolysis of Shi Xishi glass improves its transmittance below SiN * (SiH * + hv-> [Si H]). A 248 * micron excimer irradiation was used to perform a similar experiment. For this set of experiments, an exposure dose of 15 mJ / cm2 / pulse was used for one million pulses. According to the contraction effect caused by laser, using 248 nm irradiation to excite requires about 10 times the exposure of 193 nm to achieve the same effect. The results obtained suggest that the irradiation conditions used for 193 nm and 248 nm irradiation are comparable. The measured internal transmission of 193 nm before and after 248 irradiation is shown in Table 丨. Table 1% T change after% Τ before glass IN-T = / cm T / cm IN △ Transmittance 11801RM15,20 mm 99.45 99.62 0.17 11801 {^ 15,89 mm · 99.40 99.56 0.16 119907RM7B, 40 mm 99.20 99.37 0.17 119907RM7B, 55 millimeters 99.19 99. 35 0.16 We also noticed that the transmission of 248 nanometers also increased after irradiation, as shown in the data in Table 2. (Please read the notes on the back before filling out this page) f- Order $ 1 printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs This paper applies the standard of China National Standards (CNS) M (210 × 297 mm) 19583412 A7 B7 V. Invention Description (ιδ) Table 2 %% change after lamp before glass IN-T = / cm τ 11801RM15, 20 mm 99.92 11801RM15, 89 mm 99.91 119907RM7B, 40 mm 99.91 119907RM7B, 55 mm 99.91 / cm IN △ Transmission 99. 99 0. 07 99.98 0.07 99.99 0.09 99.99 0.08 Consumption cooperation between employees of the Central Government Bureau of the Ministry of Economic Affairs and a group of fused silica glass with different H2 content of Du Yin Bi are also exposed to non-electricity generated by bulbs in the <300 nm ultraviolet range Coherent continuous illumination source. The change in transmittance of H2 = 2.3-3.2 mol / cm3 glass after 24 hours of Xe bulb exposure is shown in Figure 21. We observed an increase of about 0.15%. Irradiation of low vapor pressure mercury lamps has also been used to affect the increase in transmittance. The data shown in Figure 22 again shows that after 24 hours of irradiation, the transmittance increased by about 0.2 ° / 0. Those skilled in the art will appreciate that various modifications and changes can be made to the present invention without departing from the spirit and scope of the invention. Therefore, we can say that various modifications and changes are included in the scope of the patent application of the present invention and its equivalents. (Please read the notes on the back before filling out this page) Fun-、 1Τ ✓ Millimeters 9 2 ^ Ξ ^

Claims (1)

583412 Li Yanguo A8 B8 C8 D8 20 Printed by the Consumer Cooperatives of the Central Bureau of Standard Vehicles of the Ministry of Economic Affairs1. An ultraviolet lithography method comprising: providing a radiation source below 200nm to generate photons for photolithography, h for Photolithographically improved light lithographic printing optical element of transmissive fused fused silica glass, which transmits less than · nm light lithographic photons. Photolithographically improved light lithographic printed optical element of transmissive fused silica glass, using less than 200nm Photolithographic printing of photons to form a photolithographic printing pattern, reducing the photolithographic printing pattern and projecting the photolithographic printing pattern onto a radiation-sensitive photolithographic printing medium to form a photolithographic printing pattern. 2. The method according to item 1 of the patent application, wherein a radiation source below 200 nm to generate photolithographic photons includes providing ArF excimer lasers and generating a variety of 193nm photolithographic photons. 3. The method according to item 1 of the scope of patent application, wherein a photolithographic optical element for providing photolytically improved transmission fused silica glass is provided, which comprises a photolithographic optical element preform for providing photolytically improved transmission fused silica glass. Objects, and optical lithographic printing optical element preforms forming optical lithography with improved transmission fused silica glass are optical lithographic optical elements. 4. The method according to item 1 of the scope of patent application, wherein the preform for providing a photolithographically improved optically lithographically printed optical element with improved transmission fused silica glass includes a fused silica glass object providing an optical element, which is less than 200. ηπι Untransmitted internal transmittance of T (% / cm) and photolytically exposed fused silica glass to &lt; 300 nm photon irradiation to produce photolithographically modified transmissive fused silica glass objects at less than 200nm The internal transmittance IN (% / cm) will be increased such that In-T = △ transmittance and △ transmittance g0.7. This paper uses China National Standard (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before filling out this page)-Packing_ Order 583412 ABCD 2 Patent Application Scope Central Bureau of Standards Printed by the Employee Consumer Cooperative 5. The method according to item 4 of the scope of patent application, in which photolithographically exposing the stone slab glass to &lt; 3 m photon irradiation includes providing <coffee line and projecting <300 nm light onto fused silica On the glass. 6: A method according to item 5 of the scope of patent application, wherein the method includes optically operating &lt; 300nm light. 7. The method according to item 4 of the scope of patent application, which provides a county with an untransmitted transmittance of T (Van) below 300 nm, which includes the provision of fused silica glass containing non-full hydrogen-containing dopants. & The method according to item 4 of the scope of patent application, which provides a transmission rate below the unexposed transmittance (%% / an). What to do ^ The outline includes providing a plurality of stone syrup particles together in the presence of chlorine, where Hz is added to the fused silica glass. 9. The method of claim 4 in the scope of patent application, wherein the method includes: in the presence of a hydrogen towel to guide the deposition of Shiling Shishi to the county stone, the county object, where the provided production: . 10. The method according to item 9 of the scope of patent application, wherein the Sip species has photolytically capable of removing absorption of ultraviolet light below 300 nm. H. The method according to item 9 of the scope of patent application, wherein the direct formation of fused silica glass has a layered structural riding rate, and the method includes suppressing and removing the formed streaks. 12. The method according to item 9 of the scope of application for a patent, wherein the fused stone glass has a content of &lt; 2x1017 molecules / cubic centimeter. , Fused, optical element fused silica glass, which has not been irradiated below 300 (Please read the precautions on the back before filling in this page.) Equipment, 1T 22583412 A8 B8 C8 D8 VI. The scope of patent application for the internal transmittance is T (% / cm), and the fused silica glass is photolytically exposed to &lt; 3 〇〇nm photon irradiation to provide photolytically improved transmission fused silica glass, which will increase the internal transmittance IN (% / cm) below 300nm, where IN-T = △ transmittance (% / cm) and △ Transmittance ^ 0.07. 14. The method according to item 13 of the scope of patent application, wherein the method further comprises using the photolytically modified transmission fused silica glass to manipulate various photons with a wavelength of $ 248nm. 15. The method according to item 13 of the scope of patent application, wherein the fused silica glass providing the optical element has an internal transmittance of τ (〇 / 0 / cm) below 300nrF without irradiation, which includes providing the optical element. 92%。 Fused silica glass below 300nm unirradiated transmittance T is not greater than 99. 92%. 16. The method according to item 13 of the scope of patent application, wherein exposing the glass photolytically will provide: an increase in transmittance IN below 300 nm of at least 99.98% / cm. 17. The method according to item 13 of the scope of patent application, wherein providing the glass and exposing the glass photolytically includes increasing the transmittance of the glass so that the transmittance ^ 0.09. 18 · According to the method of applying for the scope of patent application No. 13, which provides glass and printed by the Consumer Cooperatives of the Central Bureau of Standardization of the Ministry of Light Economy (please read the precautions on the back before filling this page). Transmittance makes △ transmittance ^ 0.16 〇19. The method according to item 13 of the patent application scope, wherein the photolytic exposure of fused silica glass to &lt; 300nm photon irradiation includes providing &lt; 300nm and projection &lt; 300nm light on fused silica glass. 20 · The method according to item 19 of the scope of patent application, which includes optically manipulating the paper. The size of the paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 583412 A8 B8 C8 _____D8 6. The scope of patent application 3 2 Ministry of Economic Affairs The bureau's consumer cooperation with Du Yin produced <300nm light. 21. The method according to item 20 of the scope of patent application, which includes providing a laser light source of 纲 nm, generating &lt; 300nm laser light beam, expanding &lt; 300nm laser light east, and projecting &lt; 300nmt emission The beam of light hits the fused silica. 22. The method according to item 13 of the scope of patent application, which includes providing a <300 nm non-homogeneous light source, generating a reflective container, placing fused silica glass in the reflective container, and projecting <300 nm light to reflect Fused silica glass. 23. The method according to item 13 of the scope of patent application, wherein providing the fused silica glass with a non-irradiated transmittance of T (% / cm) below 300 nm includes providing fused silica glass which is not full of hydrogen and contains a dopant. 24. The method according to item 13 of the scope of patent application, wherein providing the fused silica glass with an unirradiated transmittance of T (% / cm) below 300 nm includes providing a plurality of silica particles together in the presence of hydrogen, wherein Hz is added to the fused silica glass. 25. A method according to item 24 of the scope of patent application, wherein the method includes providing a raw material of molten silica precursor, supplying the raw material of silica to a conversion site burner, and using the conversion site burner to convert the silica raw material into a plurality of silica dust The particles are deposited on the surface of the heated fused silica, wherein the fused silica particles are fused into the heated fused silica surface and hydrogen molecules are added to the fused silica glass. 26. The method according to item 24 of the scope of patent application, wherein the method comprises: directing the formation of silica particles to be deposited into a molten silica object in the presence of hydrogen, wherein the provided molten silica glass includes a plurality of SiH * species . (Please read the precautions on the back before filling in this tribute) 、 1T paper with Chinese solid standard Gns) A4 specification (2ΐ〇χ297 公 [) 583412 A8 B8 C8 --__; _08 6. Scope of patent application 27 · Based on the application The method of the scope of the patent No. 26, wherein the SiH * species has photolytically removing the absorption of ultraviolet light below 300 nm. 28. The method according to item 26 of the patent application, wherein the directly formed fused silica glass has a layered structured refractive striation and the method includes suppressing removal of the formed striation. 29. The method according to item 13 of the scope of patent application, wherein the untransmitted internal transmittance of the fused silica glass below 300 nm is T (% / cm) and the H2 content of the fused fused silica glass &lt; 2χΐ 〇18 molecules / cm3. 30. The method according to item 13 of the scope of patent application, wherein providing the untransmitted transmittance of the fused silica glass below 300 nm is T (Vcm) includes providing the fused silica glass with uniform Na contamination. 31. The method according to item 13 of the scope of patent application, which includes exposing the glass to light below 300 nm with a predetermined transmittance-sensing throughput and a predetermined transmission-induction exposure time, in which the transmittance S0.10. 32. The method according to item 31 of the scope of patent application, wherein the glass is exposed to 193 nm light, the light throughput is &lt; imj / cm2 / pulse, the pulse frequency is at least 400 Hz, and the pulse number is> 800,000. . Printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs33. The method according to item 31 of the scope of patent application, in which the glass is exposed to 248 nm light, the light throughput is> i5mJ / cm2 / pulse, and the pulse number is at least one hundred Million pulses. 34. The method according to item 13 of the scope of patent application, wherein the untransmitted transmittance TS99.5% below 300nm at 193nm and the photolytic exposure of the glass result in an increased transmittance IN-99 · 7 ° / 〇 at 193nm. 35. The method according to item 13 of the scope of patent application, in which the Chinese national standard (CNS) A4 specification (210X297 mm) is applied below 193nm below the paper standard. 583412 A8 B8 C8 D8 9%。 T in the range of 99.5 to 99.8% and photolytic exposure of the glass so that at 193nm increased transmission in-99. 9%. 36. The method according to item 13 of the scope of patent application, wherein providing the fused silica glass includes providing a maximum size D &gt; 17 cm and a thickness TH> 7 cm of the fused stone glass. 37. An apparatus for improving an optical element preform of an initial molten silica glass, wherein the apparatus includes an optical element preform receiver of an initial molten silica glass to support the optical element preform, a photolytic exposure device, and the photolysis The sexual exposure device has a &lt; 300nm light source to generate &lt; 30 Onm irradiation light and an optical management system to guide &lt; 300nm irradiation light, wherein the &lt; 300mn irradiation light is projected onto a pre-molded silica glass optical element preform And through it, the preform is borne by the holder of the preform and results in an increase in internal transmittance (% / cm). 38. The device according to item 37 of the scope of patent application, wherein the &lt; 300nm light source is &lt; 300nm laser. 39. A device according to item 37 of the patent application, wherein the optical management system includes a beam expander. Printed by the Central Government Bureau of the Ministry of Economic Affairs, Bureau of Consumer Cooperatives 40. The device according to item 37 of the scope of patent application, where the <300 nm light source is a <300 nm non-homogeneous light source. 41. A device according to item 37 of the patent application, wherein the optical management system comprises a reflective container, the container comprising a supporting preform. 42. The device according to item 37 of the patent application, wherein the holder is a plurality of optical element holders to receive at least two optical element preforms. 43. The device according to item 37 of the scope of patent application, of which the &lt; 300nm light source is &lt; 26 26 583412 A8 B8 C8 D8 6. Applying for a laser with a special brake range of 300nm, the holder is a plurality of optical element preform holders to Bearing at least two optical element preforms including a first optical element preform and a second adjacent optical element preform, wherein the first preform is adjacent to the second preform, and the optical management system includes a beam expander, the The expander generates an expanded laser beam, wherein the expanded laser beam is first projected on the first preform, and then continuously projected on the second adjacent preform. (Read the notes on the back before filling this page) Consumption cooperation and printing by employees of the China Economic and Trade Bureau of the Ministry of Economic Affairs This paper is sized for China National Standards (CNS) A4 (21〇 × 297)