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Photosensitive Glass and Glass-Ceramics
Nicholas F. Borrelli
Photosensitive Glass-Ceramics
Publication details https://www.routledgehandbooks.com/doi/10.1201/9781315368801-4 Nicholas F. Borrelli Published online on: 29 Jun 2016
How to cite :- Nicholas F. Borrelli. 29 Jun 2016, Photosensitive Glass-Ceramics from: Photosensitive Glass and Glass-Ceramics CRC Press Accessed on: 02 Oct 2021 https://www.routledgehandbooks.com/doi/10.1201/9781315368801-4
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3 INTRODUCTION AND BACKGROUND AND INTRODUCTION Glass-Ceramics Photosensitive 1 From then on and even on and From new then present, up crystal the to because we start with the formation of formation the with we because start 2,3 The relevant The here point because crystal because 2 additions, it it additions, 31 - - - - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 mechanism, which has been discussed in some detail in Holand and Beall Holand and in some detail in discussed been which has mechanism, Clearly, by Ag nanoparticle. involves the abetted this aheterogeneous nucleation nucleation is, by is not known; that what process reaction(s) and aided occur actually actual of the chemistry The treatment. thermal oftogether aconsequence the as 3.3 3.4 Equations and occur reality Ynucleated In by Ag nanoparticle. X and the
initial stage of the process. Borrelli et al. Borrelli stage process. of the initial angle. However, some light (forgive sheds is one study that there pun) the on the contact well as the as metal/solid, and crystal/liquid, energies,facial metal/liquid, inter various of interplay of the the terms in agent. of Itcase ametal is described book on glass-ceramics technology. on glass-ceramics book complete discussion physics of the of nucleation Beall’s is provided Holand and in Amuch more word just for another is really crystallization. controlled ceramics words, other glass- size. In or but grain no with control amount of the temperature ahigher to glass the by would heating that produced phase be is invariably the which manner acontrolled in produced is be to that phase the with deal we will cases composition. the all In altering further diffusion, produces hence and energy free words,the composition other any local alters In fluctuation area. alocal in by composition the changes crystallization to barrier energy a lowering free of the 32 reported in both the open and patent literature. and open the both in reported and known been has glass the derived from phase forcenter ananocrystalline chapter. of the beginning atthe to situation alluded of twice-baked kind the nuclei as act can phases form to for phases these additional is that more surprising even and phases nucleate can certain noble particles metal some certain glasses, In 3.2 the Ag and the dielectric constant of the medium medium of the constant dielectric the Ag and the silver complex ofthe of the is afunction constant plasmon that dielectric resonance function of the thermal treatment. We treatment. copy expression the thermal for of here for the function absorption the Ag nuclei the a composition change(see as in the surrounding track to Section 2.5) Ce for convenience: simplified here version the to given2, schemathe repeated which is of Chapter in here. covered (Ag
Here, Here, The extension of this process to have the Ag nanoparticle act as anucleation extension as have act to The process Ag nanoparticle of the this Schematically, one adds another reaction equation, shownSchematically, equation, reaction below another 3.4, one adds Equation as
NOBLE METALNOBLE NUCLEATION XY represents the nanophase material produced by the glass constituents constituents by glass the produced material nanophase the represents +3 +hv →e+Ce n Ag (Ag 0 ) n + + heat →XY +XYheat + heat →Ag +eheat 0 ) + heat →(Ag ) +heat 4 Photosensitive Glass-Ceramics and Glass 5 used the shift in the spectral position of spectral the in shift the used +3+ (250–350 nm) 5,6 0 m ) 0 Examples from both will be be will both from Examples n
in which the Ag is embedded Ag which is embedded the in (3.3) (3.4)
4 in the the in (3.2) (3.1) - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Photosensitive Glass-Ceramics
to the size dependence of dependence size the to ment above of by use the the expression. treat silver thermal of the the a function as size speck estimate to was used peak absorption of the variation The silver the change in due occurred. size the to speck effect only asmall that indicated This treatment. thermal of the temperature of the only slightly wavelength in shift to was seen afunction as peak absorption the glass, respectively. bromine, with and without glass bromine the bromine-free For the was case Br. this in compositionglass halide where the condition on when the tion depends convenience position absorp reader. of resonance of the Note the how spectral the FIGURE 3.1FIGURE N.F. Borrelli, J.B. Chodak, D.A. Nolan, and T.P. D.A. 69(11), and N.F. Nolan, J.B. Am. Chodak, Soc. Borrelli, J. Opt. Seward, 1514, 1979. 3.5. (From Equation to position according peak the shifting thus by Br enrichment, increased being is Ag particle the surrounding index Br, refractive the containing glass the in showto that absorption at each temperature. The result of the calculation is shown in Figure 3.2. is result shown calculation of Figure the The in temperature. ateach absorption wavelength observed the match to of maximum required medium surrounding the value refractive the of index the of determine to was glass analyzed containing for bromine- the data absorption the temperature, silver heat-treating with size particle of the variation computed Using this temperature. versus heat-treatment radius the 3.2 Figure shows in inset glass. computed The the the in contained cerium the to edge absorption the altered owing by was significantly latter half-width the because band absorption the change in the than rather was used shift peak absorption The Figure 3.1 shows a typical transmission spectra after a 560°C heat treatment for treatment a 560°C heat 3.1Figure after spectra shows transmission a typical photosensitive for growth a typical crystal wasA glass halide chosen study to the
Surface plasmon absorption of an Ag nanoparticle in a glass with and without Br Br without and with aglass in Ag nanoparticle of an plasmon absorption Surface
% Transmission 100 40 60 80 0.35 C abs 2 expressed by = 2 π V λ 1 Wa m =− 0.45 veleng 5 2 () The size effect on the absorption is due absorption effect size on the The 22 1 m =+ . ++ th (µm) 2 B m A B 2 2 C/ r as discussed in Section 2.5. in discussed as 2 2
(3.5) 0.55 33 5 ) - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 34 the process can continue through a second stage. Here, the initial photosensitive stage. asecond initial Here, the through continue can process the form. will that crystal the to where is unique each mechanism Section 3.6, in specific adefine to discussed it more be difficult weas becomes will phase, nucleating the agent When is nanocrystalline yet formed. is ultimately another of what crystal irrespective argument same It environment. is the local the altering ther fur diffusion, drives then that potential chemical the alters tion Ag of nanocrystal the - by forma caused the case this of concentration in constituents local the in perturbation fluctuation phenomenon,any where thermodynamic examplea good statistical of the Nucleation acrystal. form is will ultimately ions of that the enrichment is an that seen where noble nucleation cases regioning metal Br. all effect with is is in likely the This - surround the by enriching silver initially nucleation occurs phase halide of a sodium the that observation indicates phase. This bromide sodium apure to ultimately leads temperature, heat-treating ahigher silver with about occur, to the and begins speck region atjust of the above that, aNaBr enrichment 500°C, by mechanism explained the be can of avalue NaBr that ataboutabove 560°C. assumes This essentially and 500°C T.P.D.A. Nolan, 69(11), and Am. Soc. J. Opt. Seward, 1514, 1979. N.F. J.B. (From size. Chodak, Borrelli, Ag particle the in change shows estimated Inset the Br enrichment. the indicate to plasmon absorption Ag surface of the peak the in shift the 3.2 FIGURE We see this in another phenomenon that will be described in Section 3.6, in where described be phenomenon will that another We in this see atslightly sharply rises medium index surrounding of the the seen, be can As
Refractive index (n )
Computed refractive index of the region surrounding the Ag speck from from Ag speck the surrounding region of index the refractive Computed 1 1.45 1.50 1.55 1.60 1.65 Index ofgla ss 500 No Br Te mp Photosensitive Glass-Ceramics and Glass erature (°
1.6 1.8 ln o 2.0 1.20 C) 1.25 1000/T 5 ) 1.30 600 1.35 - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 LiF, Na/Li-aluminate), which all occur in one glass sequentially in time. in sequentially one glass in occur LiF, which all Na/Li-aluminate), nucleation study of (Ag,up anew the separate processes phenomenon of Na/ three opens This crystal. 50% than havingas more defined tively glass-ceramic produced photosensi first exampletruly the of a be will This temperature. atahigher mally whichphase, would have ther produced been alkali-aluminate the phase, another nucleate yet nanocrystals produced photosensitive initially the the process—having entirely new is an on twist This phases. photonucleated LiF the and/or from NaF byphase covering nucleation the of more complex constituents glass the from phases mentioned. be also will properties unique examples, For is formed. both some where of aLi-metasilicate be the will second of description be a how developedis phase a the will NaF and first phase. The line 3.4, 3.6 and proceed. to for expressed steps by3.3, the Equations required than higher is often temperature nucleation of (AB), which was photosensitively 3.1 Equations through formed 3.4.to which by is compositional the is produced glass, (XYZ), of constituents phase the temperature. ahigher to upon heating glass the from phase crystalline different nanocrystals produced by the mechanism described above described by mechanism the produced nanocrystals glass, the composition the glass, of which is given Table in 3.1. for aphotosensitive trademark opal NaF-based Incorporated Fota-Lite is aCorning 3.3 Photosensitive Glass-Ceramics We move then next the to level of nano photosensitively crystalline produced nucleate two with We examples ananocrystal Ag nanoparticles where the start the together although occur all 3–5 steps that see we process, will actual the In above the to suggests new added set where be to the reaction yetThis another FOTA-LITE Al ZnO Glass Component Components of the Different Function of the of Descriptions Fota-Lite with Composition 3.1 TABLE SnO Sb CeO Ag Br F Na SiO – – 2 2 2 + O O O 2 2 3 3 AB + X + Y + Z + heat →XYZ +XYZheat AB Wt% 4.8 15.8 0.05 0.20 0.05 0.01 1.0 2.3 6.8 69.0 Glass matrix Thermal sensitizers,redoxagents,refining agents Optical sensitizer Sensitizer andcolorant Crystal constituents(withNaand Ag) 6–8 Function 8 further nucleates entirely an further
(3.6) 35 - - - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 ditions and thermal development providedTable thermal in ditions and are schedule 3.3. 3.2 Figure and exposure con phase. The awhite opal produce will treatment thermal light after UV was region where exposed aglass to only the that to (>600°C). result pertains The of formation phase aNaF spontaneous the atalower (500°C)phase than temperature anucleus as nano NaF acts the treatment). produce to Ag nanoparticle resulting The photosensitive (i.e., by athermal exposure light and to Ag nanoparticle an produce made be can glass composition, the glass concentration, base NBO ahigh which has addition offew Ce/Ag the with 2, Chapter volume in this to discussed As percent. be a to andcontent estimated be fluorine would measured the from estimated be can formed NaF of the amount glass. The awhite form opal to sodium, case this in ion, would and metastable prefer amobile with alkali react to thermodynamically an as Si-Fbond is fluorine the that indicating results, phase opal aNaF >600°C, reheated is glass the When is so the melting fluorine temperature. volatile at the <3% because by weightmaintained: be mainly can that of fluorine amount limited network silica aSi-F is a as the into There species. is likely glass incorporated the 36 in Fota-Lite. in 3.3 FIGURE Temp (°C) 100 200 300 400 500 600 The key element is the fluorine component. At high temperature the fluorine in the fluorine keyThe elementcomponent.temperature high fluorine At is the 0 05 Total fluence:~6J/cm Time: 1–5minutes Wavelength: 30nm Intensity: 10mw/cm Lamp: 1kWHgXe NaF Development Phase of for the the Conditions Exposure 3.2 TABLE
Typical thermal development development for phase the Typical schedule NaF of the thermal 0 100 2 2 150 200 Time (min) HT Photosensitive Glass-Ceramics and Glass 2503 00 3504 00 45 05 00 - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 by the specific exposure/thermal treatment. This distinction in appearance not was in appearance distinction This treatment. by specific exposure/thermal the a cloud be to brought but about of what particles appears nanoparticles NaF sparse is Fota-Lite not ofopacity glass solely the due simply to result of formation of the the development suggest does thermal the exposure and a different schedule. that This albeit evident with exposed state the are in properties Section 4.2 optical different Section 3.4 in in see we opaque As and state. the to will leading of scattering degree for high accounts the This nanoparticles. NaF on the superimposed separation phase evidence is clear evident of atrue still what appears are spots dark the although and (the spots). particles dark NaF 3.5b Figure shows state 20-nm heated exposed and the shows also and some is heated shows evidence that 10– of state unexposed the the 3.4. shown as Figure in apattern, produces ( region. 3.5 FIGURE development 3.3. Figure shown in thermal 3.4 FIGURE Photosensitive Glass-Ceramics The TEM image and XRD of the NaF particles are shown in Figure 3.5. shown Figure in are Figure 3.5a particles NaF of the XRD and image TEM The using asuitable that light blocking mask patterned spatially be can glass The
Thermally developed TEM images of (a) Fota-Lite: images developed (b) TEM and exposed unexposed Thermally Pattern formed in Fota-Lite by exposure through a photomask followed a photomask by the through by exposure Fota-Lite in formed Pattern (a) 50 nm (b 50 nm ) Continued 37 ) Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 38 to have the fill factor varied along the length. An applicationalong the length. haveto factor fill varied the element, 3.7. shown as Figure in transparency. maintain to size particle the NaF compositionin limit modification to a slight with a holographic as medium where used show we be can will glass how this a 193-nm with second excimer. photorefractive the 5 phenomenondiscusses Chapter 3.6. Figure in image section cross the shown in in excitation as at the surface, the wavelength, only near image the produce one can depth by absorption controlled the be can image of exposure the depth the Because exposure of must limited. the it depth be the utilize to although nm, <20 ticles are 3.5c Fota-Lite trace. glass. Figure in shows produced be XRD can the that effects discussion optical the other of in the see previously we as will appreciated, developed phase. and exposed of an trace FIGURE (CONTINUED) 3.5 in Figure 3.9. Figure in phosphor Fota-Litewhere bar, shown the layer as on patterned top is placed of the 3.8. bar, shown as Figure in along of alength edge-illuminated illumination uniform (c) Corning This is accomplished by using a photomask with an array of small openings spaced spaced openings of small by array is accomplished using aphotomask an with This scattering a gradient make to ability is the of consequence patterning Another the and excimer248-nm laser case withdone a was first the exposure in The nanopar NaF resolution the quite since good The be of can formation any image One can further extend this structure to an edge-illuminated array of LEDs of LEDs array edge-illuminated an to structure extend this further can One
1000 1500 Intensity2000 (counts2500 ) 3000 3500 500 0 Fo ta-Lite exp 10 osed andhea 20 t treate Thermally developed TEM images of (c) Fota-Lite: images developed TEM XRD Thermally 304 d [SPLB5K T wo- d = 2.3210 Photosensitive Glass-Ceramics and Glass 05 KR 1J|xra th y]
9 d = 1.6435 of this is away of this produce to 07 S> ursd ay , Au illiaumite-NaF gu st 13,201501:18p(MDI/JAD 0 ES - ) Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 (a) Photosensitive Glass-Ceramics its ability to make a rainbow of colors but the multifaceted way (literally as well of way as arainbow colors as multifaceted but make to (literally the its ability effects described in this book is the polychromatic is the book effect. this in effects described of varieties of the all from phenomenaPerhaps one most of taken fascinating the 3.4 scattering. (a) uniform more produce to 3.7 FIGURE 3.6 FIGURE OYHOAI GLASS POLYCHROMATIC
(a) Patterned exposure to produce gradient scattering, (b) LED illumination of (b) illumination LED scattering, gradient produce to (a) exposure Patterned Deep UV laser exposures to limit the opal region to the surface. the to region opal the limit to exposures laser UV Deep (b ) 10 Not only fascinating in in Not only fascinating 39 Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 (a) the NaBrF phase in this case. What is very different is its transparency in spite in of is its transparency different is very case. What this NaBrF in phase the nucleates then that Ag nanoparticle photosensitive initial the the forming in glasses plays role Ag all it still same as in The does the process. coloring the Ag in later Sn to 40 Table 3.3. Table of SnO, shown as Table in shown 3.1. in are physical and properties thermal The for addition of asomewhat the by addition stronger actionthe produced reducing processing. mal figuratively,see) as will the we develops effect ther the and time overthe exposure 3.9FIGURE U.S. al. et No. 9,011,720. Patent N.F. N. Lonnroth (From Borrelli, (b)and LED-illuminated. 3.8 FIGURE (a) The reducing action stems from the ability of Sn ability the from action stems reducing The composition same given the essentially with above for starts One Fota-Lite except +4 during the thermal treatment, which will be important in the reduction of the the in important be which will treatment, thermal the during
Photographs of the developed colors as indicated in Table in 3.4. developed indicated of colors as the Photographs LED illumination on the edge of a gradient scatterer that is (a) is that phosphor-coated scatterer of edge agradient onthe illumination LED Photosensitive Glass-Ceramics and Glass (b) (b ) +2 to give to up by electrons going 9 - ) Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Photosensitive Glass-Ceramics colors 3.11. is shown Figure in responsible TEM for the from the obtained morphology nanocrystals ofThe the 3.4.2 3.4. Table in noted ratio aspect the to related be Section 3.5 will in explained and be ior will movesmaxima) longerto wavelengthbehav This time. longer the first exposure the development after curve the development exposure of and the 3.10. is shown Figure in Table in listed by treatments 3.4. the oped color. the deeper 3.9a,bthe Figure shows devel examples be colors can of the that elevated atthe longer temperature, exposure times The second hours. to the minutes but now again exposure of is done tens at>300°C the exposed UV with from and then is treatment first the from glass is step coloring where the important This 3.4.1.2 lowerat 10–20 degree temperature. development thermal was done initial the addition, In of duration. amuchare shorter Section 3.3 (Table 3.2), of case polychromatic exposure times but the the in glasses, Fota-Lite ofA 1-kW exposures provided for the is in used all source UV Hg/Xe 3.4.1.1 3.4.1 next. discussed treatments thermal the in see development, somewhatlikely due the to lower thermal we of as the will temperature is some of and this nanocrystals of is clearly size the the to Fota-Lite. related This of the opal photosensitive relative transparent to dense the to is its glass transparency polychromatic the version is that compositionallittle difference NaBrF-based of the It is important to note the progression of the transmission minima (absorption minima progression transmission the note to of the It is important on marked as time first ofexposure the afunction as transmission measured The Composition Other properties Density Thermal expansion (×10 Strain point Annealing point Softening point of Polychromatic Properties Glass Mechanical and Thermal 3.3 TABLE P M First Exposure and Thermal Treatment Thermal and Exposure First Second Exposure and Thermal Treatment Thermal and Exposure Second rocesses icrostructures
–7 and ) M Alkali-zinc aluminasilicate Liquidus temperature= A-831°C I-834°C 2.482 83 444 484 664 P-837°C; liquidviscosity=300,000 echanis m s 41 - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Source: Yellow Deep yellow Orange Red-orange Red Magenta Purple Blue Turquoise Pale green of Particle Size and Model Prediction of the Correlation to the Aspect Ratio Correlation Aspect of to the the Prediction of Particle Size Model and Estimates with Times Exposure of Second aFunction as Developed Colors 3.4 TABLE 42 49, Phys. S.D. Stookey, 5114, J. Appl. J.E. Pierson, and G.H. Beall, 1978. 3.10FIGURE Color Transmission (1.5 mm) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 350 S.D. Stookey, G.H.Beall,andJ.E.Pierson,J.Phys. 49,5114,1978. Appl. Exposure
Time (sec) First ∞ 195 135 105 75 60 45 30 20 10 Transmission spectra of the various colors shown in Figure 3.9. Figure colors shown in various (From of the spectra Transmission a Particle Length 30 40 50 60 75 100 120 160 210 360 (Å) 450 (Maximum) Particle Width (Å) 30 30 30 30 30 35 35 40 45 60 Wa 135 195 veleng Photosensitive Glass-Ceramics and Glass 550 Eccentricity th (nm) (l/w) 1.0 1.3 1.7 2.0 2.5 2.9 3.4 4.0 4.7 6.0 105 75 Observed 60 415 440 460 480 500 520 540 580 640 770 (Å) 65 Absorption Maxima 07 45 10 10 ) Assuming Ellipsoids Assuming Ellipsoids with Axes Theoretical, 415 455 495 535 590 635 700 770 845 995 (Å) 30 10 se 20 l , w c 50 Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 reader is referred to a fuller discussion Stookey in afuller to is et referred al. reader is shown Table in This absorption. position measured of 3.4. spectra the the The of acomparison direction), make short one can the in other the and length the ellipsoid of revolution (i.e., plasmon one along having as two resonances, surface an as approximated extent be it the to that can and shaped clearly anisotropically above Ag of formation nucleus. the the what in silver-rich is used The is tip solutions. solid could easily form and tip.the NaF, crystals body-centered NaBr, all AgBr are and Ag-rich and length along at the changing continually is considered be to tail of the model 3.12 is shownstep. proposed Figure in The compositional where makeup the second color eventually the the in produces tails of presence these the that proposed only one face cube. of from It the is growth apyramidal of with a number them Section 3.4.1), one sees crystals NaF cube-shaped expected of the seeing instead Phys S.D. J. Appl. Stookey, J.E. Pierson, and G.H. Beall, 3.11FIGURE Photosensitive Glass-Ceramics It is important to bear in mind that there is excess over glass there the that Ag in and mind in bear to It is important (thein step treatment first thermal exposure and initial the Surprisingly, after
Two representative TEM images (a) and (b) of the NaF nanoparticles. (From (From Two (a) images TEM (b) nanoparticles. NaF and of representative the (b (a) ) 0.1 µ . 49, 5114, 1978. 10 0.1 µ and calculations using calculations and 10 ) 43 Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 44 FIGURE 3.13FIGURE volumeis the n particle, of the following plasmonposition using the absorption surface of where the equation say,to simplest the model that was chosen; 3.13 Figure the calculate to was used reference, 3.13. shown as this Figure in in shapes approximate different Suffice it 69(11), 1514, 1979. T.P. D.A. color. and N.F. Nolan, the J.B. (From Am. Chodak, Soc. Borrelli, J. Opt. Seward, for account to modeling the in used be of will which length Ag tip, the reduced showing the 3.12FIGURE field. applied the to respect with orientation and geometry for particle the wavelength L space, and free in 69(11), Am. Soc. 1514, 1979. T.P. D.A. and N.F. Nolan, J.B. (d) (From shell. and Chodak, Borrelli, elliptical J. Opt. Seward, tip, (b) (a) (c) ellipsoid, absorption: plasmon resonant pyramidal half-ellipsoid, surface oftion the
Possible model structures to approximate the pyramidal tip for the calcula for tip the pyramidal the approximate to Possible structures model Schematic drawing approximation of the shape of the pyramidal structure structure pyramidal of the shape of the approximation drawing Schematic CV 5 nucl Silver nucl Silver ) ab s eu eu = s s () Na Na 21 πλ 5 F F ) (a) (c) nL 0 32 0 is the refractive index of the glass matrix, λ refractive index is matrix, the glass of the w is the electric depolarization factor appropriate factor appropriate depolarization electric is the Na Na ⋅+ l l () X X εε 21 Photosensitive Glass-Ceramics and Glass {} silver colorcenter Photo-re (d (b Silver halide-enriche ) ) nL w 0 duce w 2 () / l d anisotropic l − 1 2 + d ap ε 2 2 ex (3.6) is the V - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 shown in Figure 3.16.shown Figure in is protocol is shown Table in data treatment spectral exposure thermal 3.5 the and complete phase. The opal the or atwhichfor colors hour point tinting appear, an of 200°C–400°C above, sample atatemperature is exposeddescribed while the (seesensitive made 3.15). been Figure has phase NaF polychromatic the case in As phototosensitive color, the produce to ability is the after glass which is produced pho NaF-based effects of we observe in example optical can variety ofAnother the c 3.4.3 growth. of longer pyramidal longernomenon the is more that nuclei exposure produces expense the atperhaps (see 3.14). Figure more nanocrystals thus and Apossible explanation phe for this of more Ag nuclei growth the likely indicates alone, which more than resonance the Ag of plasmonincrease an step first see we the we after If absorption look atthe silver-rich color. the silver to tip longer deeper exposure, the second the metal; the is not fortip clear. that role the areason exposure is reduce second to of The the the growth pyramidal of the longerfrustrates the that first exposure argued be It can atTable longest the Looking exposure produces shortest tip. the 3.4, that it appears moves then increased. exposure and is blue first exposure the to the est initial as (absorption longest is atthe maximum) wavelengthsion minimum for short the color. we If 3.10, look aparticular to atFigure leading step - transmis the we that see 1978. Phys (From S.D. J. Appl. Pierson, and Stookey, exposure. first J.E. G.H. Beall, 3.14FIGURE Photosensitive Glass-Ceramics Transmission (1.5 mm) What is not well understood is the role of the initial exposure as the determining determining the exposure as role is not is well the initial ofWhat the understood 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10 350 ) oloring
Strength of the Ag surface plasmon absorption as a function of time of the of the of time afunction as plasmon absorption Ag surface of the Strength Clear 10secs F Ye ota 195 135 105 llow 75 60 45 30 20 450 - L ight Wa veleng 5506 th (nm) 50 . 49, 5114, 750 45 - - - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 46 FIGURE 3.16 FIGURE 3.15FIGURE Sample Treatments Thermal Fota-Lite for and Colored Times Exposure 3.5 TABLE 1 4 3 2 Mag =2.50KXW
Photo of the colors produced in Fota-Lite. in colors produced ofPhoto the SEM showing the structure of exposed and thermally developed Fotoform. thermally and of exposed structure showingSEM the Xe LampExposure 30 seconds 90 seconds 60 seconds 45 seconds Step 1 D =9mm 2 µm 540°C/40 min,cool, Photosensitive Glass-Ceramics and Glass 560°C/20 min Heat Treatment Step 2 EHT =10.00 kV Flood expose whileon Sig 3.5—several hours hot platesetting Xe LampExposure nal A=RBSD Step 3 Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 perature below 600°C. The exposure and thermal treatment are listed in Table in listed are 3.8. treatment thermal exposure and below The 600°C. perature developing Ag nuclei, the atatem phase we now Li-metasilicate can the produce thermally light and exposing UV to glass agents then Ag the of and and Ce tizing spontaneously. However, crystallizes temperature photosensi the by adding certain is shown Table in material 3.7.glass-ceramic the produce to treatment thermal exposure and after properties mechanical and mal covered be Section 3.5.3. in will that properties interesting and different additional has which phase also converts it ~800°C aLi-disilicate to temperature above wherebying ahigher phase to aLi-metasilicate heating produces 650°C and glass-ceramic. Li-aluminosilicate overshoot first study of the Fotoform his accident produced in that 3.5 effect. by same the one providedSection 3.4 the in as onsame polychromatic it since glass, is produced ishow exposure the develop to long mechanism initial is. phase The the NaF the another of Stookey’sanother is This characteristics. nonetheless, same only of ~20% many the it shares crystalline; it is because aglass-ceramic as not does legally it qualify still speaking, ties. Strictly proper unique with aglass-ceramic into glass the words, other itglass. In transforms the parent of properties and chemical the mechanical alters it isence that significantly polychromatic differ second Br the components such case.in F and The additional as developed composition base of constituents glass the any special the is not from from the distinctivephase ways. and that is first The two important Foto-Lite in ent from noble ofFotoform nucleated is but quite differ the phases one that is another metal Photosensitive Glass-Ceramics So once again, weSo have once again, composition above glass unstable when an heated that a composition base The of Fotoform is shown Table in 3.6 of its ther alisting and It is upon unstable heat aluminosilicate. alkali Fotoform amixed is essentially The colors are weaker than in the polychromatic the version. in on hue than weaker depends colors The are The FOTOFORM Even his mistakes turned into significant inventions! significant into turned mistakes his Even 6–8 discoveries in the late 1950s, which ironically was a temperature 1950s, late was discoveries the atemperature in which ironically Sb SnO Al CeO Au Ag Na K SiO (Corning Code8603) Fotoform/Fotoceram of FotoformComposition 3.6 TABLE Li 2 2 2 O 2 2 O O O O 2 2 2 3 3 1.6 Wt% 0.4 0.003 0.014 79.6 0.001 0.11 4.1 9.3 4.0 47 ------Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Properties of Fotoform Properties Mechanical and Thermal TABLE 3.7 48 Thermal Mechanical Electrical Dissipation factor, at100KHz Young’s modulus/ Specific heat/J/(g·K) Maximum safeprocessing Thermal conductivity/W/(m·K) Coefficient ofthermal Dielectric constant,at100KHz Density/g/cm log Modulus ofrupture,abraded/ Dielectric strength/volts/mil to10mil Loss factor, at100KHz Hardness (Knoop)/KHN Poisson’s ratio temperature/°C sample thickness,DCunderoil ·10 21°C 350°C 250°C 25°C 25°C Expansion (25°C–300°C)/K Wilson Turkon 21°C 150°C 200°C 200°C psi GPa 25°C 21°C 150°C MPa 10 volume resistivity/Ω cm 6 psi 3 100 –l Fotoform Glass Photosensitive Glass-Ceramics and Glass 1.2 1.1 0.008 2.365 0.88 0.75 11.15 7.62 0.050 8690 77 4500 0.061 9.06 0.22 60 8.4 ·10 4.90 6.27 450 450 –6 Fotoform OpalGlass-Ceramic 12.00 1.2 12,100 83 8.9 ·10 0.004 2.380 1.5 0.88 550 1.5 500 5.73 0.014 83 0.023 6.14 0.21 7.23 8.81 4000 –6 Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Photosensitive Glass-Ceramics ArF excimer laser KrF excimer laser 172-nm excimer lamp Ti-sapphire Quadrupled YAG Tripled YAG 254-nm germicidal to develop the dense crystalline phase. By wavelength, using ashorter developto such a crystalline dense as the Source Treatments for Thermal Fotoform Used and Exposure 3.8 TABLE (Li on forhere convenience) photosensitively the that in phase Li-metasilicate produced abbreviation an from as (note FF use we Fotoform ofties that the will material one distinctive of proper the describe to used term is the machinability Chemical c 3.5.1 applications thereof: HgXe 1-kWlamp intensity ofintensity 10 mW/cm which is about 50 μ 3.17. shown Figure in are examples hole of size different patterns or holes etch to niques visas completely a1–2 of piece glass. thick Some through mm - tech photolithographic using glass standard the allows pattern optically one then to photosensitive This treatment. property somewhat specific exposure/thermal on the developed of etch the rate The region of order is of 13 the μ glass. the than so much etch rate greater the makes that glass or no intervening 3.16. Figure in indicated as crystallites, dendritic of the by overlapping the is facilitated contiguous etching morphology and differential The femtosecond laser lamp The following section covers the different unique aspects of the material and the the and following material ofThe the covers aspects section unique different the The resolution of any pattern is limited by the size of the metasilicate grain, grain, metasilicate of by size the the resolution is limited The of any pattern acontiguous form overlapping little with grains pattern the that property It is the 2 2. 3. 1. SiO between crystallized (exposed) (unexposed) glass the regions and crystallized regionsbetween density large difference utilizing lens arrays lenses and Microoptics schedules thermal and sure by acombination produced of expo composite material CTE Controlled state crystallized the and glass the solubility between HF in difference large due the to machinable Chemically 3 ) is roughly 20 times more soluble in diluted HF than the unexposed glass. unexposed the more soluble than HF times ) is roughly 20 diluted in he m ical M m. A typical exposure using a1-kW Atypical m. a360-nm with HgXe lamp 248 nm(2J)1–20shots 193 nm(2J)1–20shots 172 nm(5–60min) (~2 µJ)40fs/20kHz-/800nm-translation 1 kHz/266nm/2W-translation 50mm/s translation50mm/s 200 kHz(400µJ)/355-nm ~5 mW/cm ~10 mW/cm achinability 20 µm/s 2 is 8 minutes so the energy required is oforder of 5 J/ the required energy so the is 8 minutes 2 /(2–7 min) 2 Energy Delivered /(4–8 min) 540°C/30 min,600°C/30min 540°C/30 min,600°C/30min 540°C/30 min,600°C/30min 540°C/30 min,600°C/30min 540°C/30 min,600°C/30min 540°C/30 min,600°C/30min 540°C/30 min,600°C/30min 540°C/30 min,600°C/30min m/minute depending depending m/minute Thermal Treatment cm - 49 - 2
Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 50 Length = 405.59 µm
Length = 220.39 µm Length = 216.90 µm
Length = 412.60 µm
Length = 597.99 µm
Length = 597.94 µm Photosensitive Glass-Ceramics and Glass
Length = 517.48 µm Length = 510.50 µm Length = 202.83 µm
Length = 790.40 µm Length = 604.90 µm
Length = 199.67 µm
FIGURE 3.17 Chemically etched hole pattern in exposed and thermally developed Fotoform. Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 (a) Photosensitive Glass-Ceramics can be estimated from the confocal distance, which is approximately λ distance, confocal the from estimated be can This (focused) intensity high the to beam. of the would portion process restricted be by glass of multiphoton valence amultiphoton the and the The process. from directly the photo the been observed that Ce that observed been 248-nm excimer ~1 laser 248-nm W/cm FIGURE 3.19FIGURE 3.18FIGURE intensity that multiphoton processes will occur. multiphoton will that intensity processes 3.18. Figure in shown shows the exposure pattern. A distinct advantage of a multiphoton process is that the advantage of the amultiphoton Adistinct is that shows process exposure pattern. the 3.19 Figure at800 nm. is transparent glass the because glass inside the anywhere subsequent the crystallization photoreaction and the initiate light one can 800-nm an graph of the depth of the grating. of the depth of the graph A focused 800-nm fs-laser can also be used, which produces sufficiently whichhigh produces used, be also fs-laser can A focused 800-nm sensitizer Ce sensitizer
A 248-nm excimer laser exposure to produce shallow depth of penetration. depth shallow produce to exposure excimer laser A 248-nm An 800-nm femtosecond exposure of (a) a chirped grating, and (b) and amicro grating, of (a) exposure femtosecond achirped 800-nm An +3 +3 could be operative even with 800-nm light. In fact, it In has light. operative could be even 800-nm with is not necessary that is a photoelectron can be produced produced be is can aphotoelectron that is not necessary 2 ~0.1 J/cm 100 µm 2 per pulse, we can limit the depth, as depth, the we pulse, limit per can 11 This means that the excitation the that of means This (b ) /(NA) 2 . Using Using . 51 - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 others. among interconnects, fiber optical and lens bars scanner in seen are technique 3.21.shown Figure in 3.20. is shown lenses Figure SEM process photoin formed in of An The the surface. aspherical form will tension softglass of the surface because then and surface the above to material crystalline out by squeezed surrounding be denser will soft glass regions, the light is blocked aphotomask uses where the one circular then in If tube. outnonexposed of region a toothpaste analogous squeezing to above surface the glassy the squeeze can exposed area the net effect is that The material. surrounding therefore the densificationinfluence flow can the the of is soft and glass under of unexposed the that (600°C) means phase develop to used crystalline perature the tem the since features surface produce to used be can density difference glass. This region by is that more dense ~15% treatment, nonexposed the thermal and sure than lens arrays utilizing the effect. the utilizing lens arrays application of interesting Fotoform it isAnother that provides away micro make to s 3.5.2 exposure. of 100-nJ/cm the Fordepth the is capable ofbeam focusing just view cross-section below shows The surface. the the 52 FIGURE 3.20 FIGURE 200-nJ/cm 24, 2520, 1985. 2520, 24, W.L. Phys. and J. Appl. Morgan, development. N.F. Bellman, D.L. R.H. Morse, (From thermal Borrelli, and by exposure rial The applications for the lens arrays made by this essentially photolithographic photolithographic essentially by applications made this for lensThe arrays the 13 M 2 exposure it was 150 μ ILE
Schematic representation of the way lenses are formed in aFotoform mate in formed way of are the lenses representation Schematic ™ L ens A rrays Photosensitive gla SMILE lenses Ultra 11,12 violet ra ermal treatmen When the metasilicate phase is produced by expo is produced phase metasilicate the When m. Ex (step 1) (step 2) po ys 2 sure exposure the depth was 100 depth exposure μ the Photosensitive Glass-Ceramics and Glass ss 11 ) material surroundin Opaque Ma t sk g m and for m and the - - - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Photosensitive Glass-Ceramics Source: Li-Aluminosilicate of Diagram the SystemPhase 3.9 TABLE book Beall’s (see Holand and possibly be temperatures to phases (LAS) higher silicate atthe formed for allows silica addition of alumino for alumina the of anumber lithium particular, In (>800°C), shown as Table in temperature ahigher to by heating 3.9. thermally produced compositionin such a The ofway modified Fotoformhaveto as be can phases other c 3.5.3 W.L. Phys and J. Appl. Morgan, Bellman, D.L. Morse, R.H. N.F. of lens. (From asingle section of across Borrelli, (b) picture SEM and an Figure 3.20, 3.21 FIGURE (a) Hoboken, NJ,2012. W. HolandandG.H.Beall,Glass-Ceramic Technology, SecondEdition,John Wiley &Sons, ontrolled 4 for Li the
(a) SEM photographs of the lenses formed by the process shown in shown in process by(a) the formed lenses of the photographs SEM 50 Li 2 O Li 2 SiO 60 3 F CTE 2 Li O-Al 70 4 2 Si 40 Li Li 2 O 2 4 80 Si SiO 5 2 2 O Li O oto 4 2 5 3 SiO -SiO
90 1200
3
100 for 1000 0 30 Tr 2
idymit Cristobalite
phase diagram, reproduced here as Table as here reproduced 3.9). diagram, phase
0 100 m
SiO
1400
LiAlSi e 1200 2 (b
2 20
O 1400 ) 6 10 LiAlSi 20 2 O 6 10 β- . 24, 2520,. 24, 1985. Sp 30 od
umene s 40
Al
50 2 O 3 .s . 11 ) 53 - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Condition/Treatment aMaterial aVarietyfor Producing with Materials CTE of Composite Development Protocols Thermal Used and Compilation of Exposure 3.10 TABLE 54 can make FF with Au with low with only and/or FF Ag without make Au.can and tions. question amultitude of in is ways. answered this Au-nucleated is an 3.23, there whether ask to Fotoform. sense Figure fore In makes well. as produced Itever, be there can Au 2 nanoparticles that Chapter we in noted Until now, we have always situation where photonucleating the Ag is the agent; how o 3.5.4 treatment. heat the in gradient athermal exposure and usingpiece acombination of localized asingle in variation is possible CTE aquasi-continuous produce to principle in or lower It higher something produce CTE. in one can by phase temperature, this of amount the of By 7ppm. aCTE which phase, varying has Li-metasilicate the produce to exposure values, is required an CTE intermediate for three that the Note phases. Li-metasilicate and quartz alpha crystalline-stuffed LAS CTE high the are phases 14-ppm For by XRD. the the dominant sample, indicated the as 14 and respectively. 7ppm/C, ppm/C, 3 ppm/C, values representative of of CTE the for SEM measurement three the and spectrum, acomposite value. determining thus by XRD, the indicated as phases crystalline listed of the mixture a different containing each valuescomposition composite of yields listed the CTE, that the acomposite 3–14 produce to order from range in CTE ppm/C. values different with of of phases of anumber these mixture acontrolled produce exposure conditionsby and it judicious was found one can choice that thermal of the Source: No exposure, 800°C–850°C/2h Exposed, 600°C/2h+725°C/2 Exposed, 600°C/2h Exposed, 850°C/2h No exposure, 875°C/2h No exposure, 900°C/2h Table 3.11 noble ion of a number the combinations composi in with lists metal spodumene low is beta is the phase CTE dominant sample, 3-ppm For the the XRD the acompilation CTE, of the are 3.22a–c shown results Figure The in Table for single the 3.10 treatments exposure/thermal of the shows asummary have phases ofA number these lowexpansion coefficientsthermal thus,of (CTE); has lowP has and Ag, sufficient one be to has noto Au.Au the opal There form, for has Ag and Au, less Ag Lhas Au, Au and K has M has only, less Nhas Au, Ag only,O has N.F. BorrelliandJ.F. Schroeder, U.S.Patent Application, 2014. ther V ariations 14 CTE (ppm) 12–14 9 7 5 4 3 Photosensitive Glass-Ceramics and Glass Alpha-quartz, Li-metasilicate,glass Alpha-quartz, beta-spodumene,Li-metasilicate Li-metasilicate, glass Spodumene, Li-disilicate,Li-metasilicate,glass Less spodumene,Li-disilicate,glass Beta-spodumene, Li-disilicate,glass Phase Assembly 14 - - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Photosensitive Glass-Ceramics
5 [1114719 raw] 609 PJD HT FF/RT/900 C/2 hr 01-074-1106-Lithium-LiAlS4O4 04-009-8780> Li2Si2O4-Lithium silicon oxide
C) 4.5 20.0 d=3.4641 4 A 3.5 15.0 3 ) B ts d=0.5091
2.5 oun Beta spodumene+Li-disilicate (c 2 d=3.7457 10.0 d=3.8599
1.5 d=8.8824 3 ppm Intensity 1 Delta L/L/(T-25) (ppm/deg 0.5 5.0 d=4.578 d=2.3948 d=3.1458 d=5.404 d=5.789
0 d=1.8989 d=1.9089 d=7.332 d=2.2925 d=2.9200 d=1.3742 d=1.9244 d=2.0602 d=1.4229 d=1.5316 d=1.4613 d=2.6277 d=2.1017 d=1.8089 d=1.0312 d=2.0171 d=1.4417 d=1.2241 d=1.3138 d=1.2492 d=2.1990 d=1.3075
0.0 100.0 200.0 300.0 400.0 d=1.7422 d=1.3416 d=1.0007 d=1.5909 Temperature (°C) ×103 10 20 30 40 50 60 70 80 Two-theta (deg) Corning [SPLBXXR1Jxray]x1\D4Erika Data Borne 257184 ursday, June 05, 2014 10:27a (MDI/JADES)
C
Corning 10.0 kV 9.4 mm × 250 YAGBSE 200 µm
(a)
FIGURE 3.22 CTE (A), XRD (B), and SEM (C) data for the following values of the composite: (a) CTE = 3 ppm/C. (Continued) 55 Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 56
9 C) 8 7 700 6 Li-metasilicate 600
25)·(ppm/deg 5 B T- 4 500 A ) 3 ts oun 400 (c
lta L/L /( 2
De 1 300 0 Intensity
0.0 100.0 200.0 300.0 400.0 200 Temperature (°C)
100 Photosensitive Glass-Ceramics and Glass 0 10 20 30 40 50 60 70 Two-theta (deg) C
Mag = 2.50 K XWD = 9 mm 2 µm EHT = 10.00 kV Signal A = RBSD
(b)
FIGURE 3.22 (CONTINUED) CTE (A), XRD (B), and SEM (C) data for the following values of the composite: (b) CTE = 7 ppm/C. (Continued) Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Photosensitive Glass-Ceramics
18
C) 16 14 A 12 10 -25)·(ppm/deg
8 s)
6 ount
(c B
lta L/L /T 4 De 2 Alpha quartz Li-metasilicate Intensity 0 0.0 100.0 200.0 300.0 400.0 Temperature (°C)
Two-theta (deg)
C
Corning 10.0 kV 9.5 mm × 100 YAGBSE 500 µm (c)
FIGURE 3.22 (CONTINUED) CTE (A), XRD (B), and SEM (C) data for the following values of the composite: (c) CTE = 14 ppm/C. (From 57 N.F. Borrelli and J.F. Schroeder, U.S. Patent Application, 2014.14) Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 58 residual Ag residual nucleated other versions.the Tablevided 3.11. 3.23 FIGURE the surface plasmon resonance absorption of Au (see the Appendix in Chapter 2). of Chapter Au plasmon absorption in (see resonance surface Appendix the the 9). Au-nucleated the which that notice is consistent sample is Also rose-colored, with (see features absorption Section 9.2 different produce can Chapter in Ag particle the morphology of different where the it phase how that is known Li-metasilicate on the some Ag reduced being must the of come from tints variety this that is conjectured 3.25. is shown Figure Ag in reduction. This of aconsequence It this as of tints variety developedments. exposed and It that is not known generally a Fotoform produce can ing the nuclei. Ag the residual ing This The lack of lowThe color the in Ag versions is not enough there fact is due that the to Ag/Au 3.24, of Figure we standard show someIn to of also SEM comparison an K Sb ZnO Na Ag Au Ag Au SnO CeO Li Al SiO (Mol%) L-P in Figure 3.23 Shown Glasses of the Composition Glass 3.11 TABLE 2 2 2 O 2 2 O O O O 2 + 2 2 3 3 after forming the Ag nanoparticles; that is, all the Ag is used up in form up Ag in is used the is, all that Ag nanoparticles; the forming after
Combinations of other nucleating noble metals whose compositions are pro are whose compositions noble nucleating metals of other Combinations 1.56 0.67 2.54 17.9 0 0 0.06 0.003 0 0.006 0.08 2.4 74.8 K KL 1.56 0.67 2.54 17.9 0 0.0004 0.06 0 0 0.006 0.08 2.4 74.8 + is capable of being reduced during the thermal treat thermal the is capable during of reduced being L MN 1.56 0.67 2.54 17.9 0 0 0 0.003 0 0.006 0.08 2.4 74.8 Photosensitive Glass-Ceramics and Glass M 1.56 0.67 2.54 17.9 0 0.0004 0 0 0 0.006 0.08 2.4 74.8 N OP 1.56 0.67 2.54 17.9 0 0 0.06 0 0.007 0.006 0.08 2.4 74.8 O 1.56 0.67 2.54 17.9 0.0025 0 0 0 0 0.006 0.04 2.4 74.8 P - - - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Photosensitive Glass-Ceramics
Standard fotoform Low CTE
Corning 10.0 kV 8.6 mm × 5.00 k YAGBSE 10.0 µm Corning 10.0 kV 8.5 mm × 5.00 k YAGBSE 10.0 µm
Low Ag Au
Corning 10.0 kV 8.3 mm × 5.00 k YAGBSE 10.0 µm Corning 10.0 kV 8.2 mm × 5.00 k YAGBSE 10.0 µm 59 FIGURE 3.24 Comparison of SEM images of the morphology of the crystal structure produced with the different photonucleating elements (see Table 3.11). Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 glass that initially formed NaF upon heating to a higher temperature. ahigher to upon heating NaF formed initially that glass crystalline phase. The example phase. (Na The is nepheline crystalline entirely new nucleation an producing occurs, where afurther process of the tinuation 60 360 nm (within the range of the Ce of (within range the the 360 nm of range 300– the in Typical lines UV producing lamps, exposure Hg uses or Hg/Xe e 3.6.2 above. described by mechanism the produced nanocrystals photosensitive 3.4) initial situation the (Equation phase this isIn Fota-Lite; is, NaF that by3.1 Equations 3.4. described 3.5 process of acontinuation through Equation the as was expressed stage that in crystalline second aseparate through continues process where here the demonstrated be phenomenon will that is another Section 3.2,in there nucleated by aphotosensitively However, Ag nanoparticle. produced was as discussed glass the from phase acrystalline chapter produces this in far thus discussed process The n 3.6.1 3.6 Li-disilicate. converts phase a to crystal the and 800°C to is heated material developed patterned crystallites. phology onLi-metasilicate of how Ag reduced is 3.25 FIGURE 5–10 mW/cm 5–10 shown Table in 3.12. is and phase, aluminate of the amount the for increase to silica by substituting alumina version is amodified case the that shownFota-Lite positionof in of this in Table 3.1 Another version called Fotoceram™, is obtained if the exposed and thermally thermally exposed and the version if Fotoceram™,Another called is obtained EODSAE NUCLEATION SECOND-STAGE x a p F/ osure 2
with exposure times ranging from 5–60 minutes. The level The minutes. of excitation 5–60 is from ranging exposure with times N Various tints that can be produced in Fotoform as a consequence of the mor of the aconsequence Fotoform as in produced be can that Various tints ep heline
and T her m al D +3 e photoexcitation spectrum). The UV intensity is is intensity photoexcitation UV The spectrum). v elo Photosensitive Glass-Ceramics and Glass pm ent 3 [AlSiO 4 ] 4 ) 8 4 Now acon we describe produced from the same same the from produced 15 The glass com glass The - - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 intensity forintensity was a 2–3W,10-Hz rate rep yielding a 0.6-J/cm 3.27. is shown glass unexposed Figure the in and portion exposed crystallized sample of the 3.26 shown a treated Figure and in are 690°C to heated sample both nonexposed exposed of and results an XRD nepheline. The the produce thermally region unexposed not where does the is atemperature use to optimum desired The require less exposure times. Putting in these units, the range was range ~3–36 the units, these in J/cm Putting less exposure times. require exposures intensity will where higher is, ×time intensity energy; that the to proportional Photosensitive Glass-Ceramics NaF phase that is the nucleus is the that phase for phase.NaF production nepheline of the the In other words, the it is further. is not phase anything sufficient NaF to do the ing composition so the theynucleate phase nepheline provide fluctuation developin the themselves shown Ag do it not nanoparticles been that has system. Experimentally total the compositionin fluctuation local coulddestabilize any induced and lization crystal spontaneous to unstable very question in are glasses the is that clearly true nucleation phenomenon. is for standard What the literature the in with dealt erally photonucleated suggests Ag of no particle simple what is gen explanation terms in a from was produced nuclei aNaF turn from in phase that of aNa-aluminosilicate stage of second for nucleation glass ation phenomenon. this the mechanism from The expansion. thermal in regions unexposed difference exposed due and the to the developed be can stresses between controlled since have toughness improved fracture could body the structure appropriately patterned an In structure. patterned the from properties or optical (opaque mechanical different the translucent) to may utilize to be wavelength. 248-nm of of the penetration depth of the because surface of 0.1of J/cm were 1–10exposure times excimer energy apulse with laser using a248-nm minutes In addition, samples addition, were YAGIn exposed atripled with (355 laser nm). Typical for 600°C–700°C ofhold from 2–10 ranged times treatments h. thermal typical The The main significance of this demonstration unique is a photonuclestudy of a this of significance main The glass-ceramic nepheline photo-patterned the from may advantages arise that The 2 for exposures intended only to produce the nepheline phase near the the near phase nepheline for the only produce to exposures intended K CeO Br− F− ZnO Na Al Ag SnO Sb SiO Weight% (NaNucleates Nepheline NaF Where Glass of the Composition 3.12 TABLE 2 2 O 2 2 O O O 2 2 3 3 3 [AlSiO TSR 16.1 6.1 1 3.3 1.6 29.1 44 0.01 0.1 0.2 0.02 4 ] 4 ) 2 energy per pulse. The pulse. The per energy 2 . 61 - - - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 62
[1159357 raw] 250TSR not exposed 690 C/2 hr [1159356 raw] 250TSR exp 2side 60 min HgXe each 690 C/2 hr 01-083-2372> Nepheline-Na Al Si O 01-083-2372> Nepheline-Na6 65Al6 24Si5 76O32 14.0 6 65 6 24 5 76 32 00-012-0257> Cryolite-Na3AlF6 d = 3.0093 4000 d = 3.8403 00-052-1294> KAI2(AlSi3O10)F2-potassium aluminum silicate fluoride
12.0 3500 d = 3.2723 3000 10.0 d = 4.186 d = 3.2704 d = 3.0077 ) ) ts ts 2500 d = 3.6090 8.0 d = 4.186 coun coun
2000 d = 2.8857 d = 2.3459 6.0 Photosensitive Glass-Ceramics and Glass d = 4.329 Intensity ( Intensity ( 1500 d = 2.3433 d = 2.3078 4.0 d = 2.5777 d = 3.0172 1000 d = 4.997 d = 1.5617 d = 2.4991 d = 2.0932 d = 2.4009 d = 1.3859 d = 3.6259 d = 3.7080 d = 1.9019 d = 8.659 d = 1.6182 d = 2.7474
2.0 d = 1.4304 d = 2.6666 d = 4.539 d = 1.7915 d = 1.6951 d = 1.9658 d = 1.4710 d = 2.5302 d = 2.4373 d = 2.1652
500 d = 1.8845 d = 1.3736 d = 1.2802 d = 1.5243 d = 6.011 d = 2.0344 d = 1.3159 d = 1.3951 d = 1.2034 d = 1.7210 d = 1.8429 d = 1.7635 d = 1.6657 d = 1.2078 d = 1.2304 d = 1.3472 d = 1.2189
0 ×103 10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80 Two-theta (deg) Two-theta (deg) Corning [SPLBKKR1xray]z Current Data Borelli 298560 ELS> ursday, January 29, 2015 07:25a (MDI/JADES) Corning [SPLBKKR1xray]z Current Data Borelli 298560 ELS> ursday, January 29, 2015 07:24a (MDI/JADES) (a) (b)
FIGURE 3.26 XRD trace of exposed and developed glass of the glass in Table 3.10: (a) unexposed and heated and (b) exposed and heated to 690°C. (From N.F. Borrelli et al., U.S. Patent Application, 2014.15) Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 ment of 550°C/2 h, the XRD continued to show little crystal with a large glassy halo glassy halo alarge with show to continued crystal ment little of 550°C/2 XRD the h, Photosensitive Glass-Ceramics by adding more alumina to enhance the LAS phase. LAS the enhance to more alumina by adding exposed region. the in nothing with (LiAlSi of aslight showed Li-aluminosilicate amount and of presence area LiF the unexposed the from measured XRD opposite behaved The manner. the LiF in the regions, unexposed the in clear nanophase) exposedNaF remains regions the and in (formsphotosensitive above opalized where described becomes Fota-Lite glass glass the to system. NaF It the was in found contrary that Na-aluminosilicate the to similar way, amanner in similar possibly then alithium-aluminosilicate one could produce a in produced nucleated could aphotonucleated be suggests phase if NaF LiF that (nepheline) a Na-aluminosilicate produce Ag photo one can fact an that from The l 3.6.3 3.27 FIGURE For an exposure of 60 minutes at350 at10 exposure ofFor minutes nm 60 an mWcm shown composition Table observation, the that to in was altered on this Based 3.13 i F/
L i - Exposed glass heated to 690°C whose XRD is shown in Figure 3.26. Figure shown is in whose XRD 690°C to heated glass Exposed A lu m F− Na Al Br− ZnO Li Ag CeO K SiO Heating to after 550°CPhase LAS Leading to the Composition Glass 3.13 TABLE inosilicate 2 2 2 O 2 O O O 2 2 3 16 2.25 0.03 0.78 7.23 0.71 6.03 0.03 0.04 7.22 75.68 2 with a thermal develop athermal with 2 O 63 6 ) - - 4
Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 64
[691165.raw] 250 TNI 550 C no exp [1168455.raw] 250 TNI no exposure HT 550 C/2 hr/atm 01-070-2535> Quartz-SiO2 00-031-0707> Virgilite-LixAlxSi3–xO6 01-073-0252> Aluminum-LiAlSiO4 99-000-4198> Villiaumite-NaF 00-052-0065> Li9AlSiO8-lithium aluminum silicate 01-071-4681> Griceite-LiF 4500 d=3.4169 d = 3.4296 20.0 4000
3500 d = 4.412 ) ) ts ts 15.0 oun oun 3000 (c (c
2500 Intensity Intensity Photosensitive Glass-Ceramics and Glass 10.0 2000 d = 2.5459
1500 d = 2.3300 d = 2.0139 d = 1.8613 5.0 1000 d = 1.8550 d = 4.397
d = 1.3982 500 d = 1.5886 d = 1.4179 d = 2.5404 d = 2.1980 d = 2.0390 d = 2.3099 d = 2.6939 d = 1.5542 d = 1.7084 d = 2.4138 d = 1.6747 d = 1.4707 d = 1.8004 ×103 0 10 20 30 40 50 60 70 10 20 30 40 50 60 70 Two-theta (deg) Two-theta (deg) Corning Incorporated XRD Lab [xray]
FIGURE 3.28 XRD of the glass exposed for 60 minutes at 10 mW/cm2 and treated at 550°C/2 h: (a) nonexposed and (b) exposed. Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 Photosensitive Glass-Ceramics REFERENCES nucleation. Zr standard the with phase LAS the 550°C crystallize than to amuch to temperature glass higher one LiF glass wouldno the formed; have in the fluorine to heat withoutout the that explanation of it this support should by pointed be is not In light. aided that manner thermal aspontaneous but so nucleates phase in does LAS the indeed LiF the is that sample rest of was were not the the exposed. exposed and areas circular clear the 3.29b), reverse the in exposure(Figure mode and 1.5-mm circle the areas, light in sure up of block asituation to made represents where is opaque used expo dots amask the 3.29a, shown Figure in effect which is more phase. graphically The LAS crystalline the (see phase LAS 3.28). Figure beta-quartz by stuffed the dominated was condition that was produced but now exposed region the a well-crystallized in now (b). opaque are holes that open (a); small circles was covered of with by clear light consists amask exposure the where and 3.29 FIGURE above opposite effect. the exposure has where the behavior NaF/nepheline system the to this discussed compare to theless interesting exposed is always phase. It the is There none in phase LAS ofgrowth. the some hint nuclei many too therefore frustrate are is not that effectiveof very there LiF that in of formation nuclei tiny many the is that conjecture the itself. exposed For part the
1. 2. 4. 3. The explanation of this effect is purely conjectural at this point. The conjecture conjecture The point. atthis explanation effect is purelyThe of conjectural this of formation the obvious frustrates The case conclusion this exposure in the is that Columbus, OH, 1985. OH, Columbus, Ball Crystal the S.D. of Center Stookey, the to Journey No. 5, American Ceramic Society, 1971. Ceramic No. 5, American G.H. Beall, Sons, Hoboken, NJ, Hoboken, Sons, 2012. Technology W. Glass-Ceramic G.H. Beall, and Holand D.A. and Duke G.H. Beall
Image showing where the exposure light was blocked in the region that now that region the was blocked in light exposure the showing where Image Advances in Nucleation and Growth and Nucleation in Advances (a) 3 In other words, the LiF can be an effective an be nucleating can agent words, LiF other the In , J. Mater. Sci . 4, 340, 1969.. 4, 340, , L.L. Hench and F.F (eds.), Hench and , L.L. Freiman , Second Edition, John Wiley & John Edition, , Second (b) , American Ceramic Society, Ceramic , American 65 - - Downloaded By: 10.3.98.104 At: 02:48 02 Oct 2021; For: 9781315368801, chapter3, 10.1201/9781315368801-4 66
11. 10. 13. 12. 14. 15. 16. 5. 6. 7. 8. 9. 1979. T.P. D.A. and N.F. Nolan, J.B. Am Chodak, Soc. Borrelli, J. Opt. Seward, S.D. Stookey, Chem Eng. Ind. S.D. Stookey, Chem Eng. Ind. S.D. Stookey, U.S. No. Patent 2,684,911, 1954. N.F. Borrelli, N. Lonnroth et al., U.S. al., et No. Patent 9,011,720.N.F. N. Lonnroth Borrelli, 1985. W.L. Phys and J. Appl. Morgan, N.F. Bellman, D.L. R.H. Morse, Borrelli, Phys S.D. J. Appl. Stookey, J.E. Pierson, and G.H. Beall, 2005. Technology N.F. Microoptics Borrelli, Opt W. and Appl. J.A. Durbin, Lama, N.F. Bellman, R.H. Borrelli, N.F. Borrelli and J.F.N.F. and U.S. 2014. Application, Borrelli Patent Schroeder, N.F. U.S. al., et 2014. Application, Patent Borrelli N.F. Borrelli, G.H. Beall, and J.F. and U.S. 2015.N.F. G.H. Beall, Application, Patent Schroeder, Borrelli, . 51, 805, 1959. . 45, 115, 1953. , Second Edition, Marcel Dekker, New Dekker, York, Marcel Edition, , Second Photosensitive Glass-Ceramics and Glass . 49, 5114, 1978. . 30(25), 3633, 1991. . 69(11), 1514, . 24, 2520,. 24,