WO2000061511A1 - Large photosensitivity in lead silicate glasses - Google Patents

Large photosensitivity in lead silicate glasses Download PDF

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Publication number
WO2000061511A1
WO2000061511A1 PCT/US2000/009138 US0009138W WO0061511A1 WO 2000061511 A1 WO2000061511 A1 WO 2000061511A1 US 0009138 W US0009138 W US 0009138W WO 0061511 A1 WO0061511 A1 WO 0061511A1
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Prior art keywords
lead silicate
silicate glass
grating
photo
induced
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PCT/US2000/009138
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French (fr)
Inventor
Steven R. J. Brueck
Xiangcun Long
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The University Of New Mexico
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Publication date
Application filed by The University Of New Mexico filed Critical The University Of New Mexico
Priority to AU42049/00A priority Critical patent/AU4204900A/en
Priority to CA002369584A priority patent/CA2369584A1/en
Priority to EP00921773A priority patent/EP1183214A4/en
Publication of WO2000061511A1 publication Critical patent/WO2000061511A1/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02057—Optical fibres with cladding with or without a coating comprising gratings
    • G02B6/02076—Refractive index modulation gratings, e.g. Bragg gratings
    • G02B6/02114—Refractive index modulation gratings, e.g. Bragg gratings characterised by enhanced photosensitivity characteristics of the fibre, e.g. hydrogen loading, heat treatment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/0025—Other surface treatment of glass not in the form of fibres or filaments by irradiation by a laser beam
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/62—Surface treatment of fibres or filaments made from glass, minerals or slags by application of electric or wave energy; by particle radiation or ion implantation
    • C03C25/6206—Electromagnetic waves
    • C03C25/6208—Laser
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
    • C03C3/0745—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc containing more than 50% lead oxide, by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/124—Geodesic lenses or integrated gratings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02057—Optical fibres with cladding with or without a coating comprising gratings
    • G02B6/02076—Refractive index modulation gratings, e.g. Bragg gratings
    • G02B6/02123—Refractive index modulation gratings, e.g. Bragg gratings characterised by the method of manufacture of the grating
    • G02B6/02133—Refractive index modulation gratings, e.g. Bragg gratings characterised by the method of manufacture of the grating using beam interference
    • G02B6/02138—Refractive index modulation gratings, e.g. Bragg gratings characterised by the method of manufacture of the grating using beam interference based on illuminating a phase mask

Definitions

  • This invention is made with government support by the Air Force Office of Scientific Research and by the Defense Advanced Research Projects Agency. The government may have certain rights in this invention.
  • the present invention relates to lead silicate glasses.
  • a method for inducing a refractive index change in a lead silicate glass material comprising: providing a lead silicate glass material; and irradiating the lead silicate glass material to increase the index of refraction of said lead silicate glass material.
  • Figure 1 illustrates an experimental arrangement for writing gratings in lead
  • Figure 2 illustrates a depth profile of the diffraction efficiency for UV-laser
  • Figure 3 illustrates the photo-induced refractive index changes vs. heavy metal lead cation in mol.% (solid circles) and exponential fit (solid line);
  • Figure 4 illustrates the dispersion of An for lead silicate glass SF59
  • Figure 5A is a scanning electron micrograph of surface relief patterns in a first portion of ZF7 sample after 248-nm irradiation through a 738-nm phase mask with a period of 738 nm;
  • Figure 5B is a scanning electron micrograph of surface relief patterns in a second portion of ZF7 sample of Figure 5A after 248-nm irradiation through a 738-nm phase mask with a double period of 369 nm;
  • Figure 6 is a depth profile of the diffraction efficiency for UV laser induced grating on lead silicate glass.
  • the term "lead silicate glass” refers to any silicate glass including any amount of PbO.
  • lead silicate glass grating refers to a lead silicate glass having the properties of a Bragg grating. Such a grating may be formed on a bulk silicate glass, formed in a fiber, waveguide, etc.
  • photo-induced lead silicate glass grating refers to a lead silicate glass grating formed by irradiating a lead silicate glass with any form of electromagnetic radiation.
  • Lead silicate glass has a very large third-order optical nonlinearity.
  • ⁇ (2) « 1 pm/V optical non linearity
  • the induced refractive index change is permanent and shows no decay after heating up to 360°C over one hour. Dispersion of the refractive index change suggests that the photosensitivity is associated with changes in the intrinsic glass absorption edge.
  • the present invention encompasses using mam- other wavelength of electromagnetic energy to irradiate lead silicate glasses. Also, the present invention encompasses various irradiation sources in addition to the Q-switched YAG laser and the KrF excimer laser described below. Furthermore, although the irradiation of only a few lead silicate glass compositions, ranging from the range from 19- to 70- mol.% are described below, the present invention encompasses irradiating virtually any lead silicate glass composition.
  • the large photosensitivity of the lead silicate glasses formed by the method of the present invention may find application in telecommunications, see A. Othonos, Rev. Sci. Instrum. 68, 4309 (1997), and data storage, see A. Partovi, T. Amsterdam, V. Mizrahi, P. J. Lemaire, A. M. Glass and J. W. Fleming, Appl. Phys. Lett. 64, 821 (1994).
  • a few mol.%> PbO can be doped into glasses to enhance the photosensitivity of silica glass fibers.
  • a hydrogen-loading technology is used to enhance the photosensitivity in germanosilicate fibers.
  • the index difference, An between irradiated and non-irradiated material saturates at about 0.01 for hydrogen- loaded fibers with limited stability at elevated temperatures.
  • a stronger photosensitivity would be desirable.
  • inexpensive materials with high optical quality, high photosensitivity, large refractive index change, long shelf life are still necessary.
  • a large photosensitivity in silica- based glass would make it possible to fabricate planar lightwave circuits (PLC) devices by direct UV-writing.
  • Lead silicate glasses ZF7 and the Schott glass series F2, SF2, SF11, SF6, and SF59 were chosen to study the dependence of photo-induced refractive index change on the lead composition.
  • the lead-oxide content varied from 18.7 mol.% to 57 mol.%.
  • the detailed materials compositions of the glasses are listed in Table 1 below:
  • the optical absorption edge varied with the lead content of the glasses.
  • the optical band gap is 2.71 eV for 80 mol.% PbO glass increasing to 3.38 eV for 50 mol.% PbO silicate glass, see A. Barbulescu and Lucia Sincan, Phys. Stat. Sol. (a) 85, K129 (1984).
  • Figure 1 illustrates the experimental arrangement used for writing gratings in lead silicate glasses.
  • the source is a 266-nm, fourth harmonic Q-Switched YAG laser.
  • the silica phase mask with period of 738 nm is designed for 248-nm.
  • the silica prism is used to completely reject the zero-order transmitted light as well as to separate the glass samples from the phase mask.
  • Figure 2 illustrates a depth profile of the diffraction efficiency for UV-laser induced grating on the lead silicate glasses SF59 and (F2). The diffraction efficiency drops sharply as the surface relief grating with -100 nm (20 nm) depth is removed.
  • Figure 3 illustrates the photo-induced refractive index changes vs. heavy metal lead cation in mol.% (solid circles) and exponential fit (solid line). The data point denoted by
  • Figure 4 illustrates the dispersion of An for lead silicate glass SF59.
  • the index change values were normalized to the value at 633 nm.
  • the solid line is a fit to a simple Sellmeier dependence with a characteristic wavelength of 353 nm.
  • the irradiation source was the frequency-quadrupled output of a Q-Switched YAG laser (-10 ns,10-Hz repetition rate) at 266 nm.
  • a strong zero-order beam was observed for 266-nm illumination.
  • the zero-order light was eliminated with a 45° silica prism, see Figure 1, which also changed the incident angles to 5.7° giving a - 1.3- ⁇ m period grating.
  • Another advantage of using this arrangement was that the glass samples were kept far from any optical surfaces eliminating any potential contamination due to glass photo-ablation.
  • the high spatial and temporal coherence of the YAG laser is essential in this configuration.
  • the laser energy was - 6-mJ/pulse over an area of 0.4x0.6 cm " giving an incident energy density of 25 mJ/cnr per pulse. All of the polished glass samples were irradiated under the same conditions for this composition comparison study, i.e. 25 mJ/crrf per pulse fluence for 10 min. with 10-Hz repetition rate.
  • a He-Ne laser beam was used to measure the diffraction efficiency of the grating following irradiation. Both surface relief and refractive index gratings were observed for all of the glasses studied. The highest diffraction efficiency (20%) was obtained for the highest lead content (SF59 - 57 mol.%) glass.
  • the photo- induced grating provided a relatively high diffraction efficiency ( ⁇ - 1%) once the - 100-nm surface relief grating was removed.
  • ⁇ - 1%) a very shallow surface relief grating with height of 20 nm diffracted only - 0.2% of the incident light.
  • An(z) Ane ⁇ a ' ' " , where An is the index modulation at the surface of sample.
  • the photo-induced refractive index change ⁇ rc and the UV absorption length ctuv are plotted in Figure 3 against the lead cation mol.%.
  • the photo-induced index change refers to the left-hand (logarithmic) scale, the absorption length is on the righthand (linear) scale. Both parameters are well correlated to the mol.% PbO.
  • the index change is exponential in Pb content, the absorption length is linear in Pb content.
  • Two recent reports of photosensitivity in PbO related glasses are also plotted in Figure 3.
  • the laser wavelengths were 488 nm and 514 nm from Ar + laser, 596.3 nm, 632.8 nm and 1150 nm from He-Ne lasers, 883.5 nm and 918.3 nm from a tunable TkSapphire laser.
  • the refractive index changes at various wavelengths normalized to that at 633 nm are shown in Figure 4.
  • the solid curve in the figure is a fit to a simple Sellmeier curve:
  • the photo-induced diffraction gratings after polishing away the surface relief structures, were heated to temperatures of 100°-, 200°-, 250°-, and 360°C for 1-hour intervals. After each heat treatment the grating diffraction efficiency was measured at room temperature. No decay of the diffraction efficiency was observed even at 360°C.
  • the photo-induced refractive index change in lead silicate glass is strongly correlated with the PbO composition.
  • a large index change as high as 0.21 at 633 nm extrapolated to 0.17 at 1550 nm is observed in SF59 glass.
  • the dispersion is consistent with a modification to the glass structure.
  • the index change is permanent and shows no decay when the glass heated to temperatures as high as 360°C for one hour.
  • Figure 5 A is a scanning electron micrograph of surface relief patterns in a first portion of ZF7 sample after 248-nm irradiation through a 738-nm phase mask with a period of 738 nm.
  • Figure 5B is a scanning electron micrograph of surface relief patterns in a second portion of ZF7 sample of Figure 5 A after 248-nm irradiation through a 738- nm phase mask with a double period of 369 nm.
  • Figure 6 is a depth profile of the diffraction efficiency for UV laser induced grating on lead silicate glass.
  • the diffraction efficiency drops sharply as the surface relief grating with -70 nm height is removed.
  • the measured (solid circles for first order and open circles for second order) and modeled, see Equation 1, diffraction efficiency indicate a peak refractive index modulation Ano 0.09 ⁇ 0.02 with an exponential decay length of 125 nm resulting form the strong absorption at the 248-nm writing wavelength.
  • ZF7 lead silicate glass PbO - 70.93 wt%, Si0 2 -27.27 wt%, Na 2 0 - 0.6 wt%, K 2 0 - 1.0 wt%, As 2 0 3 - 0.3 wt%) had the highest percentage lead content of the compositions investigated.
  • the optical transmission is similar to the
  • SF glass series from Schott Glass Co.. with a UV-cutoff around 350 nm. All of the lead glasses investigated: F2, SF11, SF6, and ZF7 are photosensitive at 248 nm. A detailed study is presented below for only ZF7 glass. This glass is photosensitive across a wide spectral region range including 193 nm (ArF laser), 248 nm (KrF laser), 266 nm (4th harmonic of Q-switched YAG laser). No photosensitivity was observed for irradiation at 355 nm (3 r harmonic of Q-switched YAG laser), very close to the optical absorption edge.
  • the same silica phase mask (period 738 nm) was used for grating formation at all wavelengths, resulting in varying contrast between the fundamental and second- spatial harmonic grating exposures.
  • the measure phase mask power transmission was 12.5% for the zero order, 37.5% for the ⁇ 1 orders and 6.25% for the ⁇ 2 orders.
  • the glass sample was placed in physical contact with the surface of the silica phase mask.
  • the incident pulse energy density was 132 mJ/cm per pulse with a repetition of 10 Hz.
  • FIGS. 5 A and 5B are scanning electron micrographs (SEMs) showing the induced surface relief grating on the lead silicate glass after 10 min. of irradiation.
  • SEMs scanning electron micrographs
  • the grating surface was then polished in steps to remove the surface relief grating and observe the diffracted light from the induced index grating.
  • An additional surface-relief grating with a large 100- ⁇ m period and 1900-nm depth was made in the neighborhood of the photo-induced grating by standard lithography and etching.
  • the depth of the physical grating was measured with a stylus profilometer before any polishing and after the final polishing step.
  • a linear dependence of the polish depth vs. polish time was assumed giving a polish depth of -25 nm for each step.
  • the diffraction efficiencies of the grating were monitored after each polish step as shown in Figure 6 for the same grating shown in Figures 5 A and 5B.
  • the diffraction efficiency drops sharply from 10.8% down to 0.4% as the top 75-nm surface layer is polished away, corresponding to the removal of the surface-relief grating.
  • the efficiency of both first- order and second-order diffraction signals are comparable over the depth range from 75 nm to 300 nm, suggesting that gratings with periods of both d and d/2 were induced with comparable intensities.
  • An is the index modulation at the surface of the sample.
  • the refractive index change may be evaluated Ano can be evaluated using Equation 1 above.
  • Equation 1 0.09 ⁇ 0.02 and nm "1 .
  • a high diffraction efficiency grating (10%) was induced in lead silicate glass by irradiation with a pulsed. 248-nm KrF excimer laser through a silica phase mask.
  • the primary scattering mechanism was surface relief.

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Abstract

The present invention provides a method for inducing a refractive index change in a lead silicate glass material comprising: providing a lead silicate glass material; and irradiating the lead silicate glass material to increase the index of refraction of said lead silicate glass material. The present invention also provides a photo-induced lead silicate glass grating.

Description

LARGE PHOTOSENSITIVITY IN LEAD SILICATE GLASSES
CROSS-REFERENCE TO RELATED APPLICATIONS
This application makes reference to co-pending U.S. Provisional Patent
Application No. 60/ 128,622, entitled "Large Photo sensitivity in Lead silicate Glasses," filed April 9, 1999; and co-pending U.S. Provisional Patent Application No.
60/130,268, entitled "Large Photosensitivity in Lead silicate Glasses," filed April 21, 1999, the entire disclosure and contents of which are hereby incorporated by reference.
GOVERNMENT INTEREST STATEMENT
This invention is made with government support by the Air Force Office of Scientific Research and by the Defense Advanced Research Projects Agency. The government may have certain rights in this invention.
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to lead silicate glasses.
Description of the Prior Art
Photosensitivity. the long-term change of glass refractive index following optical irradiation, has found application in telecommunications see A. Othonos. Rev. Sci.
Instrum. 68. 4309 (1997). and data storage, see A. Partovi. T. Erdogan. V. Mizrahi. P. J. Lemaire. A. M. Glass and J. W. Fleming, Appl. Phys. Lett. 64. 821 (1994). The preponderance of the investigations in optical fiber have been devoted to germanosilicate glasses with Δn, the index difference between irradiated and non- irradiated material, saturating at about 0.01 for hydrogen loaded fibers with limited stability at elevated temperatures, see A. Othonos, Rev. Sci. Instrum. 68, 4309 (1997). For data storage, crystalline phase change materials have been explored because of the large index changes available. However, these materials are not useful for fiber applications. Therefore, there exists a need for glasses with higher photosensitivity for improved performance in both fiber and volume storage applications.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a method for forming lead silicate glass materials having large, thermally stable photosensitivities.
It is another object of the present invention to provide a method for forming lead silicate glass materials that may be for used in telecommunications, integrated optics and data storage technologies.
It is yet another object of the present invention to provide a method for forming glasses with higher photosensitivity for improved performance in both fiber and volume storage applications.
According to a first broad aspect of the present invention, there is provided a method for inducing a refractive index change in a lead silicate glass material comprising: providing a lead silicate glass material; and irradiating the lead silicate glass material to increase the index of refraction of said lead silicate glass material.
According to a second broad aspect of the present invention, there is provided a photo-induced lead silicate glass grating. Other objects and features of the present invention will be apparent from the following detailed description of the preferred embodiment.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be described in conjunction with the accompanying drawings, in which:
Figure 1 illustrates an experimental arrangement for writing gratings in lead
silicate glasses;
Figure 2 illustrates a depth profile of the diffraction efficiency for UV-laser
induced grating on lead silicate glasses SF59 and (F2);
Figure 3 illustrates the photo-induced refractive index changes vs. heavy metal lead cation in mol.% (solid circles) and exponential fit (solid line);
Figure 4 illustrates the dispersion of An for lead silicate glass SF59;
Figure 5A is a scanning electron micrograph of surface relief patterns in a first portion of ZF7 sample after 248-nm irradiation through a 738-nm phase mask with a period of 738 nm;
Figure 5B is a scanning electron micrograph of surface relief patterns in a second portion of ZF7 sample of Figure 5A after 248-nm irradiation through a 738-nm phase mask with a double period of 369 nm; Figure 6 is a depth profile of the diffraction efficiency for UV laser induced grating on lead silicate glass.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
It is advantageous to define several terms before describing the invention. It should be appreciated that the following definitions are used throughout this application.
Definitions
Where the definition of terms departs from the commonly used meaning of the term, applicant intends to utilize the definitions provided below, unless specifically indicated.
For the purposes of the present invention, the term "lead silicate glass" refers to any silicate glass including any amount of PbO.
For the purposes of the present invention the term "lead silicate glass grating" refers to a lead silicate glass having the properties of a Bragg grating. Such a grating may be formed on a bulk silicate glass, formed in a fiber, waveguide, etc.
For the purposes of the present invention the term "photo-induced lead silicate glass grating" refers to a lead silicate glass grating formed by irradiating a lead silicate glass with any form of electromagnetic radiation.
Description
Lead silicate glass has a very large third-order optical nonlinearity. The third- order nonlinear refractive index for Schott lead silicate glass SF59 is «2 = 5 x 10"19 m7W, [χ ' = 6.2 x 10"" m /V~] which is 30 times that of pure silica glass [χ ) = 2.0 x 10~22m2/V2]. see E. -M. Vogel, M. J. Weber and D. M. Krol, Phys. & Chem. Glasses, 32. 231 (1991). Recently a large second-order optical non linearity (χ(2) « 1 pm/V) induced by thermal poling and electron beam scanning was reported in these materials, see M. Qiu, F. Pi and G. Orriols, Appl. Phys. Lett, 73, 3040 (1998); and M. Qiu, T. Mizunami. H. Koya, F. Pi, and G. Orriols, in Proceedings of Nonlinear Optics: Materials, Fundamentals, and Applications (IEEE, Piscataway, N 1998), p. 370. The present invention takes advantage of the fact that these large nonlinearities appear to be related to the photosensitiviy of lead silicate glasses.
In the present invention a large photo-induced refractive index change (as high as An = 0.21 ± 0.04 ) is obtained in lead silicate glasses by irradiation with the frequency quadrupled output of a Q-switched YAG laser (266 nm). An approximately exponential relationship exists between the photo-induced refractive index change and the lead cation mole fraction over the composition range from 18.7% to 57%. The induced refractive index change is permanent and shows no decay after heating up to 360°C over one hour. Dispersion of the refractive index change suggests that the photosensitivity is associated with changes in the intrinsic glass absorption edge.
A similarly large photo-induced refractive index change (as high as
An0 = 0.09 ± 0.02 ) in permanent gratings formed in lead silicate glass with a UV exposure at 248 nm using a KrF excimer laser beam.
Although in the examples described below only two wavelength lengths of light are used to irradiate lead silicate glasses, the present invention encompasses using mam- other wavelength of electromagnetic energy to irradiate lead silicate glasses. Also, the present invention encompasses various irradiation sources in addition to the Q-switched YAG laser and the KrF excimer laser described below. Furthermore, although the irradiation of only a few lead silicate glass compositions, ranging from the range from 19- to 70- mol.% are described below, the present invention encompasses irradiating virtually any lead silicate glass composition.
The large photosensitivity of the lead silicate glasses formed by the method of the present invention may find application in telecommunications, see A. Othonos, Rev. Sci. Instrum. 68, 4309 (1997), and data storage, see A. Partovi, T. Erdogan, V. Mizrahi, P. J. Lemaire, A. M. Glass and J. W. Fleming, Appl. Phys. Lett. 64, 821 (1994). For fiber grating application, a few mol.%> PbO can be doped into glasses to enhance the photosensitivity of silica glass fibers. Currently, a hydrogen-loading technology is used to enhance the photosensitivity in germanosilicate fibers. The index difference, An, between irradiated and non-irradiated material saturates at about 0.01 for hydrogen- loaded fibers with limited stability at elevated temperatures. For some fiber applications, such as fiber filters and fiber dispersion compensators, see N. M. Litchinitser, B. J. Eggleton and D. B. Patterson, J. Lightwave Technol., 15, 1303 (1997), a stronger photosensitivity would be desirable. For volume optical holographic data storage, inexpensive materials with high optical quality, high photosensitivity, large refractive index change, long shelf life are still necessary. Also, a large photosensitivity in silica- based glass would make it possible to fabricate planar lightwave circuits (PLC) devices by direct UV-writing.
The present invention will now be described by way of example.
EXAMPLE 1
A detailed investigation of the dependence of the photo-induced refractive index change on composition for lead silicate glasses was conducted. The heavy metal cation lead contributes to the large photosensitivity. An exponential relationship was found between the photo-induced refractive index change and lead concentration over the range from 19- to 57- mol.%. The largest index change (An = 0.21±0.02 at 633 nm) was obtained in SF59 glass by irradiation with a 266-nm laser source at a fluence of 25 mJ/cnr per pulse (10 ns, 10 Hz, 10 min) and a total dose of 150 J/cm . The induced refractive index change is permanent and does not exhibit any decay after heating to 360°C for over an hour. The dispersion of the photo-induced index is consistent with a change in the absorption near the fundamental absorption edge of the glass. Extrapolating to telecommunications wavelengths, the index change is An - 0.16.
Lead silicate glasses ZF7 and the Schott glass series F2, SF2, SF11, SF6, and SF59 were chosen to study the dependence of photo-induced refractive index change on the lead composition. The lead-oxide content varied from 18.7 mol.% to 57 mol.%. The detailed materials compositions of the glasses are listed in Table 1 below:
Figure imgf000009_0001
The optical absorption edge varied with the lead content of the glasses. The optical band gap is 2.71 eV for 80 mol.% PbO glass increasing to 3.38 eV for 50 mol.% PbO silicate glass, see A. Barbulescu and Lucia Sincan, Phys. Stat. Sol. (a) 85, K129 (1984).
Figure 1 illustrates the experimental arrangement used for writing gratings in lead silicate glasses. The source is a 266-nm, fourth harmonic Q-Switched YAG laser. The silica phase mask with period of 738 nm is designed for 248-nm. The silica prism is used to completely reject the zero-order transmitted light as well as to separate the glass samples from the phase mask. Figure 2 illustrates a depth profile of the diffraction efficiency for UV-laser induced grating on the lead silicate glasses SF59 and (F2). The diffraction efficiency drops sharply as the surface relief grating with -100 nm (20 nm) depth is removed. The measured (circles) and modeled, see Equation 1 below, diffraction efficiency (line) indicate peak refractive index modulations of An = 0.21 ±0.04 (0.007±0.002) with an exponential decay length of 118 nm (303 nm) resulting from the strong absorption at the 266-nm writing wavelength.
Figure 3 illustrates the photo-induced refractive index changes vs. heavy metal lead cation in mol.% (solid circles) and exponential fit (solid line). The data point denoted by
"#" is from S. Mailis, A. A. Anderson, S. J. Barrington, W. S. Brocklesby, R. Greef, H.
N. Rutt, R. W. Eason, N. A. Vainos and C. Grivas, Opt. Lett. 23, 1751 (1998) for glass
55GeO2-20PbO-10ZnO-5K2O (in mol.%) and "■" from S. Radic, R. J. Essiambre, R.
Boyd, P. A. Tick and N. Borrelli, Opt. Lett. 23, 1730 (1998).for glass 47SnF2-47PO2.5- 4PbO-2SnCl2 (in mol.%).
Figure 4 illustrates the dispersion of An for lead silicate glass SF59. The index change values were normalized to the value at 633 nm. The solid line is a fit to a simple Sellmeier dependence with a characteristic wavelength of 353 nm.
The irradiation source was the frequency-quadrupled output of a Q-Switched YAG laser (-10 ns,10-Hz repetition rate) at 266 nm. A silica phase mask (738-nm period), optimized for 248-nm excimer laser was used. A strong zero-order beam was observed for 266-nm illumination. The zero-order light was eliminated with a 45° silica prism, see Figure 1, which also changed the incident angles to 5.7° giving a - 1.3-μm period grating. Another advantage of using this arrangement was that the glass samples were kept far from any optical surfaces eliminating any potential contamination due to glass photo-ablation. The high spatial and temporal coherence of the YAG laser is essential in this configuration. The laser energy was - 6-mJ/pulse over an area of 0.4x0.6 cm" giving an incident energy density of 25 mJ/cnr per pulse. All of the polished glass samples were irradiated under the same conditions for this composition comparison study, i.e. 25 mJ/crrf per pulse fluence for 10 min. with 10-Hz repetition rate. A He-Ne laser beam was used to measure the diffraction efficiency of the grating following irradiation. Both surface relief and refractive index gratings were observed for all of the glasses studied. The highest diffraction efficiency (20%) was obtained for the highest lead content (SF59 - 57 mol.%) glass. This high diffraction efficiency arises primarily from the ~100-nm deep surface relief grating. In contrast, only a weak diffraction signal was observed for F2 glass which has lowest lead content (18.7 mol.%). To extract the photo-induced refractive index change, we incrementally polished away both the surface relief grating and the underlying index grating and monitored the diffraction efficiency η after each polish step. The details of the technique are described in our previous report1. As an example, the diffraction efficiency η vs. polish depth for glass SF59 and glass F2 were shown in Figure 2. For SF59, the photo- induced grating provided a relatively high diffraction efficiency (η - 1%) once the - 100-nm surface relief grating was removed. For F2, a very shallow surface relief grating with height of 20 nm diffracted only - 0.2% of the incident light. It is assumed that the modulation of the refractive index decreases exponentially with depth (attenuation coefficient auv) because of the UV-absorption of the glass, that is An(z) = Ane~a' ' " , where An is the index modulation at the surface of sample. Following a previously developed theory, see N. Uchida, J Opt. Soc. Am. 63. 280 (1973)., the refractive index change An can be evaluated using the diffraction efficiency formula for a vertical, unslanted grating with s-polarized incident light:
Figure imgf000011_0001
λ υy cosθ j
where η is the diffraction efficiency, h is the cumulative polish depth, λ the wavelength of the diffracted light, and θ the incident angle in the medium. Using Equation 1 to fit the measured data, we found the photo-induced index changes An are
0.21 and 0.007 for glasses SF59 and F2, respectively. The photo-induced index changes An and absorption av. obtained for all of the measured glasses are listed in Table 2 below:
Figure imgf000012_0001
The photo-induced refractive index change Δrc and the UV absorption length ctuv are plotted in Figure 3 against the lead cation mol.%. The photo-induced index change refers to the left-hand (logarithmic) scale, the absorption length is on the righthand (linear) scale. Both parameters are well correlated to the mol.% PbO. The index change is exponential in Pb content, the absorption length is linear in Pb content. Two recent reports of photosensitivity in PbO related glasses are also plotted in Figure 3. One reported that photo-induced refractive index change, An as high as 0.01, was obtained for the 55GeO2-20PbO-10ZnO-5K2O (in mol.%) glass film system deposited by excimer laser ablation, see S. Mailis, A. A. Anderson, S. J. Barrington, W. S. Brocklesby. R. Greef, H. N. Rutt, R. W. Eason, N. A. Vainos and C. Grivas. Opt. Lett. 23, 1751 (1998). This photo-induced refractive index change An vs. lead mol.% fits well with our data as shown in Figure 3 by the "#" symbol. The other reported saturated photo-induced refractive index change An- 0.001 is obtained after irradiation with a pulsed XeCl excimer laser (309 nm) in 47SnF2-47P02 5-4PbO-2SnCl2(in mol.%), see S. Radic. R. J. Essiambre, R. Boyd, P. A. Tick and N. Borrelli, Opt. Lett. 23, 1730 (1998). The sample was capped by Si02 plates during exposure to eliminate formation of a surface relief grating. This data point is lower than would be obtained by extrapolating the Pb concentration dependence we observe (symbol "■"in Figure 3). For very high lead mol.% compositions, the photo-induced refractive index change must saturate. An exponential dependence of the third-order nonlinear susceptibility Z<J) on Pb mole fraction has been reported previously, see E. M. Vogel, M. J. Weber and D. M. Krol. Phys. Chem. Glasses 32, 231 (1991). Several lasers with various wavelengths were used to measure the dispersion of the photo-induced refractive index change An in SF59 glass. The laser wavelengths were 488 nm and 514 nm from Ar+ laser, 596.3 nm, 632.8 nm and 1150 nm from He-Ne lasers, 883.5 nm and 918.3 nm from a tunable TkSapphire laser. The refractive index changes at various wavelengths normalized to that at 633 nm are shown in Figure 4. The solid curve in the figure is a fit to a simple Sellmeier curve:
Figure imgf000013_0001
with o - 353 nm close to the band-edge value of - 370 nm, suggesting that the photosensitivity is associated with local modifications to the glass structure rather than with impurity levels. At telecommunications wavelengths of 1.3 and 1.55 μm, the An is - 0.8 of that at 633 nm with very little dispersion since these wavelengths are far removed from the absorption band-edge of the glass.
Finally the thermal stability of the photo-induced index change was examined. The photo-induced diffraction gratings, after polishing away the surface relief structures, were heated to temperatures of 100°-, 200°-, 250°-, and 360°C for 1-hour intervals. After each heat treatment the grating diffraction efficiency was measured at room temperature. No decay of the diffraction efficiency was observed even at 360°C.
In summary, the photo-induced refractive index change in lead silicate glass is strongly correlated with the PbO composition. There is an exponential relationship between the photo-induced refractive index change and the lead concentration in mol.% PbO over the range from 18.7- to 57-mol.%. A large index change as high as 0.21 at 633 nm extrapolated to 0.17 at 1550 nm is observed in SF59 glass. The dispersion is consistent with a modification to the glass structure. The index change is permanent and shows no decay when the glass heated to temperatures as high as 360°C for one hour. These large, thermally stable photosensitivities are attractive for applications in telecommunications, integrated optics and data storage.
EXAMPLE 2
Strong, permanent surface-relief and refractive index gratings were written in lead silicate glasses by irradiation with the output of a pulsed KrF excimer laser (248 nm) through a phase mask. Diffraction efficiencies as high as 10% were obtained. The diffraction efficiency of the refractive index grating after removal of the surface-relief grating showed that a very large photo-induced refractive index change (Ann = 0.21±0.04) was obtained in ZF7 lead silicate glass (40 mol.% PbO).
Figure 5 A is a scanning electron micrograph of surface relief patterns in a first portion of ZF7 sample after 248-nm irradiation through a 738-nm phase mask with a period of 738 nm. Figure 5B is a scanning electron micrograph of surface relief patterns in a second portion of ZF7 sample of Figure 5 A after 248-nm irradiation through a 738- nm phase mask with a double period of 369 nm.
Figure 6 is a depth profile of the diffraction efficiency for UV laser induced grating on lead silicate glass. The diffraction efficiency drops sharply as the surface relief grating with -70 nm height is removed. The measured (solid circles for first order and open circles for second order) and modeled, see Equation 1, diffraction efficiency indicate a peak refractive index modulation Ano = 0.09±0.02 with an exponential decay length of 125 nm resulting form the strong absorption at the 248-nm writing wavelength.
Various lead-content silicate glasses were investigated with lead compositions varying from 40% to 71%. ZF7 lead silicate glass (PbO - 70.93 wt%, Si02 -27.27 wt%, Na20 - 0.6 wt%, K20 - 1.0 wt%, As203 - 0.3 wt%) had the highest percentage lead content of the compositions investigated. The optical transmission is similar to the
SF glass series from Schott Glass Co.. with a UV-cutoff around 350 nm. All of the lead glasses investigated: F2, SF11, SF6, and ZF7 are photosensitive at 248 nm. A detailed study is presented below for only ZF7 glass. This glass is photosensitive across a wide spectral region range including 193 nm (ArF laser), 248 nm (KrF laser), 266 nm (4th harmonic of Q-switched YAG laser). No photosensitivity was observed for irradiation at 355 nm (3r harmonic of Q-switched YAG laser), very close to the optical absorption edge.
The same silica phase mask (period 738 nm) was used for grating formation at all wavelengths, resulting in varying contrast between the fundamental and second- spatial harmonic grating exposures. For normal incidence KrF laser illumination, the measure phase mask power transmission was 12.5% for the zero order, 37.5% for the ±1 orders and 6.25% for the ±2 orders. The glass sample was placed in physical contact with the surface of the silica phase mask. The incident pulse energy density was 132 mJ/cm per pulse with a repetition of 10 Hz.
After a few minutes of UV laser irradiation, a strong grating was observed in the glass sample. The strength of the grating, monitored by first-order diffraction of a HeNe laser beam initially increased with exposure time and saturated for exposure times of - 10 min. Figures 5 A and 5B are scanning electron micrographs (SEMs) showing the induced surface relief grating on the lead silicate glass after 10 min. of irradiation. In Figure 5 A, a grating with a period d = 738 nm is clearly seen. In Figure 5B, corresponding to a different location on the same grating, the frequency-doubled period d/2 is evident. This differs from observations of grating formation in As2S3 glass where the grating is mainly due to photoexpansion and the response drops off dramatically for short period gratings, see S. Ramachandran, S. G. Bishop, G.P. Guo, and D. J. Brady. IEEE Photon. Tech. Lett. 8, 1041 (1996). Atomic force microscope (AFM) images of the ZF& surface show similar results. The height of the surface relief grating is approximately 70 n. The inhomogeneity of the grating is likely due to optical effects related to the finite spatial and temporal coherence of the KrF laser source, see P. E. Dyer, R. J. Farley. R. Giedl, Opt. Commun.. 115, 327, (1995), coupled with the multiple scattered orders from the phase-mask and the varying contact distances. A HeNe laser beam was used to measure the diffraction efficiency of the grating. Diffraction is observed at angles corresponding to the fundamental grating (probing only the variation at period d) and at the second-order angle (involving interference between the second-order diffraction from the period d grating and the first-order diffraction from the period d/2 grating). The diffraction efficiencies were 10.8% (first-order angle) and 4.1% (second-order angle) for an s-polarized HeNe beam at an incident angle (external) of θext = 60°. For the measured 70-nm height, h, of the surface relief grating and the refractive index difference between the glass and air An = 0.8, the diffraction efficiency, η, may calculated using the following formula:
Figure imgf000016_0001
The diffraction efficiency calculated, η = 10.03% was very close to the measured value of 10.8%. suggesting that the surface relief grating is responsible for the majority of the diffracted signal. To confirm this hypothesis, a drop of index matching fluid (n - 1.8) was placed atop the grating and another ZF7 glass plate was pressed to grating surface; the diffraction efficiency was reduced to - 0.8%.
The grating surface was then polished in steps to remove the surface relief grating and observe the diffracted light from the induced index grating. An additional surface-relief grating with a large 100-μm period and 1900-nm depth was made in the neighborhood of the photo-induced grating by standard lithography and etching. The depth of the physical grating was measured with a stylus profilometer before any polishing and after the final polishing step. A linear dependence of the polish depth vs. polish time was assumed giving a polish depth of -25 nm for each step. The diffraction efficiencies of the grating were monitored after each polish step as shown in Figure 6 for the same grating shown in Figures 5 A and 5B. The diffraction efficiency drops sharply from 10.8% down to 0.4% as the top 75-nm surface layer is polished away, corresponding to the removal of the surface-relief grating. The efficiency of both first- order and second-order diffraction signals are comparable over the depth range from 75 nm to 300 nm, suggesting that gratings with periods of both d and d/2 were induced with comparable intensities.
It is assumed that the modulation of the refractive index decreases exponentially with depth (attenuation coefficient ui , because of the UV-absorption of the glass, that is
Figure imgf000017_0001
where An is the index modulation at the surface of the sample. Following a previously developed theory, see N. Uchida, J. Opt. Soc. Am., 63, 280 (1973, the refractive index change may be evaluated Ano can be evaluated using Equation 1 above.
Using Equation 1 to fit the data in Figure 6 the following results are obtained: Ann = 0.09±0.02 and
Figure imgf000017_0002
nm"1. The shallowness of the induced grating is mainly caused by the large ZF7 absorption coefficient at the 248-nm KrF excimer laser wavelength. If we use a source with wavelength between 300 and 350 nm to write a grating in the lead silicate glass, a much larger penetration length should be obtained since a lower absorption coefficient is expected for these wavelengths. Diffraction efficiency as high as 90% may be obtained if the thickness is a uniform index grating could be extended 4.2 μm for the same refractive index change of An = 0.09.
This large photo-induced index change may be due to color centers in lead silicate glass. It has been reported, see K.W. Delong. V. Mizrahi. G. I. Stegeman, M. A. Saifi. and M. J. Andrejco, J. Opt. Soc. Am., B7, 2210 (1990). that color centers were formed in a lead silicate glass through two-photon absorption of a pulsed doubled- YAG laser (532 nm). No photosensitivity was observed in these bulk glasses for irradiation at 532-nm at intensities up to the threshold for surface damage.
In summary, a high diffraction efficiency grating (10%) was induced in lead silicate glass by irradiation with a pulsed. 248-nm KrF excimer laser through a silica phase mask. The primary scattering mechanism was surface relief. By monitoring the diffraction efficiency as the surface was polished down, a photo-induced refractive index change An as high as 0.09 extending -125 nm into the glass was deduced.
Although the present invention has been fully described in conjunction with the preferred embodiment thereof with reference to the accompanying drawings, it is to be understood that various changes and modifications may be apparent to those skilled in the art. Such changes and modifications are to be understood as included within the scope of the present invention as defined by the appended claims, unless they depart therefrom.

Claims

WHAT IS CLAIMED IS:
1. A method for inducing a refractive index change in a lead silicate glass material comprising: providing a lead silicate glass material; and irradiating said lead silicate glass material to increase the index of refraction of said lead silicate glass material.
2. The method of claim 1, further comprising doping a silicate glass material with PbO to form said lead silicate glass material.
3. The method of claim 1, wherein said lead silicate glass material comprises about 19 mol.% to about 70 mol.% PbO.
4. The method of claim 1, wherein said lead silicate glass material comprises about 19 mol.% to about 57 mol.% PbO.
5. The method of claim 1, wherein said lead silicate glass material comprises about 40 mol.% to about 70 mol.% PbO.
6. The method of claim 1, wherein said lead silicate glass material is irradiated by a 266-nm laser source.
7. The method of claim 6, wherein said 266-nm laser source has a fluence of 25 mJ/cm" per pulse.
8. The method of claim 6. wherein said lead silicate glass material is irradiated with a total dose of 150 J/cm'.
9. The method of claim 1. wherein said lead silicate glass material is irradiated by a 248-nm laser source.
■ 7
10. The method of claim 1 , wherein said lead silicate glass material comprises a lead silicate fiber.
11. The method of claim 1 , wherein said lead silicate glass material comprises a lead silicate glass grating.
12. An irradiated lead silicate glass material made according to the method of claim 1.
13. A photo-induced lead silicate glass grating.
14. The photo-induced lead silicate glass grating of claim 13, wherein said photo- induced lead silicate glass grating comprises about 40 mol.% to about 70 mol.% PbO.
15. The photo-induced lead silicate glass grating of claim 13, wherein said photo- induced lead silicate glass grating has an efficiency of at least 10%.
16. The photo-induced lead silicate glass grating of claim 13, wherein said photo- induced lead silicate glass grating comprises a grating in a fiber.
17. The photo-induced lead silicate glass grating of claim 13, wherein said photo- induced lead silicate glass grating comprises a grating in a waveguide.
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