WO2007105708A1 - Verre comprenant un materiau formant un reseau precipite dans celui-ci et son procede de fabrication - Google Patents

Verre comprenant un materiau formant un reseau precipite dans celui-ci et son procede de fabrication Download PDF

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Publication number
WO2007105708A1
WO2007105708A1 PCT/JP2007/054904 JP2007054904W WO2007105708A1 WO 2007105708 A1 WO2007105708 A1 WO 2007105708A1 JP 2007054904 W JP2007054904 W JP 2007054904W WO 2007105708 A1 WO2007105708 A1 WO 2007105708A1
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Prior art keywords
glass
producing
glass according
less
laser
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English (en)
Japanese (ja)
Inventor
Kiyotaka Miura
Yasuhiko Shimotsuma
Koji Fujita
Kazuyuki Hirao
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Kyoto University NUC
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Kyoto University NUC
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Priority to JP2008505152A priority Critical patent/JP5256455B2/ja
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    • 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
    • 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

Definitions

  • the present invention relates to a glass in which an element that is a network former, such as Si or Ge, is deposited, and a method for producing the same.
  • silica glass can be irradiated with a laser, electron beam, ion beam, etc. to break the bond between Si and ⁇ (oxygen), and a region with less oxygen than usual can be formed inside the glass.
  • a laser a high level, peak intensity, and photon (photon) density can be realized, and a so-called “multiphoton process” in which multiple photons interact with glass can be realized.
  • a laser is used.
  • a femtosecond laser is considered to be suitable for forming the above-mentioned various devices because it has little influence on the structure of the glass except for the focal point (condensing point) of the irradiation.
  • Japanese Patent Laid-Open No. 2005-127924 states that “if femtosecond laser irradiation causes oxygen depletion to proceed, silicon crystals are precipitated in quartz glass (silica glass). (Paragraph [0017]).
  • an element that is a network former, such as Si, is precipitated inside.
  • the first object is to provide a glass and a method for producing the same.
  • the present invention provides a glass in which fine particles of elements that are network formers, specifically, Si and Ge, are dispersed and precipitated, and a method for producing the same. Objective.
  • the glass manufacturing method (first manufacturing method) of the present invention is a method for manufacturing glass (glass A — 2) in which a first element that is a network former is precipitated.
  • the glass contains the first element and a second element having a standard oxidation-reduction potential that is negatively larger than that of the first element, and oxygen contained in the glass is less than the stoichiometric ratio.
  • Glass A-1 is irradiated with a laser to precipitate the first element in the glass A-1 to obtain the glass A-2.
  • the glass on which the first element is precipitated by the laser irradiation may be further heat-treated.
  • the glass of the present invention includes a first element that is a network former and a second element that has a negative negative oxidation potential greater than that of the first element, and is a laser. This is a glass in which the first element is precipitated inside by irradiation.
  • the glass of the present invention (second glass: glass B-2) includes a first element that is a network former, and a second standard oxidation-reduction potential that is negatively greater than that of the first element. And glass in which fine particles of the first element are dispersed and precipitated.
  • the glass B_2 of the present invention has a first element that is a network composition and a standard oxidation-reduction potential that is more negative than the first element. It can be said that it is a glass that contains a large second element and whose emission derived from the first element as a simple substance is measured by irradiation with ultraviolet rays.
  • the glass production method (second production method) of the present invention is a method for producing glass B-2 of the present invention.
  • the second production method includes a first element that is a network former and a second element that has a negative standard oxidation-reduction potential that is negatively greater than that of the first element, and oxygen that is contained therein.
  • the glass (glass B-1) having less than the stoichiometric ratio is heat-treated, whereby the fine particles of the first element are dispersed and precipitated in the glass B-1, thereby obtaining the glass B-2.
  • the glass contains oxygen that satisfies the stoichiometric ratio
  • the glass if the average valence of the total power thione (network former, intermediate, network modifier) contained in the glass is n, the glass generally has the formula It can be described as MO (M: cation, ⁇ : oxygen).
  • MO metal-oxide-semiconductor
  • ⁇ oxygen
  • the oxygen content is stoichiometric n / 2
  • Glasses with less than can be described by the formula M 0 (0 X X n / 2).
  • the average valence n is the valence of each cation in the glass (for example, Si is 4, A1 is 3, Ca is 2, and Na is 1) weighted by the number of moles of the cation in the glass. It is a weighted average value.
  • a glass A_ containing a second element having a negative standard oxidation-reduction potential that is negatively larger than that of the first element to be deposited and containing less than the stoichiometric ratio of oxygen. l is irradiated with laser. Elements with a higher standard redox potential are easier to bind to oxygen, so the second element is more likely to bind to oxygen than the first element.
  • Glass A-1 is in a state of less oxygen than normal glass.
  • the glass contains the second element that is easy to combine with oxygen rather than simply irradiating the laser, and the glass is in an oxygen-deficient state. It is possible to promote the breaking of the bond between the first element and oxygen by irradiation of the first element, and the first element can be precipitated inside the glass.
  • a glass B containing a second element having a standard oxidation-reduction potential that is negatively larger than that of the first element to be precipitated and containing less than the stoichiometric ratio. Heat 1 and heat it. Since the standard oxidation-reduction potential is negatively large and the element is more likely to bind to oxygen, the second element is more likely to bind to oxygen than the first element.
  • Glass B-1 is in a state of less oxygen than normal glass.
  • the glass contains the second element that is easy to combine with oxygen rather than simply being heat-treated, and the glass is oxygen-deficient so that the first heat treatment can be performed. The breakage of the bond between the element and oxygen can be promoted, and the fine particles of the first element can be dispersed and precipitated inside the glass.
  • FIG. 1 is a view for explaining the structure of glass formed by the production method of the present invention in Examples.
  • FIG. 2 is a diagram illustrating the structure of glass formed by the production method of the present invention in Examples. It is a figure for clarification.
  • FIG. 3 is a view showing a light absorption spectrum and an emission spectrum of the second glass of the present invention formed in the examples.
  • the composition of the glass is described as that each cation is present in the glass as a stoichiometric oxide.
  • the A1 oxide has a force S that should be expressed as AlO (0 ⁇ x ⁇ 3/2) when oxygen is less than the stoichiometric ratio. It is described as being bound to a specific oxygen, ie Al 2 O 3.
  • the laser that irradiates the glass A-1 has a high peak intensity and can realize the multiphoton process described above, thereby facilitating the breaking of the bond between the first element and oxygen.
  • femtosecond laser with a pulse width of the pulse laser is a femtosecond (10 13 to 10-15 seconds).
  • the wavelength of the femtosecond laser applied to the glass A-1 is usually about 200 to 1600 nm.
  • the shorter the wavelength the more the breakage of the bond between the first element and oxygen can be promoted.However, when the wavelength is excessively short, it becomes difficult for the laser to penetrate into the glass or the glass A_ 1 Since the break of the bond between the first element and oxygen is also promoted at portions other than the laser focus (condensing point) inside, it is difficult to form a device having a fine structure.
  • the oscillation source of the femtosecond laser is not particularly limited.
  • it is a titanium sapphire laser that is commonly used as a femtosecond laser.
  • the glass A_l may be irradiated with two or more types of lasers having different repetition frequencies.
  • the first femtosecond laser having a relatively small repetition frequency may be
  • the glass A-1 may be irradiated with a second femtosecond laser having an extremely high repetition frequency.
  • the first laser breaks the bond between the first element and oxygen by the first laser, and the first laser is deposited, and the second laser
  • the first element deposited in the previous laser irradiation can be agglomerated.
  • the two or more types of lasers may be irradiated at the same time, and the irradiation timing may be mutually Shift and irradiate it.
  • the output of the femtosecond laser applied to glass A-1 is not particularly limited.
  • the repetition frequency is usually about 0.05 / J or more and the repetition frequency is 1 kHz. Is usually about 0 .: J to lmJ.
  • the wavelength, repetition frequency, output, and the like of the femtosecond laser applied to the glass A_1 may be arbitrarily set according to the type of the first element. The same applies to the case of irradiating one type of laser as well as the case of irradiating two or more types of lasers with different repetition frequencies.
  • the first element may be deposited in the vicinity of the focal point in the glass A-1 by irradiating a laser so that the focal point is located inside the glass A_l. .
  • a periodic structure or a line composed of the deposited first element can be formed inside the glass A-1, and the deposited first 1 It is also possible to form a circuit with elemental force.
  • a general laser optical system may be applied as a laser optical system for irradiating the glass A-1.
  • the size of the region where the first element precipitates in the glass A-1 can be controlled by adjusting the numerical aperture (NA) of the objective lens. More specifically, the size of the region can be increased by decreasing the NA value.
  • NA numerical aperture
  • the first element contained in the glass A-1 is not particularly limited as long as it is a glass network former.
  • it may be at least one selected from Si and Ge.
  • An S-type semiconductor can be formed by combining Ge and a doping element to form an n-type or p-type semiconductor. Therefore, when the first element is at least one selected from Si and Ge, a semiconductor element or a semiconductor circuit can be formed inside the glass. In order to form p-type semiconductors or n-type semiconductors inside the glass, for example, the doped elements (eg As, Ga, Glass A_1 further containing P or the like may be used.
  • the doped elements eg As, Ga, Glass A_1 further containing P or the like may be used.
  • the first element has a wide range of compositions that can become glass, and a wide range of devices that can be formed. More specifically, it is a general substance that constitutes a semiconductor device. Therefore, Si is preferable.
  • the glass A-2 contains Si, which is a network composition, and the second element, which has a negative negative oxidation potential with a large standard redox potential. It can be said that this is glass in which Si is deposited inside. Depending on the state of Si precipitation, this is a glass containing Si as a network former and a second element having a negative standard oxidation-reduction potential that is negatively larger than that of Si, with Si agglomerates precipitated inside. It can be said.
  • the glass A_2 includes a network former Ge and a second element having a negative standard oxidation-reduction potential larger than that of Ge. It can be said that this is a glass with Ge deposited inside by irradiation. In addition, depending on the state of Ge precipitation, it may be a glass containing Ge as a network former and a second element having a negative standard oxidation-reduction potential that is negatively larger than that of Ge, and having Ge agglomerates precipitated inside. I can say that.
  • the second element is not particularly limited as long as the standard oxidation-reduction potential (standard electrode potential E °) is negatively larger than that of the first element.
  • the second element is at least one selected from Al, Ti, and Zn. If it is.
  • the standard redox potential is the most negative (that is, the bondability with oxygen is the largest), and the breakage of the bond between the first element and oxygen can be further promoted.
  • the element of 2 is preferably A1.
  • the standard redox potential is the smallest when the standard redox potential is the most negative.
  • the content of the second element in the glass A-1 is not particularly limited. For example, it may be 1 mol% or more and 30 mol% or less in terms of oxide, and may be 5 mol% or more and 18 mol% or less. It is preferable.
  • the combination of the first element and the second element is not particularly limited, but it is preferable that the first element is Si and the second element is A1.
  • the glass A-1 and the glass A-2 after the laser irradiation are so-called aluminosilicate glass.
  • composition of the glass A_l is not particularly limited as long as it contains the first element and the second element.
  • the first element is Si and the second element is A1
  • it is expressed in mol%, and the actual white birch becomes 70 ⁇ Si ⁇ 99, 1 ⁇ A1 O ⁇ 30 force.
  • Preferably it is comprised of O ⁇ 18. “Substantially” means glass A-1 and glass raw material. This means that trace components such as impurities of origin may be contained in a range of less than 0.1 mol%.
  • Glass A-1 may further contain at least one selected from alkali metal elements and alkaline earth metal elements.
  • the alkali metal element has an action of reducing the melt viscosity of the glass.
  • Alkaline earth metal elements have the effect of lowering the melt viscosity of glass and the properties of glass A-1 such as strength and water resistance.
  • the alkali metal element is particularly preferably Na as long as it is at least one selected from Li, Na and K, for example.
  • the alkaline earth metal element is particularly preferably Ca as long as it is at least one selected from Mg, Ca, Sr and Ba.
  • the content of the alkali metal element in the glass A-1 is usually 60 mol% or less in terms of oxide. If the content is excessively high, the devitrification temperature of glass A-1 decreases.
  • the composition of glass A-1 is, for example, mol In terms of%, it should be substantially 10 ⁇ SiSi99, 1 ⁇ A11 ⁇ 30, 0 and NaO ⁇ 60.
  • glass A-1 contains an alkaline earth metal element
  • the content of the alkaline earth metal element in glass A-1 is usually 60 mol% or less in terms of oxide. If the content is excessively high, the devitrification temperature of glass A-1 decreases.
  • composition of glass A-2 on which the first element is deposited by laser irradiation is basically the same as that of glass A_l before laser irradiation, except for the portion where the first element is deposited. .
  • the method for forming glass A-1 irradiated with laser is not particularly limited.
  • the compound of the first element and the simple substance of the second element, or the contained oxygen is less than the stoichiometric ratio.
  • a raw material (glass raw material) containing the second element compound is melted and formed.
  • the compound of the first element and the simple substance of the second element are included.
  • the raw material is melted to form glass A-1.
  • the present invention relates to a compound of the first element which is a network former and a single element of the second element having a negative standard oxidation reduction potential larger than that of the first element, or oxygen contained therein in a stoichiometric amount.
  • a glass A-1 is formed by melting a raw material containing a compound of a second element that is less than the stoichiometric ratio, and the formed glass A-1 is irradiated with a laser so that the first element is introduced into the glass. It can also be implemented as a method of precipitation.
  • the compound of the first element is not particularly limited, but when the first element is Si, for example, it may be SiO.
  • the compound of the second element in which the oxygen is less than the stoichiometric ratio is not particularly limited.
  • the element of 2 is A1, for example, it may be any non-stoichiometric oxide of A1 represented by the formula Al 0 (0 ⁇ X ⁇ 3Z2).
  • the simple substance of the second element may be, for example, an A-spin (metal A1 particle) when the second element is A1.
  • the raw material to be melted may contain at least one selected from an alkali metal element compound and an alkaline earth metal element compound, if necessary. In this case, the melt viscosity of the raw material can be reduced.
  • the raw material may be melted in the air or in a reducing atmosphere.
  • a reducing atmosphere is used to deposit the first element more reliably. You can melt the raw material below.
  • the reducing atmosphere may be an atmosphere that does not contain oxygen, for example.
  • the glass on which the first element is precipitated by laser irradiation may be further heat-treated.
  • the heat treatment can agglomerate the first element precipitated in the glass, and if the aggregate of the first element is already precipitated before the heat treatment, the size of the aggregate can be increased. In other words, the size of the aggregate of the first element precipitated in the glass can be controlled by the heat treatment.
  • the temperature of the heat treatment may be appropriately set according to the size of the agglomerates precipitated inside the glass, but is usually the glass transition temperature (Tg) or higher of the glass A-1 and the crystallization temperature (Tc). The following is sufficient.
  • the heat treatment method is not particularly limited, and for example, an electric furnace or the like maintained at the heat treatment temperature is used. Glass that has been irradiated with a laser may be accommodated in a thermal furnace and held for a predetermined time.
  • the glass A-2 obtained by the first production method of the present invention has a structure in which the first element is precipitated inside the glass.
  • the glass A-2 may contain the first element inside the glass. It has a structure in which aggregates are deposited.
  • the specific structure of the aggregate is not particularly limited, but depending on the production method, an aggregate having crystallinity, for example, crystalline Si can be precipitated inside the glass.
  • the refractive index as SiO is approximately 1.5.
  • the refractive index of is about 3.4. That is, by depositing Si as the first element inside the glass, it is possible to form a portion having a higher refractive index than the surroundings inside the glass. Such a part can be applied as an optical waveguide depending on its shape.
  • glass A_2 on which various devices such as a semiconductor element, a semiconductor circuit, and a photonic crystal are formed can be formed.
  • Glass B-2 of the present invention contains a first element that is a network former and a second element that has a higher standard oxidation-reduction potential than the first element, and the fine particles of the first element Has a structure in which it is dispersed and deposited inside.
  • Glass B-2 is expected to have various applications.
  • the first element is at least one selected from Si and Ge
  • glass B-2 is dispersed in at least one selected from Si fine particles and Ge fine particles.
  • it can be a glass that emits light upon irradiation with ultraviolet rays.
  • Such glass B-2 can be applied as a light emitting material, for example.
  • the glass containing dispersed Si fine particles and the glass containing dispersed Ge fine particles have a peak wavelength in the spectrum of light emitted by irradiation with ultraviolet rays. Can be an area.
  • ultraviolet irradiation can be achieved by adjusting the precipitation ratio of Si particles to Ge particles in glass B_2.
  • the emission spectrum of the glass B_2 can be controlled, and for example, it is possible to use the glass B-2 that emits white light when irradiated with ultraviolet rays.
  • the precipitation ratio between Si fine particles and Ge fine particles is It can be controlled by adjusting the composition of S-Bl, more specifically, the molar ratio of SiO and GeO contained in glass B-1.
  • composition of the glass B-2 of the present invention is basically the same as that of the glass B-1 before the heat treatment, except for the portion where the first element is precipitated.
  • the temperature at which the glass B_l is heat-treated is usually the glass B_
  • the method of the heat treatment is not particularly limited.
  • the glass B-1 may be accommodated in a heating furnace such as an electric furnace kept at the heat treatment temperature and held for a predetermined time.
  • the first element contained in the glass B-1 is not particularly limited as long as it is a glass network former.
  • it may be at least one selected from Si and Ge.
  • the second element contained in glass B-1 is not particularly limited as long as the standard oxidation-reduction potential is negatively larger than that of the first element.
  • the second element is at least one selected from Al, Ti, and Zn. I just need it.
  • the standard redox potential is the most negative (that is, the bond with oxygen is the largest), and the breakage of the bond between the first element and oxygen can be further promoted.
  • the element of 2 is preferably A1.
  • the standard redox potential is the smallest when the standard redox potential is the most negative.
  • the content of the second element in the glass B-1 is not particularly limited. For example, it may be 1 mol% or more and 30 mol% or less in terms of oxide. 5 mol% or more 18 mol % Or less is preferred.
  • composition of the glass B_l is not particularly limited as long as it contains the first element and the second element.
  • the first element is Si and the second element is A1
  • it is expressed in mol% and, in fact, 70 ⁇ Si ⁇ 99, 1 ⁇ A1 O ⁇ 30 82 ⁇ Si ⁇ 99, 1 ⁇ A1
  • glass B-1 may contain trace components such as impurities originating from the glass raw material in a range of less than 0.1 mol%.
  • the first element is Ge and the second element is A1
  • it is expressed in mol%, and it is 70 ⁇ Ge ⁇ 99, 1 ⁇ A1 O ⁇ 30 force. It is preferable that it consists of 82 ⁇ GeO ⁇ 99, 1 ⁇ A l O ⁇ 18.
  • glass B-1 contains both Si and Ge
  • glass B-1 is expressed in mol% and is essentially from 70 ⁇ SiO + GeO ⁇ 99, 1 ⁇ A10 ⁇ 30. Yes, 82 ⁇ Si ⁇ +
  • GeO ⁇ 99, 1 ⁇ A1 O ⁇ 18 Preferably, GeO ⁇ 99, 1 ⁇ A1 O ⁇ 18.
  • Glass B-1 may further contain at least one selected from alkali metal elements and alkaline earth metal elements.
  • the alkali metal element has an action of decreasing the melt viscosity.
  • Alkaline earth metal elements have the effect of reducing the melt viscosity in the same way as alkali metal elements, and also have the effect of improving the properties of glass B-1 such as strength and water resistance.
  • the alkali metal element is particularly preferably Na, as long as it is at least one selected from Li, Na and K, for example.
  • the alkaline earth metal element is particularly preferably Ca as long as it is at least one selected from Mg, Ca, Sr and Ba.
  • glass B-1 contains an alkali metal element
  • the content of the alkali metal element in glass B-1 is usually 60 mol% or less in terms of oxide. If the content is excessively high, the devitrification temperature of glass B-1 decreases.
  • the composition of glass B-1 is, for example, mol In terms of%, it should be substantially 10 ⁇ SiSi99, 1 ⁇ A11 ⁇ 30, 0 and NaO ⁇ 60.
  • the composition of glass B-1 is, for example, mol Displayed in%, in effect, 10 ⁇ GeO 99, 1 ⁇ A1 O ⁇ 30, 0 ⁇ Na O ⁇ 60.
  • the composition of glass B-1 For example, in terms of mol%, 10 ⁇ SiO + GeO 99, 1 ⁇ A1 O ⁇ 30, 0 ⁇ Na 0 ⁇ 60.
  • the content of the alkaline earth metal element in glass B-1 is usually 60 mol% or less in terms of oxide. When the content is excessively high, the devitrification temperature of glass B-1 decreases.
  • the method for forming the glass B-1 to be heat-treated is not particularly limited.
  • the first element compound and the second element alone or the oxygen contained therein is less than the stoichiometric ratio.
  • a raw material (glass raw material) containing a compound of the two elements may be melted.
  • the amount of oxygen contained in the glass B_l can be further reduced and the bond breaking between the first element and oxygen can be further promoted, the compound of the first element and the simple substance of the second element are included. It is preferable to melt the raw material to form glass B-1.
  • the present invention relates to a compound of the first element which is a network former and the second element alone having a negative standard oxidation reduction potential larger than that of the first element, or oxygen contained therein in a stoichiometric amount.
  • a compound of the first element which is a network former and the second element alone having a negative standard oxidation reduction potential larger than that of the first element, or oxygen contained therein in a stoichiometric amount.
  • the compound of the first element is not particularly limited, but when the first element is Si, for example, when it is SiO, the first element is Ge, for example, GeO. That's fine.
  • the compound of the second element in which the oxygen is less than the stoichiometric ratio is not particularly limited.
  • any non-stoichiometric oxide of A1 represented by the formula Al 0 (0 ⁇ X 3/2) may be used.
  • the simple substance of the second element may be, for example, an A-tung (metal A1 particle).
  • the raw material to be melted may contain at least one selected from an alkali metal element compound and an alkaline earth metal element compound, if necessary. In this case, the melt viscosity of the raw material can be reduced.
  • the melting of the raw material may be performed in the air or in a reducing atmosphere.
  • glass B-1 has a composition with a relatively small content of the second element (as oxide)
  • the raw material may be melted in a reducing atmosphere.
  • the reducing atmosphere may be an atmosphere that does not contain oxygen, for example.
  • the prepared glass raw material batch was put into an alumina crucible, and the crucible was accommodated in a furnace in an atmospheric atmosphere, and the raw material batch was melted at 1400 ° C to obtain a molten glass.
  • the crucible is taken out from the furnace, cooled to room temperature, and the resulting glass is cut and polished for evaluation.
  • a femtosecond laser pulse width 150 fs, wavelength 800 nm, repetition frequency 1 kHz, output 300 ⁇
  • the laser Femtosecond lasers with different repetition frequencies pulse width 150 fs, wavelength 800 ⁇ m, repetition frequency 200 kHz, output 3 ⁇ J
  • An objective lens with a numerical aperture (NA) of 0.3 was used for both laser irradiations.
  • FIG. 1 shows (A) is an SEM image of the part, (b) is an EDS image focusing on the Si in the part, and (c) is an EDS image focusing on oxygen in the part. In the EDS images of (b) and (c), the region containing more elements of interest is shown brighter.
  • the graph in Fig. 1 with energy (keV) on the horizontal axis and strength (cps) on the vertical axis shows the EDS measurement results for the Si region and glass matrix shown in (a).
  • the glass sample 1 formed in Example 1 was irradiated with a femtosecond laser (pulse width 150 fs, wavelength 800 nm, repetition frequency 200 kHz, output 3 ⁇ J) so that the focal point was located inside the sample.
  • a femtosecond laser pulse width 150 fs, wavelength 800 nm, repetition frequency 200 kHz, output 3 ⁇ J
  • An objective lens with a numerical aperture (NA) of 0.3 was used for laser irradiation.
  • the sample irradiated with the laser was placed in an electric furnace set at 550 ° C, heat-treated for 60 minutes, and then cooled to room temperature. Note that Tg in sample 1 is approximately 470 ° C, and Tc is approximately 690 ° C.
  • the heat-treated sample was polished to expose a portion near the laser focal point in the sample.
  • a region made of Si (about 7 ⁇ in the major axis direction) was formed in that area.
  • (a) in Fig. 2 is an SEM image of the relevant part
  • (b) is an enlarged view of the region part made of Si in the SEM image of (a)
  • (c) focuses on Si in the relevant part.
  • (D) is an EDS image focusing on the oxygen in the part. In the EDS images for Si and oxygen, the upper right part of the part is dark, that is, the power at which the Si and oxygen signals disappear. S because it was scraped off.
  • a glass raw material batch is placed in a reducing atmosphere (not nitrogen atmosphere).
  • a glass sample for evaluation (Sampnore 2) was obtained in the same manner as in Example 1 except that the sample was melted under an atmosphere of the same.
  • the glass raw material batch was melted in a reducing atmosphere by putting the prepared glass raw material batch into an alumina crucible, and storing the crucible in the furnace under the reducing atmosphere and heating to 1400 ° C. .
  • Example 2 the sample 2 was irradiated with the laser and then evaluated by SEM and EDS. As a result, the sample 1 was located near the focal point of the laser inside the sample 2. The same Si region was formed. In addition, when the region made of Si was evaluated by TEM and ESR, it was found that the region was made of crystalline Si.
  • a glass sample A as a comparative example was produced in the same manner as in Example 1 except that a glass raw material batch was prepared.
  • the portion of the silica glass near the focal point of the laser was observed by SEM and EDS, but the region made of Si was not formed.
  • Al particles 36: 36: 28.
  • the number of moles of A-tachi was the value obtained by dividing the weight of A-tung by the atomic weight of A1 (27.0).
  • the prepared glass raw material batch was put into an alumina crucible, and the crucible was accommodated in a furnace in an air atmosphere, and the raw material batch was melted at 1500 ° C to obtain a molten glass.
  • the crucible was taken out from the furnace and cooled to room temperature, and the obtained glass was cut and polished to obtain a glass sumnore for evaluation (Sampnore 3).
  • sample 3 was placed in an electric furnace set at 550 ° C and heat-treated for 60 minutes, and then cooled to room temperature. Note that Tg in sample 3 is approximately 480 ° C, and Tc is approximately 690 ° C.
  • the value was divided by the atomic weight (27.0).
  • Example 4 a glass sample for evaluation (sample 4) was obtained in the same manner as in Example 3. [0120] When the state of the obtained sample 4 was observed with an optical microscope, particulate matter was not confirmed inside the glass. It is considered that the A-tachi added to the glass raw material melted during melting.
  • ultraviolet light (wavelength: 280 to 400 nm) was irradiated to the heat-treated Sampnore 4 to evaluate the light absorption spectrum and emission spectrum of the Sampnore.
  • Figure 3 shows the evaluation results.
  • a glass sample for evaluation (Sampnore 5) was obtained in the same manner as in Example 4 except that the glass raw material batch was melted in a reducing atmosphere (in a nitrogen atmosphere containing 3% by volume of hydrogen) instead of in an air atmosphere. It was.
  • the glass raw material batch was melted in a reducing atmosphere by putting the prepared glass raw material batch into an alumina crucible and placing the crucible inside the furnace under the reducing atmosphere and heating to 1500 ° C. .
  • the sample 5 after the heat treatment was irradiated with ultraviolet rays (wavelength 280 to 400 nm) to evaluate the light absorption spectrum and emission spectrum of the sample, and the same results as in Example 4 were obtained. Obtained.
  • Example 4 Weigh and mix SiO, CaCO and Al 2 O as glass raw materials so that A raw material batch was prepared. Next, a glass sample for evaluation (Comparative Example Sample B) was obtained in the same manner as Example 4.
  • a glass in which an element that is a network former such as Si is deposited can be formed.

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  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un verre comprenant un élément tel que Si, qui est un matériau formant un réseau, précipité dans celui-ci, et son procédé de fabrication. Le verre comprend des particules fines d'un élément formant un réseau, spécifiquement Si, Ge ou analogues, précipitées dans celui-ci dans un état dispersé. Un faisceau laser est appliqué sur un verre comprenant un premier élément en tant que matériau formant un réseau et un second élément ayant un potentiel standard d'oxydation/réduction, qui est plus grand dans une direction négative que le premier élément, contenant de l'oxygène en une quantité inférieure au rapport stœchiométrique de façon à faire précipiter le premier élément dans le verre. En variante, un verre comprenant un premier élément en tant que matériau formant un réseau et un second élément ayant un potentiel standard d'oxydation/réduction, qui est plus grand dans une direction négative que le premier élément, contenant de l'oxygène en une quantité inférieure au rapport stœchiométrique, est soumis à un traitement thermique de façon à disperser et faire précipiter des particules fines du premier élément dans le verre.
PCT/JP2007/054904 2006-03-13 2007-03-13 Verre comprenant un materiau formant un reseau precipite dans celui-ci et son procede de fabrication Ceased WO2007105708A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103666475A (zh) * 2013-12-11 2014-03-26 昆明理工大学 一种稀土掺杂玻璃频率转换发光材料及制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160271A (ja) * 1997-08-20 1999-03-02 Res Dev Corp Of Japan 金属微粒子分散ガラス及びその製造方法
JPH1171139A (ja) * 1997-08-26 1999-03-16 Res Dev Corp Of Japan 微結晶分散ガラス及びその製造方法
JP2001235609A (ja) * 2000-02-22 2001-08-31 Central Glass Co Ltd 非金属粒子析出ガラス及びその作製方法
JP2004107612A (ja) * 2002-03-05 2004-04-08 Dainippon Printing Co Ltd 希土類元素含有微粒子およびそれを用いた蛍光プローブ
JP2004352542A (ja) * 2003-05-28 2004-12-16 National Institute Of Advanced Industrial & Technology ナノ粒子で装飾された無機成形体及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160271A (ja) * 1997-08-20 1999-03-02 Res Dev Corp Of Japan 金属微粒子分散ガラス及びその製造方法
JPH1171139A (ja) * 1997-08-26 1999-03-16 Res Dev Corp Of Japan 微結晶分散ガラス及びその製造方法
JP2001235609A (ja) * 2000-02-22 2001-08-31 Central Glass Co Ltd 非金属粒子析出ガラス及びその作製方法
JP2004107612A (ja) * 2002-03-05 2004-04-08 Dainippon Printing Co Ltd 希土類元素含有微粒子およびそれを用いた蛍光プローブ
JP2004352542A (ja) * 2003-05-28 2004-12-16 National Institute Of Advanced Industrial & Technology ナノ粒子で装飾された無機成形体及びその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103666475A (zh) * 2013-12-11 2014-03-26 昆明理工大学 一种稀土掺杂玻璃频率转换发光材料及制备方法

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