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WO2018097350A1 - CÉRAMIQUES D'α-SIALON À CONVERSION ASCENDANTE TRANSPARENTES POLYCRISTALLINES TRIPLEMENT DOPÉES ET PROCÉDÉ POUR LES PRÉPARER - Google Patents

CÉRAMIQUES D'α-SIALON À CONVERSION ASCENDANTE TRANSPARENTES POLYCRISTALLINES TRIPLEMENT DOPÉES ET PROCÉDÉ POUR LES PRÉPARER Download PDF

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Publication number
WO2018097350A1
WO2018097350A1 PCT/KR2016/013581 KR2016013581W WO2018097350A1 WO 2018097350 A1 WO2018097350 A1 WO 2018097350A1 KR 2016013581 W KR2016013581 W KR 2016013581W WO 2018097350 A1 WO2018097350 A1 WO 2018097350A1
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molded body
ceramic molded
triple
sialon
doped polycrystalline
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English (en)
Korean (ko)
Inventor
이수완
세트리유알아즈
정상훈
김성호
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Industry University Cooperation Foundation of Sun Moon University
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Industry University Cooperation Foundation of Sun Moon University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials

Definitions

  • the present invention relates to alpha sialon ceramics having a translucent and upconverting property in a triple-doped visible region and an infrared region in which erbium, holmium and thulium are formed, and a method of manufacturing the same.
  • Up-conversion materials are based on oxides and oxy-fluoride glasses. However, these materials exhibit poor chemical stability and mechanical properties and are therefore limited in their many applications.
  • translucent polycrystalline ceramics have been introduced as up-conversion materials.
  • Lanthanide-doped yttria and YAG materials exhibit up-conversion properties that can collect light in the infrared region that covers most of the solar spectrum and convert it to high energy wavelengths, which can be applied to solar cell windows. -Can also be applied to displays [see: S. Chen, Y. Wu, New opportunities for transparent Ceramics, Amer. Ceram. Soc. Bull., 92 (2013) 32-7 and T.R. Hinklin, S.C. Rand, R.M. Laine, Transparent, Polycrystalline Upconverting Nanoceramics: Towards 3-D Displays, Advanced Materials, 20 (2008) 1270-3].
  • sialon a silicon nitride present with alumina
  • the sialon ceramic material is different from silicon nitride because aluminum and oxygen are included in the crystal structure. Ceramic products made of sialon exhibit high strength even at high temperatures and have high hardness suitable for industrial applications. In particular, sialon has superior hardness to alumina at high temperatures.
  • compounds such as yttria and magnesia are typically added to aid in sintering. During sintering, these compounds react with silica on the silicon nitride surface, intentionally added silica, or with silica present as an impurity.
  • phase chemistry of the sialon intergranular phase is more complex than that of silicon nitride ceramic systems. See F. Riley, J. Amer. Ceram. Soc. 83 [2] (2000) 259]. Almost completely densified sialon ceramics can be obtained at lower grain boundaries by the insertion of metal cations into the silicon nitride lattice. According to numerous documents and patents, intergranular phases are known to degrade the properties of ceramics because they generally lead to high temperature degradation and reduced strength. See U.S. Pat. No.
  • the best known crystalline phases in the sialon family are the alpha and beta phases, which are based on the alpha and beta phases of silicon nitride. On sialon, some of the silicon and nitrogen atoms are replaced by aluminum and oxygen atoms.
  • the betasialon phase is generally represented by the formula Si 6 - z Al z O z N 8 -z , where 0 ⁇ z ⁇ 4.2. In this structure, no additional metal ions are included in the crystal lattice.
  • the alpha sialon phase is generally represented by the formula Mx (Si, Al) 12 (O, N) 16 where x is 0 ⁇ x ⁇ 2, M is an element such as Mg, Y, Ce, Sc, or other rare earth materials. Indicates. More specifically, stoichiometrically M m / v Si 12-mn Al m + n O n N 16-n [GZ Cao and R. Metselaar, " ⁇ '-Sialon Ceramics: A Review", Chem. Mat. Vol. 3 No 2, 242-252 (1991), where v is the balance of M. Two formulas are used interchangeably in the present invention. Suitable M ions in this structure are not suitable in beta sialon structures.
  • alpha sialon represents equiaxed crystal grains in the microstructure of ceramics and is therefore used as a high strength material.
  • the equiaxed microstructure has better light transmittance and higher intensity.
  • An object of the present invention is to provide a triple doped sialon ceramic body having high temperature stability and strength while having excellent light transmission and upconversion light emission characteristics in the infrared region and the visible region. It is yet another object of the present invention to provide a method of making triple doped translucent sialon ceramics having upconversion properties.
  • the present invention is a ceramic molded body, (Ho, Tm, Er) x Si 12 -m- n Al m + n O n N 16 -n (0 ⁇ x ⁇ 2, 1.0 ⁇ m ⁇ 1.5 And an alpha sialon crystal structure represented by 1.0 ⁇ n ⁇ 1.5).
  • the ceramic molded body is, Si 6 - can further include a z Al z O z N 8 -z oxynitride glass phase structure of beta-SiAlON represented by (0 ⁇ z ⁇ 4.2).
  • upconversion may occur at a wavelength of at least one of 560 nm, 657 nm, 679 nm, and 805 nm.
  • upconversion may occur at at least two wavelengths of 560 nm, 657 nm, 679 nm, and 805 nm.
  • the ceramic molded body may have an energy transfer efficiency of 96.4% or more at a wavelength of 1530 nm.
  • the method for producing a ceramic molded body of the present invention alpha-silicon nitride, Er 2 O 3 , Al 2 O 3 , Tm 2 O 3 , Ho 2 O 3 And mixing AlN powder to prepare a mixed powder, compressing the mixed powder to prepare a compact, and compressing the compact into a nitrogen atmosphere at a temperature of 1700 to 1900 ° C. at a pressure of 25 to 30 MPa.
  • the ceramic molded body may have a thickness of 200 ⁇ m to 500 ⁇ m.
  • the present invention relates to transparent alpha sialon ceramics doped with erbium, holmium and thulium, wherein the observed hardness and fracture toughness of the sintered alpha sialon ceramics are YAG, Y 2 O 3 and other commercial optically active polycrystalline light transmissive ones. Higher than ceramics.
  • FIG. 1 is a graph showing an XRD pattern according to an embodiment of the present invention.
  • Figure 2 shows the HRTEM micrograph and SAD pattern according to an embodiment of the present invention.
  • FIG. 3 is a graph showing an upconversion emission spectrum according to an embodiment of the present invention.
  • FIG. 4 is a photograph for showing light transmittance of a sample according to an embodiment of the present invention.
  • 5 is a graph showing an upconversion emission spectrum according to an embodiment of the present invention.
  • FIG. 6 is a graph illustrating a downconversion emission spectrum according to an embodiment of the present invention.
  • FIG. 7 is a graph showing an absorption spectrum according to an embodiment of the present invention.
  • FIG. 8 is a graph showing radiation attenuation according to an embodiment of the present invention.
  • sialon ceramics are well known as structural engineering materials, they are not well known for their optical properties.
  • the inventors of the present invention have developed sialon ceramics different from the existing ones, which are naturally translucent and exhibit upconversion emission characteristics. Translucent sialon ceramics are produced under controlled composition and sintering conditions. The inventors have confirmed that the alpha sialon ceramics are stabilized with metal cations and manufactured alpha sialon ceramics stabilized with erbium cations.
  • Erbium is known to exhibit upconversion in a number of host materials, ie Y 2 O 3 , YAG and other oxide ceramic nanopowders.
  • Alpha sialon has a unique crystal structure, which is suitable for metal ions in a unit cell and has two lattice positions to stabilize the structure.
  • the erbium cation was doped at this lattice position and the physical and optical properties were studied.
  • erbium, holmium, and thulium were co-doped in triple, and the upconversion emission characteristics thereof were studied.
  • the crystal phase was confirmed by XRD pattern analysis.
  • the main crystalline phase was represented by alpha sialon and included small amounts of beta sialon, AlN polytype, and vitrified intergranular phases. Nevertheless, the sialon ceramics produced in the present invention are preferably considered as alpha sialon ceramics.
  • the ceramic molded body may be represented by the following chemical formula.
  • x, m and n are in the range of 0 ⁇ x ⁇ 2, 1.0 ⁇ m ⁇ 1.5 and 1.0 ⁇ n ⁇ 1.5.
  • Ho, Tm, Er includes all three cationic elements, and a small amount of other elements may be added during the manufacturing process or for other reasons.
  • Ho and Tm are doped at the same weight ratio, and the relative weight of Er
  • T3 erbium-only sample (E3), holmium-only sample (H3), holmium-erbium co-doped sample (HE5), and thulium and erbium-doped sample (TE5) were also prepared and characterized.
  • m and n are each limited to the range of 1.0 to 1.5, but when m or n is less than 1.0, the upconversion characteristics are drastically reduced.
  • E3 erbium-only sample
  • H3 holmium-only sample
  • HE5 holmium-erbium co-
  • the transmittance in the visible light range was found between m and n of 1.0 to 1.5 based on the Tm, but the visible light transmittance of the m or n range of 2.0 was found to be close to zero.
  • the visible light transmittance is an important characteristic, through which it was confirmed that m and n is preferably in the range 1.0 ⁇ 1.5.
  • beta sialon may be partially produced at the interface of alpha sialon, and the chemical formula is as follows:
  • the method for preparing the alpha sialon ceramic molded body co-doped with the erbium, holmium and thulium of the present invention is as follows:
  • the weight ratios of erbium, holmium and thulium were 1.78 to 7.13 wt%, respectively, and the sum of the erbium, holmium and thulium concentrations was approximately 11 wt%.
  • the approximate meaning here is that it is difficult to fit 11 wt% mathematically, so that some errors may occur experimentally.
  • the thickness of the manufactured molded article is in the range of 200 to 500 ⁇ m.
  • the thickness of the molded product is made thinner than 200 ⁇ m, no suitable strength is obtained. Samples in the present invention used that made to a thickness of 200 ⁇ m. If the molded body is not in the temperature range and pressure range presented in step c), the permeability is low, or the strength is difficult to apply the application.
  • the alpha sialon of the present invention is a crystal structure stabilized by erbium, holmium and thulium ions.
  • all samples are composed of isometric, isotropic polyhedral grains, which are general alpha sialon grain shapes. This grain shape allows for better optical light transmission. Translucent ceramics are required for various applications due to their excellent mechanical properties.
  • Luminescent ceramics are also known as phosphors.
  • Such phosphorescent light-transmitting ceramics are light-transmissive in the visible light spectrum because these materials absorb different wavelengths of visible light at the emission center.
  • sialon ceramics having a hexagonal structure most of the light is scattered through grain boundaries. When the grain size is adjusted to 500 nm or less, it shows partial light transmittance in the visible region.
  • the sialon ceramics produced in the present invention showed much higher light transmittance in the infrared region. The light transmittance varies with thickness, and the thinner it is, the higher the light transmittance in the visible region.
  • Figure 4 is a photograph showing the light transmittance for a 500 ⁇ m thick HTE55 sample. As shown in FIG. 4, it was confirmed that the visible light transmittance was excellent.
  • Absorption spectrum is shown in FIG. In the absorption spectra of the thorium-doped sample (T3) and the holmium-only sample (H3), no absorption band around 980 nm was observed. Therefore, traditional 980 nm pumping cannot be used for thulium doped alpha sialon or holmium doped alpha sialon.
  • triple doped samples of erbium, holmium and thulium indicate that the co-doped samples can be excited by a 980 nm laser.
  • several pairs of absorption bands can be observed in the visible region (approximately 400-700 nm), allowing for up-converted luminescence with erbium, holmium, and thulium through triple-doped alpha-sialon.
  • FIG. 5 The light spectrum excited to the 980 nm laser at room temperature for each sample is shown in FIG. 5.
  • FIG. 6 is a downconversion spectrum.
  • the only thulium doped only one sample (T3) and a holmium-doped sample (H3) did not show up-conversion emission, since there is 3 + Ho and Tm 3 + can be excited at 980nm.
  • Erbium-doped sample (E3) showed strong green light, weak red light and infrared light emission.
  • FIG. 5B a frequency downconversion band was observed around 1530 nm, and this downconversion can be applied to a near infrared communication window.
  • HTE55, HTE75, HTE11 strong red light emission appeared around 657 nm and 679 nm, while strong infrared light emission was around 805 nm.
  • the energy transfer efficiency was calculated using the emission lifetime at 1530 nm wavelength, and the respective values were compared, and the contents thereof are shown in Table 2 below.
  • the light emission lifetime? Is obtained using a radiation attenuation curve generated during downconversion. 8 shows the radiation attenuation curve of downconversion occurring at 1530 nm.
  • the light emission life is calculated by Equation 1 below using a radiation attenuation curve.
  • A, B 1 , B 2 , and B 3 represent the amplitudes of the respective attenuation elements, and ⁇ 1 , ⁇ 2 , and ⁇ 3 represent the light emission lifetimes of the respective attenuation elements.
  • the energy transfer efficiency is related to the light emission life and is calculated by Equation 2 below.
  • ⁇ energy transfer efficiency
  • ⁇ f and ⁇ 0 are light emission lifetimes with and without acceptor ions.
  • ( ⁇ 1, ⁇ 2) is a value calculated through equation (1) using the radiation attenuation curve of Figure 8, by using this, we calculated the energy transfer efficiency from the following expression (2).
  • the value of ⁇ 1 for the case of acceptor ion for Er is represented by ⁇ f in Equation 2.
  • ⁇ 1 of E3 becomes ⁇ o of Equation 2
  • ⁇ 1 of the remaining samples is ⁇ f .
  • the HTE55 had an energy transfer efficiency of 96.4%. This is a significant improvement over the energy transfer efficiency of 66.3% of the co-doped erbium and thorium (TE5) and 71.6% of the co-doped holmium and erbium (HE5). Can be predicted.
  • TE5 co-doped erbium and thorium
  • HE5 co-doped holmium and erbium
  • This triple dope of erbium, holmium and thulium with a combination of high visible and infrared light transmittance, excellent upconversion and downconversion luminescence properties, moderately low phonon energy and excellent mechanical and thermochemical stability is expected to serve a variety of applications in the future. Application is possible.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne des céramiques d'α-SiAlON transparentes triplement dopées avec de l'erbium, du thulium et de l'holmium et un procédé pour leur préparation. Les céramiques sont caractérisées en ce que l'une conversions ascendante se produit à au moins une longueur d'onde parmi 657 nm, 679 nm, et 805 nm lorsque les céramiques sont irradiées avec une lumière de 980 nm à température ambiante. La dureté et la ténacité à la rupture observées des céramiques d'α-SiAlON frittées sont supérieures à celles d'autres céramiques transparentes polycristalline optiquement actives du commerce, notamment YAG et Y2O3.
PCT/KR2016/013581 2016-11-24 2016-11-24 CÉRAMIQUES D'α-SIALON À CONVERSION ASCENDANTE TRANSPARENTES POLYCRISTALLINES TRIPLEMENT DOPÉES ET PROCÉDÉ POUR LES PRÉPARER Ceased WO2018097350A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL2021109B1 (en) * 2018-06-12 2019-12-17 Physee Group B V Inorganic luminescent materials for solar radiation conversion devices

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4701928A (en) * 1985-10-02 1987-10-20 Board Of Trustees, Leland J. Stanford University Diode laser pumped co-doped laser
US5200374A (en) * 1990-04-06 1993-04-06 Ube Industries, Ltd. Sialon-based sintered body and process for producing same
US7075707B1 (en) * 1998-11-25 2006-07-11 Research Foundation Of The University Of Central Florida, Incorporated Substrate design for optimized performance of up-conversion phosphors utilizing proper thermal management
KR20120117577A (ko) * 2011-04-15 2012-10-24 한국에너지기술연구원 알루미늄이 결핍된 α-ＳｉＡｌＯＮ계 형광체, 그 제조 방법 및 이를 이용한 ＬＥＤ 칩 패키지

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4701928A (en) * 1985-10-02 1987-10-20 Board Of Trustees, Leland J. Stanford University Diode laser pumped co-doped laser
US5200374A (en) * 1990-04-06 1993-04-06 Ube Industries, Ltd. Sialon-based sintered body and process for producing same
US7075707B1 (en) * 1998-11-25 2006-07-11 Research Foundation Of The University Of Central Florida, Incorporated Substrate design for optimized performance of up-conversion phosphors utilizing proper thermal management
KR20120117577A (ko) * 2011-04-15 2012-10-24 한국에너지기술연구원 알루미늄이 결핍된 α-ＳｉＡｌＯＮ계 형광체, 그 제조 방법 및 이를 이용한 ＬＥＤ 칩 패키지

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LI, BIN: "Upconversion luminescence properties of Er3+/Yb3+ in transparent a-sialon ceramics", OPTICAL MATERIAL, 2015, pages 239, XP055599758, DOI: doi:10.1016/j.optmat.2014.11.034 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL2021109B1 (en) * 2018-06-12 2019-12-17 Physee Group B V Inorganic luminescent materials for solar radiation conversion devices
WO2019240578A1 (fr) * 2018-06-12 2019-12-19 Physee Group B.V. Matériaux luminescents inorganiques pour dispositifs de conversion de rayonnement solaire
US12173213B2 (en) 2018-06-12 2024-12-24 Physee Group B.V. Inorganic luminescent materials for solar radiation conversion devices

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