TWI844681B - Surface-coated phosphor particle and light emitting device - Google Patents
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Abstract
Description
本發明係關於表面被覆螢光體粒子、以及發光裝置。The present invention relates to surface-coated fluorescent particles and a light-emitting device.
至今已開發出各式各樣的螢光體。就此種技術而言，例如，已知有專利文獻1記載之技術。專利文獻1已有針對SrLiAl3 N4 ：Eu即SLAN螢光體之記載(專利文獻1之請求項1、段落0113等)。 [先前技術文獻] [專利文獻]Various types of phosphors have been developed so far. For example, the technology described in Patent Document 1 is known. Patent Document 1 describes SrLiAl 3 N 4 :Eu, i.e., SLAN phosphors (claim 1, paragraph 0113, etc. of Patent Document 1). [Prior Technical Document] [Patent Document]
[專利文獻1]國際公開第2013/175336號[Patent Document 1] International Publication No. 2013/175336
[發明所欲解決之課題][The problem that the invention wants to solve]
惟，本案發明人進行探討，結果發現上述專利文獻1記載的螢光體粒子，在高溫高濕環境下之發光強度特性方面仍有改善之餘地。 [解決課題之手段]However, the inventors of this case have conducted research and found that the fluorescent particles described in the above-mentioned patent document 1 still have room for improvement in terms of luminescence intensity characteristics in high temperature and high humidity environments. [Means for solving the problem]
已知針對藉由煅燒而得到的螢光體粒子，在高溫高濕環境下使用時發光強度會大幅降低。It is known that the luminescence intensity of fluorescent particles obtained by calcination will be greatly reduced when used in a high temperature and high humidity environment.
本案發明人更進一步探討，發現藉由對於表面被覆螢光體粒子施予適當加熱處理，能夠提升高溫高濕環境下之發光強度特性。雖詳細機制尚未知，但據推測係螢光體粒子表面層穩定化，即使在高溫高濕條件下仍可抑制發光特性的降低。The inventors of this case have further studied and found that by applying appropriate heat treatment to the surface-coated fluorescent particles, the luminescence intensity characteristics in high temperature and high humidity environments can be improved. Although the detailed mechanism is still unknown, it is speculated that the surface layer of the fluorescent particles is stabilized, which can inhibit the reduction of luminescence characteristics even under high temperature and high humidity conditions.
基於如此之知識見解而深入探討，結果發現，將令使用Cu-Kα射線進行測定而得到的該表面被覆螢光體粒子之X射線繞射圖案中之2θ在23°以上且26°以下之範圍內的最大峰部A之發光強度為IA 、2θ在36°以上且39°以下之範圍內的最大峰部B之發光強度為IB 時的IA /IB 作為指標，藉此，可穩定地評價表面被覆螢光體粒子之表面層穩定化的程度，再者，藉由將IA /IB 設定在適當之數值範圍內，可達成高溫高濕環境下之發光強度特性優異之表面被覆螢光體粒子，從而完成本發明。Based on such knowledge and insights, the inventors conducted in-depth studies and found that by using IA/IB as an indicator, the degree of stabilization of the surface layer of the surface-coated fluorescent particles can be stably evaluated. Furthermore, by setting IA / IB within an appropriate numerical range, surface-coated fluorescent particles with excellent luminescence intensity characteristics in a high-temperature and high- humidity environment can be achieved, thereby completing the present invention.
依據本發明， 可提供一種表面被覆螢光體粒子，包含： 含螢光體之粒子、及 被覆該粒子表面之被覆部； 該螢光體具有通式M1 a M2 b M3 c Al3 N4-d Od 表示之組成，惟M1 係選自於由Sr、Mg、Ca及Ba中之1種以上之元素，M2 係選自於由Li、Na及K中之1種以上之元素，M3 係選自於由Eu、Ce及Mn中之1種以上之元素，該a、b、c、及d符合下列各式； 0.850≦a≦1.150 0.850≦b≦1.150 0.001≦c≦0.015 0≦d≦0.40 0≦d/(a+d)＜0.30 該被覆部構成該粒子之最表面之至少一部分且含有AlF3 ； 令使用Cu-Kα射線進行測定而得到的該表面被覆螢光體粒子之X射線繞射圖案中，2θ在23°以上且26°以下之範圍內的最大峰部A之發光強度為IA 、2θ在36°以上且39°以下之範圍內的最大峰部B之發光強度為IB 時， IA 、IB 符合IA /IB ≦0.10。According to the present invention, a surface-coated fluorescent particle can be provided , comprising : a particle containing a fluorescent body, and a coating portion covering the surface of the particle; the fluorescent body has a composition represented by the general formula M1aM2bM3cAl3N4 -dOd , but M1 is selected from one or more elements of Sr , Mg , Ca and Ba, M2 is selected from one or more elements of Li, Na and K, M3 is selected from one or more elements of Eu, Ce and Mn, and a, b, c, and d meet the following formulas; 0.850≦a≦1.150 0.850≦b≦1.150 0.001≦c≦0.015 0≦d≦0.40 0≦d/(a+d)＜0.30 The coating portion constitutes at least a portion of the outermost surface of the particle and contains AlF 3 ; When, in an X-ray diffraction pattern of the surface-coated fluorescent particle measured using Cu-Kα rays, the luminescence intensity of the maximum peak portion A in the range of 2θ being greater than 23° and less than 26° is IA , and the luminescence intensity of the maximum peak portion B in the range of 2θ being greater than 36° and less than 39° is IB , IA and IB satisfy IA / IB ≦0.10.
又，依據本發明，可提供一種發光裝置，具有上述表面被覆螢光體粒子、及發光元件。 [發明之效果]Furthermore, according to the present invention, a light-emitting device can be provided, which has the above-mentioned surface-coated fluorescent particles and a light-emitting element. [Effect of the invention]
依據本發明，可提供在高溫高濕環境下之發光強度特性優異的表面被覆螢光體粒子、以及使用其之發光裝置。According to the present invention, surface-coated fluorescent particles having excellent luminous intensity characteristics in a high-temperature and high-humidity environment and a luminescent device using the same can be provided.
針對本實施形態之表面被覆螢光體粒子進行說明。The surface-coated fluorescent particles of this embodiment are described.
本實施形態之表面被覆螢光體粒子係包含了含螢光體之粒子、及被覆粒子表面之被覆部之螢光體粒子。The surface-coated fluorescent particles of this embodiment include particles containing a fluorescent body and fluorescent particles having a coating portion that coats the surface of the particles.
表面被覆螢光體粒子含有之螢光體具有通式M1 a M2 b M3 c Al3 N4-d Od 表示之組成。通式中，M1 係選自於由Sr、Mg、Ca及Ba中之1種以上之元素，M2 係選自於由Li、Na及K中之1種以上之元素，M3 係選自於由Eu、Ce及Mn中之1種以上之元素。通式中，a、b、c、4-d、及d表示各元素之莫耳比。The phosphor contained in the surface - coated phosphor particles has a composition represented by the general formula M1aM2bM3cAl3N4 -dOd . In the general formula, M1 is one or more elements selected from Sr, Mg, Ca and Ba, M2 is one or more elements selected from Li, Na and K, and M3 is one or more elements selected from Eu, Ce and Mn. In the general formula, a, b, c, 4-d, and d represent the molar ratio of each element.
通式中之a、b、c、及d符合下列各式。 0.850≦a≦1.150 0.850≦b≦1.150 0.001≦c≦0.015 0≦d≦0.40 0≦d/(a+d)＜0.30In the general formula, a, b, c, and d meet the following formulas. 0.850≦a≦1.150 0.850≦b≦1.150 0.001≦c≦0.015 0≦d≦0.40 0≦d/(a+d)＜0.30
M1 係選自於由Sr、Mg、Ca及Ba中之1種以上之元素，宜至少包含Sr。M1 之莫耳比a之下限，為0.850以上較理想，0.950以上更理想。另一方面，M1 之莫耳比a之上限，為1.150以下較理想，1.100以下更理想，1.050以下還更理想。藉由設M1 之莫耳比a落在上述範圍內，可改善結晶結構穩定性。 M1 is one or more elements selected from Sr, Mg, Ca and Ba, preferably including at least Sr. The lower limit of the molar ratio a of M1 is preferably 0.850 or more, and more preferably 0.950 or more. On the other hand, the upper limit of the molar ratio a of M1 is preferably 1.150 or less, more preferably 1.100 or less, and even more preferably 1.050 or less. By setting the molar ratio a of M1 to fall within the above range, the stability of the crystal structure can be improved.
M2 係選自於由Li、Na及K中之1種以上之元素，宜至少包含Li。M2 之莫耳比b之下限，為0.850以上較理想，0.950以上更理想。另一方面，M2 之莫耳比b之上限，為1.150以下較理想，1.100以下更理想，1.050以下還更理想。藉由設M2 之莫耳比a落在上述範圍內，可改善結晶結構穩定性。 M2 is one or more elements selected from Li, Na and K, preferably including at least Li. The lower limit of the molar ratio b of M2 is preferably 0.850 or more, and more preferably 0.950 or more. On the other hand, the upper limit of the molar ratio b of M2 is preferably 1.150 or less, more preferably 1.100 or less, and even more preferably 1.050 or less. By setting the molar ratio a of M2 to fall within the above range, the stability of the crystal structure can be improved.
M3 係添加至母體結晶之活化劑，亦即係構成螢光體之發光中心離子之元素，且為選自於由Eu、Ce及Mn中之1種以上之元素。M3 可依據需求之發光波長而進行選擇，宜為至少包含Eu。 M3 之莫耳比c之下限，為0.001以上較理想，0.005以上更理想。另一方面，M3 之莫耳比c之上限，為0.015以下較理想，0.010以下更理想。藉由設M3 之莫耳比c之下限落在上述範圍內，可得到充分之發光強度。此外，藉由設M3 之莫耳比c之上限落在上述範圍內，可抑制濃度淬滅(concentration quenching)且使發光強度維持在足夠之值。 M3 is an activator added to the parent crystal, that is, an element constituting the luminescent center ion of the phosphor, and is one or more elements selected from Eu, Ce and Mn. M3 can be selected according to the required luminescent wavelength, and it is preferable to contain at least Eu. The lower limit of the molar ratio c of M3 is preferably above 0.001, and more preferably above 0.005. On the other hand, the upper limit of the molar ratio c of M3 is preferably below 0.015, and more preferably below 0.010. By setting the lower limit of the molar ratio c of M3 to fall within the above range, sufficient luminescence intensity can be obtained. In addition, by setting the upper limit of the molar ratio c of M3 to fall within the above range, concentration quenching can be suppressed and the luminescence intensity can be maintained at a sufficient value.
氧(O)之莫耳比d之下限，為0以上較理想，0.05以上更理想。另一方面，氧之莫耳比d之上限，為0.40以下較理想，0.35以下更理想。藉由設氧之莫耳比d落在上述範圍內，可穩定螢光體之結晶狀態且使發光強度維持在足夠之值。 此外，螢光體中之氧元素之含量，未達2質量%較理想，1.8質量%以下更理想。氧元素之含量，未達2質量%的話，可讓螢光體之結晶狀態穩定化，使發光強度維持在足夠之值。The lower limit of the molar ratio d of oxygen (O) is preferably 0 or more, and more preferably 0.05 or more. On the other hand, the upper limit of the molar ratio d of oxygen is preferably 0.40 or less, and more preferably 0.35 or less. By setting the molar ratio d of oxygen to fall within the above range, the crystal state of the phosphor can be stabilized and the luminescence intensity can be maintained at a sufficient value. In addition, the content of oxygen in the phosphor is preferably less than 2 mass%, and more preferably less than 1.8 mass%. If the content of oxygen is less than 2 mass%, the crystal state of the phosphor can be stabilized and the luminescence intensity can be maintained at a sufficient value.
M1 及氧之莫耳比，亦即，從a、d算出之d/(a+d)之值之下限，為0以上較理想，0.05以上更理想。另一方面，d/(a+d)之值之上限，未達0.30較理想，0.25以下更理想。藉由設d/(a+d)落在上述範圍內，可讓螢光體之結晶狀態穩定化且使發光強度維持在足夠之值。The molar ratio of M1 and oxygen, that is, the lower limit of the value of d/(a+d) calculated from a and d, is preferably 0 or more, and more preferably 0.05 or more. On the other hand, the upper limit of the value of d/(a+d) is preferably less than 0.30, and more preferably 0.25 or less. By setting d/(a+d) to fall within the above range, the crystal state of the phosphor can be stabilized and the luminescence intensity can be maintained at a sufficient value.
被覆部構成上述含螢光體粒子之最表面的至少一部分。該被覆部包含了含有氟元素及鋁元素之含氟化合物。The coating part constitutes at least a part of the outermost surface of the above-mentioned fluorescent particle. The coating part includes a fluorine-containing compound containing fluorine and aluminum.
含氟化合物中，氟元素和鋁元素直接共價鍵結較理想，更具體而言，含氟化合物含有AlF3 較理想。又，含氟化合物亦可由含有氟元素及鋁元素之單一種化合物構成。In the fluorine-containing compound, it is more ideal that the fluorine element and the aluminum element are directly covalently bonded. More specifically, it is more ideal that the fluorine-containing compound contains AlF 3. In addition, the fluorine-containing compound can also be composed of a single compound containing fluorine element and aluminum element.
藉由含有含氟化合物之被覆部構成含螢光體之粒子之最表面之至少一部分，可改善構成粒子之螢光體之耐濕性。又，考量更進一步改善螢光體之耐濕性之觀點，被覆部含有AlF3 較理想。By constituting at least a portion of the outermost surface of the particle containing the phosphor with a coating containing a fluorine compound, the moisture resistance of the phosphor constituting the particle can be improved. In addition, from the perspective of further improving the moisture resistance of the phosphor, it is more preferable that the coating contains AlF 3 .
被覆部之態樣無特別限制。就被覆部之態樣而言，可列舉例如：許多粒子狀之含氟化合物分佈在含螢光體之粒子之表面之態樣、或含氟化合物連續性地被覆於含螢光體之粒子之表面之態樣。被覆部也能以包覆粒子表面的一部分或包覆整體的方式構成。The form of the coating portion is not particularly limited. For example, the form of the coating portion includes a form in which a plurality of fluorine-containing compounds in the form of particles are distributed on the surface of the particles containing the fluorescent body, or a form in which the fluorine-containing compounds are continuously coated on the surface of the particles containing the fluorescent body. The coating portion can also be configured in a manner of coating a part of the particle surface or the entire particle surface.
針對表面被覆螢光體粒子，利用使用Cu-Kα射線之X射線繞射而得到X射線繞射圖案。令得到的X射線繞射圖案中，2θ在23°以上且26°以下之範圍內的最大峰部A之發光強度為IA 、2θ在36°以上且39°以下之範圍內的最大峰部B之發光強度為IB 。 此時，本實施形態之表面被覆螢光體粒子中，IA 、IB 符合IA /IB ≦0.10。 (X射線繞射圖案之測定方法) 針對表面被覆螢光體粒子，依據下述測定條件，使用X射線繞射裝置測定繞射圖案。 (測定條件) X射線光源：Cu-Kα射線(λ=1.54184Å)， 輸出設定：40kV･40mA 光學系：集中法 檢測器：半導體檢測器 測定時光學條件：發散光柵=2/3° 散射光柵=8mm 受光光柵=開放 繞射峰部之位置=2θ(繞射角) 測定範圍：2θ=20°~70° 掃描速度：2度(2θ)/sec，連續掃描 掃描軸：2θ/θ 試樣製備：將粉末狀之表面被覆螢光體粒子承載於樣品固定架。 峰部強度為進行了背景校正而得到的值。For the surface-coated fluorescent particles, an X-ray diffraction pattern is obtained by X-ray diffraction using Cu-Kα rays. In the obtained X-ray diffraction pattern, the luminescence intensity of the maximum peak A in the range of 2θ above 23° and below 26° is IA , and the luminescence intensity of the maximum peak B in the range of 2θ above 36° and below 39° is IB . At this time, in the surface-coated fluorescent particles of the present embodiment, IA and IB satisfy IA / IB ≦0.10. (Measurement method of X-ray diffraction pattern) For the surface-coated fluorescent particles, the diffraction pattern is measured using an X-ray diffraction device according to the following measurement conditions. (Measurement conditions) X-ray source: Cu-Kα ray (λ=1.54184Å), Output setting: 40kV･40mA Optical system: Concentration method Detector: Semiconductor detector Optical conditions for measurement: Divergence grating = 2/3° Scattering grating = 8mm Receiving grating = open Position of diffraction peak = 2θ (diversion angle) Measurement range: 2θ = 20°~70° Scanning speed: 2 degrees (2θ)/sec, continuous scanning Scanning axis: 2θ/θ Sample preparation: Powdered surface-coated fluorescent particles are placed on the sample holder. Peak intensity is the value obtained after background correction.
依據本案發明人之知識見解，發現藉由對於表面被覆螢光體粒子施予適當之加熱處理，能夠提升高溫高濕環境下之發光強度特性。 雖詳細之機制尚未確定，但據推測係螢光體粒子之表面層穩定化，即使在高溫高濕條件下仍可抑制發光特性的降低所致。According to the knowledge of the inventors of this case, it is found that by applying appropriate heat treatment to the surface-coated fluorescent particles, the luminescence intensity characteristics in a high temperature and high humidity environment can be improved. Although the detailed mechanism has not yet been determined, it is speculated that the surface layer of the fluorescent particles is stabilized, which can suppress the reduction of luminescence characteristics even under high temperature and high humidity conditions.
依據如此之知識見解而深入探討，結果發現，將令利用X射線繞射法得到的X射線繞射圖案中之2θ在23°以上且26°以下之範圍內的最大峰部A之發光強度為IA 、2θ在36°以上且39°以下之範圍內的最大峰部B之發光強度為IB 時的IA /IB 作為指標，藉此，可穩定地評價表面被覆螢光體粒子之表面層穩定化的程度，再者，藉由將IA /IB 設在適當之數值範圍內，可達成在高溫高濕環境下之發光強度特性優異之表面被覆螢光體粒子。Based on such knowledge and insights, we conducted in-depth studies and found that by using IA/ IB as an indicator, when the luminescence intensity of the maximum peak A in the range of 2θ above 23° and below 26° in the X-ray diffraction pattern obtained by the X-ray diffraction method is IA, and the luminescence intensity of the maximum peak B in the range of 2θ above 36° and below 39° is IB , the degree of stabilization of the surface layer of the surface-coated fluorescent particles can be stably evaluated. Furthermore, by setting IA/IB within an appropriate numerical range, surface-coated fluorescent particles with excellent luminescence intensity characteristics in a high temperature and high humidity environment can be achieved.
IA /IB 之上限，為0.10以下，為0.09以下較理想，0.08以下更理想，0.07以下還更理想。藉此，可改善高溫高濕環境下之發光強度特性。另一方面，IA /IB 之下限無特別限制。The upper limit of I A /I B is 0.10 or less, preferably 0.09 or less, more preferably 0.08 or less, and even more preferably 0.07 or less. This can improve the luminous intensity characteristics in a high temperature and high humidity environment. On the other hand, there is no particular restriction on the lower limit of I A /I B.
此處，發光強度IA 之最大峰部A包含來自SrAlF5 之峰部。發光強度IB 之最大峰部B包含來自SLAN之峰部。Here, the maximum peak A of the luminescence intensity IA includes the peak derived from SrAlF5 . The maximum peak B of the luminescence intensity IB includes the peak derived from SLAN.
本實施形態，例如藉由適當地選擇用於表面被覆螢光體粒子之原料成分之種類、摻合量、表面被覆螢光體粒子之製造方法等，從而可控制上述IA 、IA /IB 。它們之中，就使上述IA 、IA /IB 落在預期之數值範圍之要件而言，可列舉例如：在煅燒處理之後，進行酸處理及氫氟酸處理、以及使加熱處理之溫度落在適當之範圍內等。This embodiment can control the above-mentioned IA and IA / IB by, for example, appropriately selecting the type of raw material components used for the surface-coated fluorescent particles, the amount of blending, the method of manufacturing the surface-coated fluorescent particles, etc. Among them, the requirements for making the above-mentioned IA and IA / IB fall within the expected numerical range include, for example, performing acid treatment and hydrofluoric acid treatment after calcination treatment, and making the temperature of the heat treatment fall within an appropriate range.
以下，針對表面被覆螢光體粒子之特性進行說明。The following describes the characteristics of the surface-coated fluorescent particles.
表面被覆螢光體粒子中，對於波長300nm的光照射之漫反射率，例如，為56%以上，65%以上更理想，70%以上還更理想。 此外，表面被覆螢光體粒子中，對於螢光光譜之峰部波長的光照射之漫反射率，例如，為80%以上，83%以上較理想，85%以上更理想。 藉由具有如此之漫反射率，可更提高發光效率且更改善發光強度。The diffuse reflectance of the surface-coated fluorescent particles for light irradiation with a wavelength of 300 nm is, for example, 56% or more, more preferably 65% or more, and even more preferably 70% or more. In addition, the diffuse reflectance of the surface-coated fluorescent particles for light irradiation with a peak wavelength of the fluorescent spectrum is, for example, 80% or more, more preferably 83% or more, and even more preferably 85% or more. By having such a diffuse reflectance, the luminous efficiency can be further improved and the luminous intensity can be further improved.
以波長455nm之藍光進行激發時，表面被覆螢光體粒子亦可為如下之構成：峰部波長例如落在640nm以上且670nm以下之範圍內，且其半高寬例如落在45nm以上且60nm以下。藉由具有如此之特性，可期待有優異之演色性、色彩再現性。When excited by blue light with a wavelength of 455nm, the surface-coated fluorescent particles may also have the following structure: the peak wavelength falls within the range of, for example, 640nm to 670nm, and the half-height width falls within the range of, for example, 45nm to 60nm. With such characteristics, excellent color rendering and color reproduction can be expected.
以波長455nm之藍光進行激發時，表面被覆螢光體粒子亦可為如下之構成：CIE-xy色度圖中之x值例如符合0.680≦x＜0.735。 藉由具有如此之特性，可期待有優異之色彩再現性。x值為0.680以上的話，可更期待色純度良好之紅色發光，由於x值若為0.735以上之值，會超過CIE-xy色度圖內之最大值，故符合上述範圍較理想。When excited by blue light of wavelength 455nm, the surface-coated fluorescent particles can also be configured as follows: the x value in the CIE-xy chromaticity diagram meets, for example, 0.680≦x＜0.735. With such characteristics, excellent color reproduction can be expected. If the x value is above 0.680, red light with good color purity can be expected. Since the x value of 0.735 or above exceeds the maximum value in the CIE-xy chromaticity diagram, it is more ideal to meet the above range.
以下，針對本實施形態之表面被覆螢光體粒子之製造方法進行說明。The following describes a method for manufacturing the surface-coated fluorescent particles of this embodiment.
表面被覆螢光體粒子之製造方法，係製造一種螢光體粒子(表面被覆螢光體粒子)，其具有如下組成：包含選自於由Sr、Mg、Ca及Ba構成之群組中之至少1種之元素之M1 ；選自於由Li、Na及K構成之群組中之至少1種之元素M2 ；選自於由Eu、Ce及Mn構成之群組中之至少1種之元素M3 ；及由Al及N構成之群組。The method for producing surface-coated fluorescent particles is to produce fluorescent particles (surface-coated fluorescent particles) having the following composition: M1 containing at least one element selected from the group consisting of Sr, Mg, Ca and Ba; M2 containing at least one element selected from the group consisting of Li, Na and K; M3 containing at least one element selected from the group consisting of Eu, Ce and Mn; and a group consisting of Al and N.
表面被覆螢光體粒子之製造方法，可包含：混合步驟、煅燒步驟、粉碎步驟、酸處理步驟、氫氟酸處理步驟、及加熱處理步驟。 針對各步驟進行詳述。The method for manufacturing surface-coated fluorescent particles may include: a mixing step, a calcining step, a pulverizing step, an acid treatment step, a hydrofluoric acid treatment step, and a heat treatment step. Each step is described in detail.
(混合步驟) 混合步驟，係將為了可獲得作為目的之表面被覆螢光體粒子而稱量之各原料予以混合來得到粉末狀的原料混合物。(Mixing step) The mixing step is to mix the raw materials weighed to obtain the target surface-coated fluorescent particles to obtain a powdered raw material mixture.
將原料予以混合之方法無特別限制，例如使用研缽、球磨機、V型混合機、行星式輥軋機等混合裝置進行充分地混合之方法。 又，對於會和空氣中之水分或氧氣發生激烈反應之氮化鍶、氮化鋰等，係使用內部置換成鈍性氣體環境之手套箱內或混合裝置來操作較適當。There is no particular limitation on the method of mixing the raw materials, for example, a method of using a mortar, ball mill, V-type mixer, planetary roller or other mixing device to mix them thoroughly. In addition, for strontium nitride, lithium nitride, etc. that react violently with moisture or oxygen in the air, it is more appropriate to operate in a glove box or a mixing device whose interior is replaced with a passive gas environment.
混合步驟中，將Al之莫耳比設為3時之M1 之投入量，按莫耳比計為1.10以上較理想。藉由設定M1 之投入量按莫耳比計為1.10以上，可抑制在煅燒步驟中之M1 因揮發等導致螢光體中之M1 不足，而M1 不易發生缺陷，結晶性可維持良好。據推測其結果可得到窄帶域之螢光光譜並提高發光強度。此外，在混合步驟中，將Al之莫耳比設為3時之M1 之投入量，按莫耳比計為1.20以下較理想。藉由設定M1 之投入量按莫耳比計為1.20以下，可抑制含M1 之異相的增加，可輕易利用酸處理步驟去除異相並提高發光強度。In the mixing step, when the molar ratio of Al is set to 3, the amount of M1 added is preferably 1.10 or more in terms of molar ratio. By setting the amount of M1 added to 1.10 or more in terms of molar ratio, the lack of M1 in the phosphor due to volatility of M1 in the calcining step can be suppressed, and M1 is less likely to have defects, and the crystallinity can be maintained well. It is speculated that the result can obtain a narrowband fluorescence spectrum and improve the luminescence intensity. In addition, in the mixing step, when the molar ratio of Al is set to 3, the amount of M1 added is preferably 1.20 or less in terms of molar ratio. By setting the amount of M1 added to be less than 1.20 in terms of molar ratio, the increase of the heterogeneous phase containing M1 can be suppressed, the heterogeneous phase can be easily removed by the acid treatment step, and the luminescence intensity can be improved.
混合步驟中所使用之各原料，可包含選自於由螢光體之組成所含之金屬元素的金屬單體及含該金屬元素的金屬化合物構成之群組中之1種以上。就金屬化合物而言，可列舉例如：氮化物、氫化物、氟化物、氧化物、碳酸鹽、氯化物等。其中，考量可改善螢光體之發光強度之觀點，就含M1 及M2 之金屬化合物而言可適當地使用氮化物。具體而言，就含M1 之金屬化合物而言，可列舉如：Sr3 N2 、Sr2 N、SrN2 、SrN等。就含M2 之金屬化合物而言，可列舉如：Li3 N、LiN3 等。就含M3 之金屬化合物而言，可列舉如：Eu2 O3 、EuN、EuF3 。就含Al之金屬化合物而言，可列舉如：AlN、AlH3 、AlF3 、LiAlH4 等。The raw materials used in the mixing step may include one or more selected from the group consisting of metal monomers of metal elements contained in the composition of the phosphor and metal compounds containing the metal elements. As for the metal compounds, for example, nitrides, hydrides, fluorides, oxides, carbonates, chlorides, etc. can be listed. Among them, in view of improving the luminescence intensity of the phosphor, nitrides can be appropriately used for the metal compounds containing M1 and M2 . Specifically, as for the metal compounds containing M1 , for example, Sr3N2 , Sr2N , SrN2 , SrN, etc. can be listed. As for the metal compounds containing M2 , for example, Li3N , LiN3 , etc. can be listed. Examples of metal compounds containing M 3 include Eu 2 O 3 , EuN, and EuF 3 . Examples of metal compounds containing Al include AlN, AlH 3 , AlF 3 , and LiAlH 4 .
因應必要，亦可添加助熔劑。就助熔劑而言，可列舉如：LiF、SrF2 、BaF2 、AlF3 等。可單獨使用它們或將2種以上組合使用。If necessary, a flux may be added. Examples of the flux include LiF, SrF 2 , BaF 2 , and AlF 3. These may be used alone or in combination of two or more.
(煅燒步驟) 煅燒步驟，係將上述原料之混合物例如填充至煅燒容器之內部並煅燒。(Calcination step) The calcination step is to fill the above raw material mixture into a calcination container and calcine it.
煅燒容器具備可提高氣密性之結構較理想。煅燒容器由在高溫之環境氣體下仍穩定，不易和原料之混合體及其反應產物進行反應之材質所構成較理想，例如，使用氮化硼製、碳製之容器、鉬或鉭或鎢等高熔點金屬製之容器較理想。The calcining container is preferably of a structure that can improve airtightness. The calcining container is preferably made of a material that is stable in a high temperature environment and is not easy to react with the mixture of raw materials and their reaction products. For example, a container made of boron nitride, carbon, or a container made of a high melting point metal such as molybdenum, tungsten, or the like is preferably used.
煅燒容器之內部充滿氬氣、氦氣、氫氣、氮氣等非氧化性氣體之環境氣體較理想。It is ideal that the interior of the calcining container is filled with non-oxidizing gases such as argon, helium, hydrogen, and nitrogen.
[煅燒溫度] 煅燒步驟中之煅燒溫度之下限為900℃以上較理想，1000℃以上更理想，1100℃以上還更理想。另一方面，煅燒溫度之上限為1500℃以下較理想，1400℃以下更理想，1300℃以下還更理想。藉由將煅燒溫度設在上述範圍內，可減少煅燒步驟結束後之未反應原料，並可抑制主結晶相的分解。[Calcination temperature] The lower limit of the calcination temperature in the calcination step is preferably 900°C or higher, more preferably 1000°C or higher, and even more preferably 1100°C or higher. On the other hand, the upper limit of the calcination temperature is preferably 1500°C or lower, more preferably 1400°C or lower, and even more preferably 1300°C or lower. By setting the calcination temperature within the above range, the unreacted raw materials after the calcination step can be reduced, and the decomposition of the main crystal phase can be suppressed.
[煅燒環境氣體之種類] 就煅燒步驟中之煅燒環境氣體之種類而言，例如，可適當地使用包含氮元素之氣體。具體而言，可列舉如：氮氣及/或氨氣，尤其氮氣較理想。此外，同樣地也可適當地使用氬氣、氦氣等鈍性氣體。又，煅燒環境氣體可由1種之氣體構成，亦可為多種之氣體之混合氣體。[Type of calcining environment gas] As for the type of calcining environment gas in the calcining step, for example, a gas containing nitrogen element can be appropriately used. Specifically, nitrogen gas and/or ammonia gas can be listed, and nitrogen gas is particularly preferred. In addition, inert gases such as argon gas and helium gas can also be appropriately used. In addition, the calcining environment gas can be composed of one gas or a mixed gas of multiple gases.
[煅燒環境氣體之壓力] 煅燒環境氣體之壓力可因應煅燒溫度而選擇，通常為0.1MPa･G以上且10MPa･G以下之範圍之加壓狀態。煅燒環境氣體之壓力越高，螢光體之分解溫度越高，但考量工業生產性，為0.5MPa･G以上且1MPa･G以下較理想。[Pressure of calcining environment gas] The pressure of calcining environment gas can be selected according to the calcining temperature, and is usually in the range of 0.1MPa･G or more and 10MPa･G or less. The higher the pressure of calcining environment gas, the higher the decomposition temperature of the fluorescent body, but considering industrial productivity, it is ideal to be 0.5MPa･G or more and 1MPa･G or less.
[煅燒時間] 煅燒步驟中之煅燒時間，係選擇在不會發生存在大量未反應物、或不會發生螢光體之粒子成長不足、或不會發生生產性降低等問題之時間範圍內。煅燒時間之下限，為0.5小時以上較理想，1小時以上更理想，2小時以上還更理想。此外，煅燒時間之上限為48小時以下較理想，36小時以下更理想，24小時以下還更理想。[Calcination time] The calcination time in the calcination step is selected within a time range that does not cause problems such as the presence of a large amount of unreacted products, insufficient growth of fluorescent particles, or reduced productivity. The lower limit of the calcination time is preferably 0.5 hours or more, more preferably 1 hour or more, and even more preferably 2 hours or more. In addition, the upper limit of the calcination time is preferably 48 hours or less, more preferably 36 hours or less, and even more preferably 24 hours or less.
(粉碎步驟) 粉碎步驟，係將煅燒步驟後之原料混合物(煅燒物)予以粉碎而得到粉碎物。(Crushing step) The crushing step is to crush the raw material mixture (calcined product) after the calcining step to obtain a crushed product.
藉由煅燒步驟而得到的煅燒物之狀態，會依據原料摻合、煅燒條件而為粉狀、塊狀等各種狀態。藉由分解-粉碎步驟及/或分級操作步驟，可將煅燒物製成預定尺寸之粉末狀。The state of the calcined product obtained by the calcination step may be in various states such as powder or block, depending on the raw material blending and calcination conditions. The calcined product may be made into a powder of a predetermined size by the decomposition-crushing step and/or the classification operation step.
上述之分解-粉碎步驟為了防止有來自該處理的雜質混入，與煅燒物接觸之機器之構件為由氮化矽、氧化鋁、矽鋁氮氧化物(SiAlON)等構成較理想。In order to prevent the impurities from the treatment from being mixed in during the above decomposition-crushing step, it is preferable that the machine components that come into contact with the calcined product are made of silicon nitride, aluminum oxide, silicon aluminum nitride oxide (SiAlON), etc.
又，粉碎物之平均粒徑亦能以表面被覆螢光體粒子之平均粒徑成為5μm以上且30μm以下之方式進行調整。藉此，表面被覆螢光體粒子會具有優異的激發光之吸收效率及發光效率，可適用於LED用途等。Furthermore, the average particle size of the pulverized product can be adjusted so that the average particle size of the surface-coated fluorescent particles is 5 μm or more and 30 μm or less. Thus, the surface-coated fluorescent particles have excellent absorption efficiency and luminescence efficiency of the excitation light and can be applied to LED applications.
(酸處理步驟) 酸處理步驟，係對於粉碎物使用含酸溶液進行酸處理。(Acid treatment step) The acid treatment step is to treat the crushed material with an acid solution.
含酸溶液，可使用含有酸和溶劑之混合液，為酸和有機溶劑之混合液較理想，酸和有機溶劑之混合水溶液更理想。The acid-containing solution may be a mixed solution containing an acid and a solvent, preferably a mixed solution containing an acid and an organic solvent, and more preferably a mixed aqueous solution containing an acid and an organic solvent.
酸，例如亦可使用無機酸，具體而言，可列舉如：硝酸、鹽酸、乙酸、硫酸、甲酸、及磷酸等。該等可單獨使用或將2種以上組合使用。Acids, for example, inorganic acids can also be used, and specifically, nitric acid, hydrochloric acid, acetic acid, sulfuric acid, formic acid, phosphoric acid, etc. These can be used alone or in combination of two or more.
溶劑可使用水溶劑、有機溶劑。As the solvent, an aqueous solvent or an organic solvent can be used.
有機溶劑，可列舉例如：醇、丙酮等。其中，為醇較理想。就醇而言，例如可使用甲醇、乙醇、2-丙醇等。Examples of organic solvents include alcohols and acetone. Among them, alcohols are preferred. As alcohols, for example, methanol, ethanol, 2-propanol, etc. can be used.
混合液中之有機溶劑之混合比率，例如亦能夠以相對於含有酸和溶劑之混合液100體積%，酸為0.1體積%以上且3體積%以下之方式製備。The mixing ratio of the organic solvent in the mixed solution can be prepared, for example, in such a manner that the acid is greater than or equal to 0.1 volume % and less than or equal to 3 volume % relative to 100 volume % of the mixed solution containing the acid and the solvent.
藉由酸處理，可溶解去除原料所含之雜質元素、來自煅燒容器之雜質元素、煅燒步驟產生的異相、於粉碎步驟中混入之雜質元素。由於同時也可去除微粉，故可抑制光的散射，且還改善螢光體之光吸收率。亦即，酸處理可洗淨異物等。The acid treatment can dissolve and remove impurity elements contained in the raw materials, impurity elements from the calcination container, heterogeneous phases generated in the calcination step, and impurity elements mixed in the pulverization step. Since fine powder can also be removed at the same time, light scattering can be suppressed and the light absorption rate of the fluorescent body can be improved. In other words, the acid treatment can clean foreign matter, etc.
就酸處理之一例而言，使用酸進行洗淨後，亦可使用有機溶劑進行洗淨，也可使用含有酸和有機溶劑之混合液進行洗淨。此外，亦可使粉碎物分散、浸漬在含有酸之溶液中例如約0.5小時~5小時。As an example of acid treatment, after washing with acid, washing with an organic solvent or a mixed solution containing acid and organic solvent can be used for washing. In addition, the pulverized material can be dispersed and immersed in a solution containing acid for about 0.5 hours to 5 hours.
(氫氟酸處理步驟) 氫氟酸處理，係對於酸處理步驟後之粉碎物施予氫氟酸處理。(Hydrofluoric acid treatment step) Hydrofluoric acid treatment is to treat the crushed material after the acid treatment step with hydrofluoric acid.
氫氟酸處理，就含氟元素之化合物而言，可適當地使用氫氟酸水溶液。 氫氟酸水溶液之濃度之下限，為20質量%以上較理想，25質量%以上更理想，30質量%以上還更理想。另一方面，氫氟酸水溶液之濃度之上限，為40%質量以下較理想，38質量%以下更理想，35質量%以下還更理想。 藉由令氫氟酸水溶液之濃度為上述下限值以上，可在含螢光體之粒子之最表面的至少一部分形成有含(NH4 )3 AlF6 之被覆部。另一方面，令氫氟酸水溶液之濃度為上述上限值以下，可抑制粒子和氫氟酸的反應過於激烈。For the hydrofluoric acid treatment, a hydrofluoric acid aqueous solution can be appropriately used for compounds containing fluorine elements. The lower limit of the concentration of the hydrofluoric acid aqueous solution is preferably 20 mass % or more, more preferably 25 mass % or more, and even more preferably 30 mass % or more. On the other hand, the upper limit of the concentration of the hydrofluoric acid aqueous solution is preferably 40 mass % or less, more preferably 38 mass % or less, and even more preferably 35 mass % or less. By making the concentration of the hydrofluoric acid aqueous solution above the lower limit, a coating containing (NH 4 ) 3 AlF 6 can be formed on at least a portion of the outermost surface of the particles containing the fluorescent body. On the other hand, by making the concentration of the hydrofluoric acid aqueous solution below the upper limit, the reaction between the particles and the hydrofluoric acid can be suppressed from being too intense.
粉碎物與氫氟酸水溶液的混合，可利用攪拌器等攪拌手段進行。 上述粉碎物與氫氟酸水溶液之混合時間之下限，為5分鐘以上較理想，10分鐘以上更理想，15分鐘以上更理想。另一方面，上述煅燒物與氫氟酸水溶液之混合時間之上限，為30分鐘以下較理想，25分鐘以下更理想，20分鐘以下還更理想。 藉由將上述粉碎物與氫氟酸水溶液之混合時間設在上述範圍，可穩定地在含螢光體之粒子之最表面的至少一部份形成有含(NH4 )3 AlF6 之被覆部。The mixing of the pulverized product and the aqueous hydrofluoric acid solution can be carried out by using a stirring means such as a stirrer. The lower limit of the mixing time of the pulverized product and the aqueous hydrofluoric acid solution is preferably 5 minutes or more, more preferably 10 minutes or more, and more preferably 15 minutes or more. On the other hand, the upper limit of the mixing time of the calcined product and the aqueous hydrofluoric acid solution is preferably 30 minutes or less, more preferably 25 minutes or less, and even more preferably 20 minutes or less. By setting the mixing time of the pulverized product and the aqueous hydrofluoric acid solution within the above range, a coating containing (NH 4 ) 3 AlF 6 can be stably formed on at least a portion of the outermost surface of the particles containing the fluorescent body.
本實施形態中，藉由適當地調整酸處理步驟中之酸及溶劑之種類、酸之濃度、氫氟酸處理步驟中之氫氟酸之濃度、氫氟酸處理之時間、氫氟酸處理後所進行之加熱處理步驟中之加熱溫度及加熱時間等，可形成被覆含螢光體之粒子之表面之被覆部。In this embodiment, by appropriately adjusting the types of acid and solvent in the acid treatment step, the acid concentration, the concentration of hydrofluoric acid in the hydrofluoric acid treatment step, the time of the hydrofluoric acid treatment, the heating temperature and heating time in the heat treatment step performed after the hydrofluoric acid treatment, etc., a coating portion that covers the surface of the fluorescent-containing particles can be formed.
(加熱處理步驟) 加熱處理，係將氫氟酸處理後之粉碎物在大氣中進行加熱。(Heat treatment step) The heat treatment is to heat the crushed material after the hydrofluoric acid treatment in the atmosphere.
經氫氟酸處理而得到的產物含有(NH4 )3 AlF6 作為被覆部時，藉由實施加熱處理步驟，能夠將(NH4 )3 AlF6 之一部分或全部變更為AlF3 。When the product obtained by the hydrofluoric acid treatment contains (NH 4 ) 3 AlF 6 as a coating part, a part or all of the (NH 4 ) 3 AlF 6 can be converted into AlF 3 by performing a heat treatment step.
加熱處理步驟中之加熱溫度之下限，為220℃以上較理想，250℃以上更理想。另一方面，上述加熱溫度之上限，為380℃以下較理想，350℃以下更理想，330℃以下還更理想。The lower limit of the heating temperature in the heat treatment step is preferably 220° C. or higher, more preferably 250° C. or higher. On the other hand, the upper limit of the heating temperature is preferably 380° C. or lower, more preferably 350° C. or lower, and even more preferably 330° C. or lower.
藉由令加熱溫度為上述下限以上，可藉由進行下述反應式(1)而使(NH4 )3 AlF6 變換為AlF3 。 (NH4 )3 AlF6 →AlF3 +3NH3 +3HF･･･(1)By setting the heating temperature to be higher than the above lower limit, (NH 4 ) 3 AlF 6 can be converted to AlF 3 by proceeding with the following reaction formula (1). (NH 4 ) 3 AlF 6 →AlF 3 +3NH 3 +3HF･･･(1)
另一方面，藉由令加熱溫度為上述上限以下，可良好地維持螢光體之結晶結構並提高發光強度。On the other hand, by setting the heating temperature to be below the above upper limit, the crystal structure of the phosphor can be well maintained and the luminescence intensity can be increased.
加熱時間之下限，為1小時以上較理想，1.5小時以上更理想，2小時以上還更理想。另一方面，加熱時間之上限，為6小時以下較理想，5.5小時以下更理想，5小時以下還更理想。藉由將加熱時間設在上述範圍內，可確實地使(NH4 )3 AlF6 變換為耐濕性更高之AlF3 。The lower limit of the heating time is preferably 1 hour or more, more preferably 1.5 hours or more, and even more preferably 2 hours or more. On the other hand, the upper limit of the heating time is preferably 6 hours or less, more preferably 5.5 hours or less, and even more preferably 5 hours or less. By setting the heating time within the above range, (NH 4 ) 3 AlF 6 can be reliably converted into AlF 3 with higher moisture resistance.
又，加熱處理步驟宜在大氣中或氮氣環境下實施。藉此，加熱環境之物質本身可不妨礙上述反應式(1)而產生目的之物質。Furthermore, the heat treatment step is preferably carried out in the atmosphere or in a nitrogen environment. Thus, the substances in the heating environment themselves can produce the target substance without hindering the above reaction formula (1).
以下，針對本實施形態之發光裝置進行說明。 本實施形態之發光裝置，具有表面被覆螢光體粒子及發光元件。The following is a description of the light-emitting device of this embodiment. The light-emitting device of this embodiment has surface-coated fluorescent particles and a light-emitting element.
就發光元件而言，可使用紫外LED、藍色LED、螢光燈之單體或將它們組合使用。發光元件，期望為可發出250nm以上且550nm以下波長之光，其中，為420nm以上且500nm以下之藍色LED發光元件較理想。As for the light-emitting element, a single ultraviolet LED, a blue LED, or a fluorescent lamp can be used or a combination thereof. The light-emitting element is expected to be able to emit light with a wavelength of more than 250nm and less than 550nm, among which a blue LED light-emitting element with a wavelength of more than 420nm and less than 500nm is more ideal.
就螢光體粒子而言，除了表面被覆螢光體粒子以外，還可併用擁有其它發光色之螢光體粒子。 就其它發光色之螢光體粒子而言，有藍色發光螢光體粒子、綠色發光螢光體粒子、黃色發光螢光體粒子、橙色發光螢光體粒子、紅色螢光體，可列舉例如Ca3 Sc2 Si3 O12 ：Ce、CaSc2 O4 ：Ce、β-SiAlON：Eu、Y3 Al5 O12 ：Ce、Tb3 Al5 O12 ：Ce、(Sr、Ca、Ba)2 SiO4 ：Eu、La3 Si6 N11 ：Ce、α-SiAlON：Eu、Sr2 Si5 N8 ：Eu等。As for the fluorescent particles, in addition to the surface-coated fluorescent particles, fluorescent particles having other luminescent colors can also be used in combination. As for fluorescent particles of other luminescent colors, there are blue luminescent fluorescent particles, green luminescent fluorescent particles, yellow luminescent fluorescent particles, orange luminescent fluorescent particles, and red fluorescent particles, for example, Ca3Sc2Si3O12 :Ce, CaSc2O4 : Ce, β - SiAlON : Eu , Y3Al5O12 : Ce, Tb3Al5O12 :Ce, (Sr,Ca,Ba) 2SiO4 : Eu , La3Si6N11 : Ce, α - SiAlON : Eu, Sr2Si5N8 : Eu , etc.
其它之螢光體粒子無特別限制，可因應發光裝置所要求的亮度或演色性等而適當地進行選擇。藉由使表面被覆螢光體粒子和其它發光色之螢光體粒子混合存在，可達成如日光白或燈泡色等各種色溫之白色。The other fluorescent particles are not particularly limited and can be appropriately selected according to the brightness or color rendering required by the light-emitting device. By mixing the surface-coated fluorescent particles with fluorescent particles of other luminescent colors, white of various color temperatures such as daylight white or bulb color can be achieved.
就發光裝置之具體例而言，可列舉例如：照明裝置、背光裝置、圖像顯示裝置及信號裝置。Specific examples of light-emitting devices include lighting devices, backlight devices, image display devices, and signal devices.
發光裝置，藉由具備表面被覆螢光體粒子，可達成高發光強度且同時可提高可靠性。A light-emitting device can achieve high light-emitting intensity and improve reliability by having a surface coated with fluorescent particles.
以上，就本發明的實施形態進行描述，但這些僅為本發明的範例，可採用上述以外的各種構成。此外，本發明未受限於上述實施形態，在可達成本發明之目的之範圍內的變化、改良等亦包含在本發明中。 [實施例]The above describes the embodiments of the present invention, but these are only examples of the present invention, and various structures other than the above can be adopted. In addition, the present invention is not limited to the above embodiments, and changes and improvements within the scope of achieving the purpose of the present invention are also included in the present invention. [Embodiment]
下列，參照實施例詳細地說明本發明，但本發明並不受限於該等實施例之記載。The present invention is described in detail below with reference to embodiments, but the present invention is not limited to the description of these embodiments.
＜螢光體粒子之製作＞ (比較例1) [混合步驟] 在大氣中，將AlN(德山股份有限公司製)、Eu2 O3 (信越化學工業股份有限公司製)及LiF(富士軟片和光純藥股份有限公司製)進行稱量、混合後，利用網目150μm之尼龍篩將凝集分解破碎，得到預混合物。 將預混合物移動到維持在水分1ppm以下、氧氣1ppm以下之鈍性環境氣體之手套箱中。之後，以化學計量比(a=1、b=1)中a值超過15%且b值超過20%之方式將Sr3 N2(Taiheiyo Cement Corporation 製)及Li3 N(Materion股份有限公司製)稱量後，追加摻合並混合後，再以網目150μm之尼龍篩將凝集分解破碎而得到螢光體之原料混合物。由於Sr及Li在煅燒中容易分散，故摻合了比理論值還多的量。 此處，Al之莫耳比設為3時，Sr之投入量按莫耳比計為1.15，且Eu之投入量按莫耳比計為0.01。相對於前述原料混合物及助熔劑之合計量100質量%，添加了5質量%之LiF。又，Eu如前述，Al之莫耳比設為3時之投入量，按莫耳比計為0.01。<Production of fluorescent particles> (Comparative Example 1) [Mixing step] AlN (manufactured by Tokuyama Co., Ltd.), Eu 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd.) and LiF (manufactured by Fuji Film Wako Pure Chemical Co., Ltd.) were weighed and mixed in the atmosphere, and then the aggregates were decomposed and crushed using a nylon sieve with a mesh size of 150 μm to obtain a pre-mixture. The pre-mixture was moved to a glove box with a passive ambient gas maintained at a moisture content of less than 1 ppm and an oxygen content of less than 1 ppm. After that, Sr 3 N2 (manufactured by Taiheiyo Cement Corporation) and Li 3 N (manufactured by Materion Co., Ltd.) were weighed in a chemical stoichiometric ratio (a=1, b=1) such that the a value exceeded 15% and the b value exceeded 20%, and then the raw material mixture of the phosphor was obtained by additional blending and mixing, and then the agglomerates were decomposed and crushed with a nylon sieve with a mesh size of 150μm. Since Sr and Li are easily dispersed during calcination, more than the theoretical value was blended. Here, when the molar ratio of Al was set to 3, the input amount of Sr was 1.15 in terms of molar ratio, and the input amount of Eu was 0.01 in terms of molar ratio. 5% by mass of LiF was added to the total amount of the raw material mixture and flux, which was 100% by mass. In addition, Eu is as mentioned above, and the input amount when the molar ratio of Al is set to 3 is 0.01 in terms of molar ratio.
[煅燒步驟] 然後，將原料混合物填充至附蓋之圓筒型BN製容器(電化股份有限公司製)。 然後，將填充了螢光體之原料混合物之容器從手套箱中取出後，放入附設具備有石墨隔熱材之碳加熱器之電氣爐(富士電波工業股份有限公司製)，實施煅燒步驟。 在煅燒步驟開始時，先暫時將電氣爐內進行脫氣至真空狀態後，從室溫於0.8MPa･G之加壓氮氣環境下開始進行煅燒。電氣爐內之溫度到達1100℃後，維持溫度8小時並持續進行煅燒，之後冷卻至室溫。[Calcination step] Then, the raw material mixture is filled into a cylindrical BN container with a lid (manufactured by Denka Co., Ltd.). Then, the container filled with the raw material mixture of the fluorescent body is taken out of the glove box and placed in an electric furnace equipped with a carbon heater with a graphite insulation material (manufactured by Fuji Electric Industries, Ltd.) to carry out the calcination step. At the beginning of the calcination step, the electric furnace is temporarily degassed to a vacuum state, and then calcination is started at room temperature in a pressurized nitrogen environment of 0.8MPa･G. After the temperature in the electric furnace reaches 1100℃, the temperature is maintained for 8 hours and calcination is continued, and then cooled to room temperature.
[粉碎步驟] 將得到的煅燒物利用研缽進行粉碎後，以網目75μm之尼龍篩進行分級並回收。[Crushing step] The calcined product was crushed with a mortar, and then graded and recovered with a nylon sieve with a mesh size of 75 μm.
[酸處理步驟] 對於MeOH(99%)(國產化學股份有限公司製)添加了HNO3 (60%)(和光純藥股份有限公司製)之混合溶液中加入得到的煅燒物之粉體並攪拌3小時後，進行分級而得到螢光體粉末。[Acid treatment step] The obtained calcined product powder was added to a mixed solution of MeOH (99%) (manufactured by Kokusan Chemical Co., Ltd.) and HNO 3 (60%) (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred for 3 hours and then classified to obtain a fluorescent powder.
[氫氟酸處理步驟] 藉由將得到的螢光體粉末添加至30%氫氟酸水溶液中並攪拌15分鐘而實施氫氟酸處理步驟。氫氟酸處理步驟之後，使其全部通過網目45μm之篩而分解凝集團塊，得到比較例1之螢光體粒子。[Hydrofluoric acid treatment step] The obtained fluorescent powder was added to a 30% hydrofluoric acid aqueous solution and stirred for 15 minutes to perform the hydrofluoric acid treatment step. After the hydrofluoric acid treatment step, the powder was passed through a sieve with a mesh size of 45 μm to decompose the aggregates, thereby obtaining the fluorescent particles of Comparative Example 1.
(比較例2) 對於藉由施予氫氟酸處理後並使其全部通過網目45μm之篩來將凝集團塊分解而得之螢光體粉末，在大氣環境下實施200℃、4小時之加熱處理，除此之外，經與比較例1同樣之原料投入量及程序而得到比較例2之螢光體粒子。(Comparative Example 2) The fluorescent powder obtained by decomposing the agglomerated lumps by treating with hydrofluoric acid and passing through a sieve with a mesh size of 45 μm was subjected to a heat treatment at 200°C for 4 hours in an atmospheric environment. The same raw material input amount and procedure as in Comparative Example 1 were used to obtain the fluorescent particles of Comparative Example 2.
(實施例1) 對於藉由施予氫氟酸處理後並使其全部通過網目45μm之篩來將凝集團塊分解而得之螢光體粉末，在大氣環境下實施250℃、4小時之加熱處理，除此之外，經與比較例1同樣的原料之投入量及程序而得到實施例1之螢光體粒子。(Example 1) The fluorescent powder obtained by decomposing the agglomerated lumps by treating with hydrofluoric acid and passing through a sieve with a mesh size of 45 μm was subjected to a heat treatment at 250°C for 4 hours in an atmospheric environment. In addition, the same amount of raw materials and procedures as those in Comparative Example 1 were used to obtain the fluorescent particles of Example 1.
(實施例2) 對於藉由施予氫氟酸處理後並使其全部通過網目45μm之篩來將凝集團塊分解而得之螢光體粉末，在大氣環境下實施300℃、4小時之加熱處理，除此之外，經與比較例1同樣的原料之投入量及程序而得到實施例2之螢光體粒子。(Example 2) The fluorescent powder obtained by decomposing the agglomerated lumps by treating with hydrofluoric acid and passing through a sieve with a mesh size of 45 μm was subjected to a heat treatment at 300°C for 4 hours in an atmospheric environment. In addition, the same amount of raw materials and procedures as those of Comparative Example 1 were used to obtain the fluorescent particles of Example 2.
(比較例3) 對於藉由施予氫氟酸處理後並使其全部通過網目45μm之篩來將凝集團塊分解而得之螢光體粉末，在大氣環境下實施400℃、4小時之加熱處理，除此之外，經與比較例1同樣的原料之投入量及程序而得到比較例3之螢光體粒子。(Comparative Example 3) The fluorescent powder obtained by decomposing the agglomerated lumps by treating with hydrofluoric acid and passing through a sieve with a mesh size of 45 μm was subjected to a heat treatment at 400°C for 4 hours in an atmospheric environment. The same amount of raw materials and procedures as those of Comparative Example 1 were used to obtain the fluorescent particles of Comparative Example 3.
針對實施例1、2、比較例1~3得到的螢光體粒子，藉由使用了Cu-Kα射線之粉末X射線繞射測定(XRD測定)而調查結晶相，確認係具有結晶相皆為Sra Lib Euc Al3 N4-d Od 表示之組成之螢光體。The fluorescent particles obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were examined for crystalline phases by powder X-ray diffraction measurement (XRD measurement) using Cu-Kα radiation, and it was confirmed that the crystalline phases of the fluorescent particles were all composed of SraLibEucAl3N4 -dOd .
針對得到的螢光體粒子，求出將全結晶相合計之化學組成(亦即，Sra Lib Euc Al3 N4-d Od )之各元素之下標a~d。具體而言，針對Sr、Li、Al及Eu係使用利用ICP發光分光分析裝置(SPECTRO股份有限公司製，CIROS-120)而得的分析結果，針對O及N係使用利用氧氮分析計(堀場製作所股份有限公司製，EMGA-920)而得之分析結果，並算出下標a~d。 各螢光體粒子之a~d之數值如表1所示。For the obtained fluorescent particles, the subscripts a to d of each element in the chemical composition of the entire crystalline phase (i.e., Sr a Li b Eu c Al 3 N 4-d O d ) were calculated. Specifically, for Sr, Li, Al and Eu, the analysis results obtained using an ICP emission spectrometer (CIROS-120 manufactured by SPECTRO Co., Ltd.), and for O and N, the analysis results obtained using an oxygen and nitrogen analyzer (EMGA-920 manufactured by Horiba, Ltd.) were used to calculate the subscripts a to d. The values of a to d for each fluorescent particle are shown in Table 1.
(利用X射線繞射法進行分析) 針對得到的螢光體粒子，使用X射線繞射裝置(Rigaku Corporation製UltimaIV)且使用Cu-Kα射線，並依據下述測定條件進行X射線繞射圖案測定。此外，由得到的X射線繞射圖案確認螢光體粒子之結晶結構。 (測定條件) X射線光源：Cu-Kα射線(λ=1.54184Å)， 輸出設定：40kV･40mA 光學系：集中法 檢測器：半導體檢測器 測定時光學條件：發散光柵=2/3° 散射光柵=8mm 受光光柵=開放 繞射峰部之位置=2θ(繞射角) 測定範圍：2θ=20°~70° 掃描速度：2度(2θ)/sec，連續掃描 掃描軸：2θ/θ 試樣製備：將粉末狀之螢光體粒子承載於樣品固定架。 峰部強度係進行了背景校正而得到的值。(Analysis by X-ray diffraction) For the obtained fluorescent particles, an X-ray diffraction device (Ultima IV manufactured by Rigaku Corporation) was used to measure the X-ray diffraction pattern using Cu-Kα radiation under the following measurement conditions. In addition, the crystal structure of the fluorescent particles was confirmed from the obtained X-ray diffraction pattern. (Measurement conditions) X-ray source: Cu-Kα ray (λ=1.54184Å), Output setting: 40kV･40mA Optical system: Concentration method Detector: Semiconductor detector Optical conditions during measurement: Divergence grating = 2/3° Scattering grating = 8mm Receiving grating = open Position of diffraction peak = 2θ (diversion angle) Measurement range: 2θ = 20°~70° Scanning speed: 2 degrees (2θ)/sec, continuous scanning Scanning axis: 2θ/θ Sample preparation: Powdered fluorescent particles are placed on the sample holder. The peak intensity is the value obtained after background correction.
實施例1、2、及比較例3中，2θ在24.5°以上且25.5°以下之範圍確認到對應SrAlF5 之峰部(最大峰部A)。比較例1、2中，未確認到對應SrAlF5 之峰部。 實施例1、2、及比較例1~3中，2θ在36.5°以上且37.5°以下之範圍確認到對應SLAN之峰部(最大峰部B)。 算出令最大峰部A之發光強度為IA 、最大峰部B之發光強度為IB 時之IA /IB 。結果如表1所示。In Examples 1, 2, and Comparative Example 3, a peak corresponding to SrAlF 5 (maximum peak A) was confirmed in the range of 2θ from 24.5° to 25.5°. In Comparative Examples 1 and 2, no peak corresponding to SrAlF 5 was confirmed. In Examples 1, 2, and Comparative Examples 1 to 3, a peak corresponding to SLAN (maximum peak B) was confirmed in the range of 2θ from 36.5° to 37.5°. IA / IB was calculated when the luminescence intensity of the maximum peak A was IA and the luminescence intensity of the maximum peak B was IB . The results are shown in Table 1.
此外，針對實施例1、2、及比較例3，2θ在14°以上且15°以下之範圍內確認到對應AlF3 之峰部。針對比較例1，2θ在16.5°以上且17.5°以下之範圍內確認到對應(NH4 )3 AlF6 之峰部。比較例1則觀察到對應(NH4 )3 AlF6 之小峰部。In addition, for Examples 1, 2, and Comparative Example 3, a peak corresponding to AlF 3 was observed in the range of 2θ from 14° to 15°. For Comparative Example 1, a peak corresponding to (NH 4 ) 3 AlF 6 was observed in the range of 2θ from 16.5° to 17.5°. In Comparative Example 1, a small peak corresponding to (NH 4 ) 3 AlF 6 was observed .
(利用XPS進行表面分析) 針對得到的螢光體粒子，實施利用XPS所為之表面分析。 針對實施例1、2、及比較例1，可確認螢光體粒子之最表面中存在有Al及F，且Al和F共價鍵結。(Surface analysis using XPS) The obtained fluorescent particles were subjected to surface analysis using XPS. For Examples 1 and 2, and Comparative Example 1, it was confirmed that Al and F existed on the outermost surface of the fluorescent particles, and that Al and F were covalently bonded.
藉由利用XPS所為之表面分析結果及利用上述X射線繞射法所為之分析，顯示了下述內容。 實施例1及實施例2，係螢光體粒子之最表面之至少一部分由AlF3 構成之表面被覆螢光體粒子。 比較例1之螢光體粒子，則係螢光體粒子之最表面之至少一部分由(NH4 )3 AlF6 構成之表面被覆螢光體粒子。The surface analysis results by XPS and the analysis by the above-mentioned X-ray diffraction method show the following contents. Examples 1 and 2 are surface-coated fluorescent particles in which at least a portion of the outermost surface of the fluorescent particles is composed of AlF 3. The fluorescent particles of Comparative Example 1 are surface-coated fluorescent particles in which at least a portion of the outermost surface of the fluorescent particles is composed of (NH 4 ) 3 AlF 6 .
[表1]
表1中，「-」意指無法獲得，「※」意指沒有實施。In Table 1, “-” means not available, and “※” means not implemented.
針對得到的螢光體粒子，基於以下之評價項目進行評價。The obtained fluorescent particles were evaluated based on the following evaluation items.
(漫反射率) 漫反射率係利用將積分球裝置(ISV-469)安裝至日本分光股份有限公司製紫外可見分光光度計(V-550)而進行測定。使用標準反射板(spectralon)進行基線校正，並安裝上填充有所得到的螢光體粒子之固體試樣固定架，進行對於300nm及峰部波長之光之漫反射率的測定。(Diffuse reflectance) The diffuse reflectance is measured by attaching an integrating sphere device (ISV-469) to a UV-visible spectrophotometer (V-550) manufactured by JASCO Corporation. A standard reflector plate (spectralon) is used for baseline calibration, and a solid sample holder filled with the obtained fluorescent particles is attached to measure the diffuse reflectance of light at 300nm and the peak wavelength.
(發光特性) 色度x係利用分光光度計(大塚電子股份有限公司製MCPD-7000)進行測定，並利用下列程序而算出。 填充得到的螢光體粒子俾使凹型光析管之表面成為平滑，再安裝上積分球。利用光纖將從發光光源(Xe燈)分光出455nm波長之藍色單色光導入至此積分球。將此藍色單色光作為激發光源照射螢光體之試樣，進行試樣之螢光光譜測定。 從得到的光譜資料求出峰部波長及峰部之半高寬。 此外，色度x係從螢光光譜資訊之465nm至780nm之範圍之波長區域資訊，依據JIS Z 8724：2015，算出JIS Z 8781-3：2016規定之XYZ色彩系統中之CIE色度座標x值(色度x)。(Luminescence characteristics) The chromaticity x is measured using a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.) and calculated using the following procedure. The obtained fluorescent particles are filled so that the surface of the concave cuvette becomes smooth, and then an integrating sphere is installed. The blue monochromatic light with a wavelength of 455nm from the luminescent light source (Xe lamp) is introduced into the integrating sphere using an optical fiber. The blue monochromatic light is used as an excitation light source to irradiate the fluorescent sample, and the fluorescence spectrum of the sample is measured. The peak wavelength and the half-height width of the peak are calculated from the obtained spectral data. In addition, chromaticity x is the wavelength region information from 465nm to 780nm of the fluorescence spectrum information. According to JIS Z 8724:2015, the CIE chromaticity coordinate x value (chromaticity x) in the XYZ color system specified in JIS Z 8781-3:2016 is calculated.
(高溫高濕試驗前後之發光強度比) 針對實施例1、2、比較例1~3得到的螢光體粒子，藉由下述程序而測定高溫高濕試驗開始前之發光強度(I0 )。 然後，在60℃、90%RH之環境下，載置100小時或200小時(高溫高濕試驗)。 100小時之高溫高濕試驗後之發光強度(I100 )、200小時之高溫高濕試驗後之發光強度(I200 )係藉由下述程序進行測定。 利用得到的測定值並由下式：I100 /I0 (%)、I200 /I0 (%)算出發光強度比。發光強度比之結果如表1所示。(Luminescence intensity ratio before and after high temperature and humidity test) For the fluorescent particles obtained in Examples 1, 2, and Comparative Examples 1 to 3, the luminescence intensity (I 0 ) before the start of the high temperature and humidity test was measured by the following procedure. Then, it was placed in an environment of 60°C and 90% RH for 100 hours or 200 hours (high temperature and humidity test). The luminescence intensity (I 100 ) after 100 hours of high temperature and humidity test and the luminescence intensity (I 200 ) after 200 hours of high temperature and humidity test were measured by the following procedure. The luminescence intensity ratio was calculated using the measured values obtained by the following formulas: I 100 /I 0 (%), I 200 /I 0 (%). The results of the luminescence intensity ratio are shown in Table 1.
･發光強度之測定程序 使用經玫瑰紅B(Rhodamine B)及副標準光源進行校正的分光螢光光度計(日立先端科技股份有限公司製，F-7000)，測定螢光體粒子之發光強度。又，使用附屬在分光螢光光度計之固體試樣固定架並使用激發波長455nm之螢光光譜。 各實施例及各比較例之螢光體粒子之螢光光譜之峰部波長為656nm。將螢光光譜之峰部波長的強度值作為螢光體粒子之發光強度。･Luminescence intensity measurement procedure The luminescence intensity of the fluorescent particles was measured using a spectrofluorescence photometer (F-7000, manufactured by Hitachi Advanced Technologies Co., Ltd.) calibrated with Rose Bengal B (Rhodamine B) and a sub-standard light source. In addition, a solid sample holder attached to the spectrofluorescence photometer was used and a fluorescence spectrum with an excitation wavelength of 455 nm was used. The peak wavelength of the fluorescence spectrum of the fluorescent particles in each embodiment and each comparative example was 656 nm. The intensity value of the peak wavelength of the fluorescence spectrum was taken as the luminescence intensity of the fluorescent particles.
實施例1、2之螢光體粒子，與比較例1~3相比，顯示出抑制高溫高濕試驗後之發光強度的降低之結果。因此，依據實施例1、2之螢光體粒子，可達成高溫高濕環境下之發光強度特性優異之表面被覆螢光體粒子。The fluorescent particles of Examples 1 and 2 show the result of suppressing the decrease of the luminescence intensity after the high temperature and high humidity test compared with Comparative Examples 1 to 3. Therefore, according to the fluorescent particles of Examples 1 and 2, surface-coated fluorescent particles with excellent luminescence intensity characteristics in a high temperature and high humidity environment can be achieved.
本申請案係主張以在2019年5月31日提申之日本申請案特願2019-102122號為基礎之優先權，並將其揭示之全部內容援引於此。This application claims priority based on Japanese application No. 2019-102122 filed on May 31, 2019, the entire contents of which are incorporated herein by reference.
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