TWI522444B - 表面改質矽酸鹽發光物質 - Google Patents

表面改質矽酸鹽發光物質 Download PDF

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TWI522444B
TWI522444B TW100128948A TW100128948A TWI522444B TW I522444 B TWI522444 B TW I522444B TW 100128948 A TW100128948 A TW 100128948A TW 100128948 A TW100128948 A TW 100128948A TW I522444 B TWI522444 B TW I522444B
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luminescent material
citrate
luminescent
fluorinated
earth metal
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TW201211208A (en
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李貞勳
瓦特 涂斯
岡朵拉 羅夫
德特雷夫 史塔立克
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首爾半導體股份有限公司
Litec Lp股份有限公司
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Description

表面改質矽酸鹽發光物質
本發明之例示性實施例關於基於摻雜鹼土金屬矽酸鹽化合物之無機發光物質,其能夠將高能初級輻射(亦即例如紫外線(UV)輻射或藍光)轉換成可見光譜區內較長波長之次級輻射,發光物質可在發光裝置(諸如發射有色光或白光之發光二極體(light emitting diode;LED))中用作輻射轉換器(radiation converter)。本發明之例示性實施例亦關於矽酸鹽無機發光物質,其可對空氣濕度及其他環境因素具有改良之穩定性且具有延長之使用壽命(operational lifetime)。
鹼土金屬矽酸鹽發光物質已為人所知相當長時間,其包含摻銪鹼土金屬正矽酸鹽、相應的氧正矽酸鹽以及Ba(Sr)3MgSi2O8:Eu形式之二矽酸鹽。對鹼土金屬矽酸鹽化合物之分類的概述由霍勒曼-威博格(Hollemann-Wiberg),「無機化學(Lehrbuch der Anorganischen Chemie/Inorganic Chemistry)」,第102版,(沃爾特.德.格魯伊特公司(Walter de Gruyter & Co.),柏林(Berlin),2007)記載。其製備及基本發光特性已詳細描述於各種專利及出版物中,例如:頒予特烏斯(Tews)等人之美國專利第6,489,716號;由歐華客(Ouwerkerk)等人申請之歐洲申請公開案第0550937號;由哈斯(Hase)等人申請之歐洲申請公開案第0877070號;以及嚴(W.M.Yen)等人,「磷光體手冊 (Phosphor Handbook)」,第二版,CRC出版社(CRC Press)(2007)。這些出版物指示所述發光物質具有高量子及輻射產率以將高能輻射轉換為可見光,且此發光物質類別之多個代表因這些特性而可用於發光、照明以及顯示技術之產品中。
然而,基於鹼土金屬矽酸鹽之發光物質亦具有各種不利特性。一些缺點包含所述發光物質對水、空氣濕度及其他環境因素之輻射穩定性相對較低且敏感性相對較高。敏感性視發光物質之特定組成、結構狀態及發光物質之活化劑離子之性質而定。對於波長轉換發光物質之某些當前應用,這些特性可能成問題。鑒於長壽命要求,此可適用於LED應用。一種已知解決方法為使用合適技術及材料(在粉狀無機發光物質表面上)產生障壁層(barrier layer)以減少水蒸氣之影響。
這些方法可包含以有機聚合物囊封、用奈米級氧化物(諸如SiO2或Al2O3)塗佈,或化學氣相沈積(chemical vapour deposition;CVD)所述氧化物。然而,對於矽酸鹽發光物質,可達成之保護可能不足以在所需程度上改良相應LED燈之壽命。此外,在經塗佈發光物質之狀況下,可能需要承受亮度損失、色彩位置偏移以及其他品質損耗。藉助於氣相方法微囊封發光物質粒子之製程可能不便利且成本高。
本發明之例示性實施例提供矽酸鹽發光物質,其可具 有水分穩定性、對輻射及其他環境影響之穩定性以及改良之使用壽命。
本發明之例示性實施例亦提供已經氟化無機或有機試劑進行表面處理之發光物質。
本發明之例示性實施例亦提供將精細分散之氟化物或氟化合物可偵測地固定於發光物質表面上或使所述化合物形成能夠使發光物質表面具疏水性且可修整表面缺陷之表面網狀結構。
本發明之其他特徵將在隨後描述中闡述,且在某種程度上將自所述描述而顯而易見,或可藉由實踐本發明而獲悉。
本發明之例示性實施例揭露一種表面改質矽酸鹽發光物質,其包含:(a)矽酸鹽發光物質及塗層,所述塗層包含至少一個氟化塗層,其包含氟化無機試劑、氟化有機試劑或氟化無機試劑與氟化有機試劑之組合,所述氟化塗層產生疏水性表面位點,以及(b)氟化塗層與至少一個水分障壁層之組合,所述水分障壁層包含MgO、Al2O3、Ln2O3、Y2O3、La2O3、Gd2O3、Lu2O3以及SiO2,或相應前驅物。
應瞭解,上述一般描述及下列詳細描述為例示性及說明性的,且意欲提供對所主張之本發明的進一步說明。
包含隨附圖式以提供對本發明之進一步理解,且併入本發明說明書中並構成本發明說明書之一部分,其說明本發明之實施例且連同描述一起用以說明本發明之原理。
本發明在下文中參考隨附圖式得以更充分描述,圖式中展示本發明之例示性實施例。然而,本發明可以多種不同形式實施且不應視作限於本文所闡述之例示性實施例。實際上,提供這些例示性實施例以使本發明透徹,且向熟習此項技術者完全傳達本發明範疇。在圖式中,為明晰起見,可放大層及區域之尺寸及相對尺寸。圖式中相同圖式元件符號表示相同元件。
應瞭解,當元件或層被稱作「處於」另一元件或層「上」或「連接至」另一元件或層時,其可直接處於其他元件或層上或直接連接至其他元件或層,或可存在插入元件或層。相反,當元件被稱作「直接處於」另一元件或層「上」或「直接連接至」另一元件或層時,不存在插入元件或層。
在以高能紫外線輻射、藍光、電子束、X射線或γ射線激發時且視發光物質之特定化學組成及活化劑之性質而定,根據本發明例示性實施例之發光物質可以高輻射產率及相較於先前技術顯著改良之對H2O、空氣濕度及其他環境因素之穩定性發射可見光及紅外線輻射。出於此原因,其可用於長壽命工業產品中,例如用於X射線影像轉換器中之陰極射線管及其他影像產生系統(掃描雷射束系統)、高效能光源、用於內部及外部照明之全色LED、LCD顯示器之背光、太陽能電池、溫室膜以及作為輻射轉換器之玻璃中。
包含表面改質矽酸鹽發光物質的根據本發明例示性 實施例之發光物質特徵可為其表面具有塗層,所述塗層由氟化無機或有機試劑構成以產生疏水性表面位點,或由氟化塗層與一或多個由層形成材料(layer-forming material)構成之水分障壁層的組合構成,所述層形成材料為諸如氧化物MgO、Al2O3、Ln2O3(其中Ln=Y、La、Gd或Lu)以及SiO2,或相應前驅物,或溶膠-凝膠技術。
根據本發明例示性實施例之包含表面改質矽酸鹽發光物質之發光物質可包含粉狀鹼土金屬矽酸鹽發光物質。表面改質矽酸鹽發光物質可具有下列通式:(Me1+Me2+Me3+)x˙(Si,P,Al,B,V,N,C,Ge)y˙(O,N)z:(A,F,S),其中A為由類鑭系元素或錳之族群中選出的活化劑;F為表面固定且視情況交聯之氟或氟化合物;且S特徵為具有未氟化之層形成材料的視情況存在之其他塗層。Me1+為單價金屬,Me2+為二價金屬且Me3+為由元素週期表(Periodic Table)第III族或類鑭系元素中選出的三價金屬。一些矽可由P、Al、B、V、N、Ge或C置換。係數x、y及z可具有下列範圍:0<x<5,0<y<12以及0<z<24。
根據本發明之例示性實施例,可最佳化發光特性及穩定性效能,表面改質矽酸鹽發光物質中之一些鹼土金屬離子可由其他二價離子(例如Mg、Zn)置換,或在實施合適措施以平衡電荷之情況下,由鹼金屬族或稀土金屬族之單價或三價陽離子置換。此外,P、B、V、N、Ge或C可併入表面改質矽酸鹽發光物質之陰離子次晶格中以置換一 些矽。
根據本發明之例示性實施例,鹼土金屬矽酸鹽發光物質可使用Si(OR)3X形式之氟官能化有機矽烷氟化,其中R=CH3、C2H5等且X=F官能化有機配位體,且可進行控制水解及縮合以在矽酸鹽發光物質基質上形成氟化障壁層,其可為障壁且亦可具有疏水特性。
根據本發明例示性實施例之表面改質矽酸鹽發光物質可由下列通式表徵:Sr3-x-y-zCaxBaySiO5:Euz,F,S,其中0x2,0y2以及0<z<0.5。根據本發明例示性實施例之表面改質矽酸鹽發光物質亦可由下式表徵:Sr3-x-y-zCaxBaySiO5:Euz,F,S,其中0x0.05,0y0.5以及0<z<0.25。
用作製備根據本發明例示性實施例之表面改質發光物質之基質的發光物質粉末可藉由在超過1000℃之溫度下使可用作起始物質之鹼土金屬碳酸鹽或相應金屬氧化物與SiO2之間進行多階段高溫固態反應來合成。另外,可將礦質化添加劑(例如NH4Cl、NH4F,或鹼金屬或鹼土金屬鹵化物,或三價金屬之鹵化物)添加至反應混合物中以促進反應性且控制所得發光物質之粒徑分佈。視化學計量比之特定選擇而定,有可能產生摻雜鹼土金屬矽酸鹽發光物質、更特定言之相應正矽酸鹽及氧正矽酸鹽發光物質之所需組成。
因此,劇烈混合計算量之起始物質且接著在惰性或還原氛圍中於所需溫度範圍內進行多階段煅燒製程。為最佳化發光物質特性,主要煅燒製程亦可視情況具有在不同溫度範圍內進行之若干煅燒階段。在煅燒製程結束後,將樣品冷卻至室溫且進行合適之後處理製程,所述後處理製程旨在例如消除助熔劑殘餘物、最小化表面缺陷,或微調粒徑分佈。或者亦有可能使用氮化矽(Si3N4)或其他含矽前驅物替代氧化矽作為與所用鹼土金屬化合物反應之反應物。用於產生發光物質之例示性實施例之多晶發光物質粉末之合成不限於上文所述之製備方法。
為氟化根據本發明之粉狀鹼土金屬矽酸鹽發光物質之表面,可使用不同無機氟化合物,諸如鹼金屬氟化物(例如LiF、NaF、KF)、鹼土金屬氟化物(MgF2、CaF2、SrF2、BaF2)、AlF3及稀土金屬氟化物(例如YF3、LaF3或GdF3)、NH4F及NH4HF2,以及其他無機或有機氟化合物(例如含氟胺)。將所選材料與矽酸鹽發光物質粉末混合,在所述狀況下可使用水性懸浮液。所添加之氟化劑之所需比例視化合物之溶解度及反應條件(pH值、溫度、混合強度、滯留時間等)而定且可以實驗方式確定。
在表面處理結束後,自懸浮液移出氟化發光物質,且可用合適溶劑洗滌,接著在80℃至200℃之溫度下乾燥。在冷卻及篩分後,其呈即用形式。
為達成最佳發光物質特性,視本發明發光物質之特定組成、所用氟化劑之類型及量以及其他因素而定,除乾燥 製程以外或替代乾燥製程,在300℃至600℃之溫度範圍內於還原氛圍中對根據本發明製備之發光物質進行熱後處理(熱處理)。關於製備根據本發明例示性實施例之發光物質的詳細資訊在下文中由若干工作實例給出。
工作實例A1
工作實例A1描述根據本發明例示性實施例之具有氟化表面層且具有基礎晶格組成Sr2.9Ba0.01Ca0.05SiO5:Eu0.04之發光物質的製備,所述發光物質在表1中被描述為樣品F-103且其光學數據亦提供於表1中,且發射光譜在圖1a中指定為「3」。
表1含有經不同量之NH4F處理之銪活化型氧正矽酸鍶發光物質樣品之光學及水分穩定性數據。為合成相應發光物質基質,劇烈混合化學計算量之SrCO3、BaCO3、CaCO3、Eu2O3及SiO2與0.2莫耳NH4Cl且接著在剛玉坩堝中於1400℃下在含有2%氫氣之N2/H2氛圍中進行5小時煅燒製程。在煅燒製程結束後,均質化經煅燒之材料,研磨且用H2O洗滌。隨後,將100公克經乾燥及篩分之發光物質連同1.1公克NH4F、200公克玻璃珠粒以及1公升水一起引入合適之塑膠容器中且在缸式研磨機(jar mill)上以低速劇烈混合30分鐘。沈降數分鐘時間後,首先傾析上清液且接著經由布赫納漏斗(Büchner funnel)進行抽吸過濾。之後乾燥及篩分最終產物。
工作實例A2
為製備根據本發明例示性實施例之含有發光物質之 樣品F-202,其光學數據說明於表2中且其發射光譜在圖1a中指定為「4」,將100公克工作實例A1中所述之發光物質基質與2.474公克NH4HF2混合。表2含有經不同量之NH4HF2處理之銪活化型氧正矽酸鍶發光物質樣品之光學及水分穩定性數據。在此狀況下,藉由在輥筒研磨機(roll mill)上將混合物放入1公升去離子水及400公克玻璃珠粒中來藉由濕式化學沈澱塗覆氟化表面層。處理1小時,之後自溶液移出經塗佈之發光物質且類似於工作實例A1進行後處理。
工作實例A3
此處,在剛玉坩堝中,於400℃下在含有35%氫氣之N2/H2氛圍中熱處理30公克根據工作實例A2製備之發光物質60分鐘。冷卻後,藉由篩分均質化樣品F-202T以產生本發明之例示性實施例,所述樣品之光學數據說明於表2中且其發射光譜在圖1a中指定為「5」。
工作實例A4
根據工作實例A1合成呈固態之根據本發明例示性實施例之具有基礎晶格組成Sr2.948Ba0.01Cu0.002SiO5:Eu0.04之氧正矽酸鹽發光物質,且使用前驅物材料四乙氧基矽烷(TEOS)塗佈SiO2網狀結構。出於此目的,將50公克發光物質與由1公升乙醇、18.2公克TEOS以及100毫升32%氨水組成之500毫升溶液混合,且在反應容器中攪拌2小時。此後,抽吸過濾經塗佈之發光物質,用乙醇洗滌,且在160℃下乾燥24小時。
在此製備型表面處理後,如在工作實例A1中,藉由NH4F作為氟化劑對發光物質進行氟化。出於此目的,使80公克預塗佈之發光物質與1.98公克NH4F在工作實例A1之條件下反應。由此產生根據本發明例示性實施例之發光物質,其呈樣品F-TS-600之形式。如同工作實例A1、工作實例A2以及工作實例A3中所述之發光物質,樣品F-TS-600之光學數據描述於表6中,且其發射光譜在圖1a中指定為「7」,且可具有相較於習知氧正矽酸鹽發光物質顯著改良之防潮性(moisture resistance)且其基礎晶格組成與未經塗佈之基質發光物質相同。根據本發明例示性實施例之這些發光物質之效能特徵匯總於表1、表2以及表6中。
工作實例B1
為製備呈樣品F-320形式之根據本發明例示性實施例之發光物質,合成組成為Sr2.9485Ba0.01Cu0.0015SiO5:Eu0.04之基礎晶格。出於此目的,混合化學計算量之SrCO3、BaCO3、CuO、Eu2O3、65公克SiO2以及0.3莫耳NH4Cl,將其引入合適的煅燒坩堝中且在高溫爐中煅燒24小時時段。煅燒程式具有1200℃下及1350℃下之兩個主要煅燒帶,在各溫度下維持3小時。在第一煅燒階段期間,在氫氣濃度為5%之合成氣體(forming gas)下實現煅燒,且在後續第二煅燒階段中將氫氣濃度增加至20%。
冷卻、洗滌且均質化基質材料,繼而氟化發光物質表面。為此目的,所用之氟化劑為替代NH4F或NH4HF2的 氟化鋁AlF3。為與發光物質粒子表面相互作用,在60℃下將1.2公克AlF3引入1公升H2O中且劇烈攪拌混合物1小時。隨後,將所合成之100公克發光物質基質添加至懸浮液中。反應時間可為60分鐘。類似於工作實例A1、工作實例A2、工作實例A3以及工作實例A4,後處理呈樣品F-320形式之經塗佈發光物質。光學數據展示於表3中,且其發射光譜在圖1a中指定為「6」。表3含有其他氟化之摻Eu2+氧正矽酸鍶發光物質之光學及穩定性數據。
工作實例C1
隨後之工作實例關於根據本發明例示性實施例塗佈且具有組成Sr0.876Ba1.024SiO4:Eu0.1之鹼土金屬正矽酸鹽發光物質。在本發明例示性實施例中,藉由高溫固態反應產生基質材料,其中起始混合物包括化學計算量之SrCO3、BaCO3、Eu2O3、SiO2以及0.2莫耳NH4Cl。
煅燒製程包含在氮氣氛圍中將填充有起始混合物之坩堝加熱至1275℃,經10小時時段維持此溫度以及隨後冷卻至室溫。在達到高溫勻變(ramp)時,將20%氫氣添加至保護氣體中。冷卻後,洗滌所得材料以移除助熔劑殘餘物,且接著乾燥及篩分。
為氟化基質材料,將150公克發光物質粉末及4.268公克NH4F懸浮於3公升H2O中且經2小時時段攪拌。塗佈程序結束後,抽吸過濾氟化發光物質,以得到樣品F-401,在抽吸過濾器上用乙醇洗滌,且在130℃下乾燥24小時。樣品F-401之光學數據展示於表4中,且F-401之 發射光譜在圖1b中指定為「2」。表4含有另外塗有SiO2且經氟化之發射綠光波長之鹼土金屬正矽酸鹽發光物質的光學及穩定性數據。
在另一步驟中,呈樣品F-401形式之根據本發明例示性實施例之發光物質可具有SiO2塗層。出於此目的,將50公克氟化之Sr0.876Ba1.024SiO4:Eu0.1發光物質粉末添加至由1公升乙醇、25公克TEOS以及150毫升32%氨水組成之500毫升TEOS溶液中,所述TEOS溶液在臨用前24小時製備。攪拌5小時時間後,終止反應。抽吸過濾呈樣品F-401TS形式之表面塗佈之發光物質,再用乙醇洗滌,且乾燥。樣品F-401TS之光學數據說明於表4中,F-401TS之發射光譜在圖1b中指定為「3」。
具有不同基質組成之氟化發光物質相較於在各狀況下未經處理之發光物質的發射光譜描述於圖1a及圖1b中,其展示根據本發明例示性實施例具有氟化表面結構之發光物質的發光強度(luminescence intensity)與參考物質略有不同。此亦由表1、表2、表3、表4、表5、表6以及表7中所匯總之根據例示性實施例之發光物質樣品之發光數據所證實,而在一些狀況下,量測到氟化且視情況另外塗有SiO2之樣品的發光強度略微較低。在所提及之表中亦存在因表面處理而使發光效率(luminescence efficiency)略微增強之實例。後者之效應可能歸因於在經塗佈材料之狀況下光發射略微較佳。
在圖2a及圖2b中,將根據本發明例示性實施例之氟 化Sr3SiO5:Eu發光物質之電子顯微照片與未經處理之起始物質的電子顯微照片相比較。這些顯微照片表明工作實例中所述之以合適氟化劑進行表面處理可形成特定表面結構,其可藉助於掃描電子顯微照片觀測。
圖3中所展示之發射綠光波長之鹼土金屬正矽酸鹽發光物質的電子顯微照片的情況類似。圖3中之顯微照片展示未經處理之發光物質樣品、根據本發明例示性實施例製備之氟化材料以及由起始物質產生且另外塗有SiO2之另一樣品的特徵性粒子表面。
同時,自圖4中所示之相應能量色散X射線光譜學(energy-dispersive X-ray spectroscopy;EDX)分析之結果清楚可知,表面結構含有氟。除作為發光物質基質之特徵的鍶(Sr)、矽(Si)以及氧(O)之峰以外,在根據本發明氟化之發光物質的EDX光譜中亦發現具有顯著峰高度之明顯單個反射,其基於所述峰之能量位置應明確地指定為元素氟(F)。另外,所示光譜亦含有指定為金(Au)及鈀(Pd)之反射,這是基於與分析方法有關之原因而用金及鈀塗佈發光物質樣品所致。
關於精細分散之氟化物或氟化合物固定於根據本發明例示性實施例之發光物質表面上或所述化合物在所述發光物質表面上形成網狀結構的其他證據由X射線光電子光譜學(X-ray photoelectron spectroscopy;XPS)分析之結果記錄於圖5及圖6中。固定可包含吸附及類似化學吸附或物理吸附方式。展示於圖5中之根據工作實例1具有基礎 晶格組成Sr2.9Ba0.01Ca0.05Eu0.04SiO5且經NH4F處理之發光物質的XPS光譜展示亦有可能以此固態分析方法偵測作為氟化發光物質之表面結構之組分的元素氟(F)。自XPS光譜亦可得到其他結論。舉例而言,自經NH4F氟化之氧正矽酸鹽發光物質(圖6中之曲線2)與相應發光物質基質與等量NH4F之機械混合物之樣品(圖6之曲線1)的內部校正XPS光譜之比較明顯可知,在各狀況下所測定之F 1s峰具有不同強度且亦展現結合能相對於彼此偏移,如圖6中所示。
標記為曲線2之樣品的F 1s峰之強度較低可解釋為在加工期間有一些所添加之氟自發光物質表面損失。曲線1之F 1s峰偏移至較低結合能可能指示所塗覆之氟化劑與發光物質基質表面之間形成化學鍵。
在表1、表2、表3、表4、表5以及表6中,匯總根據本發明例示性實施例組態之不同矽酸鹽發光物質之若干發光參數及穩定性測試之結果且與未改變(亦即表面未經氟化)之發光物質粉末相比較,且在一些狀況下,與市售比較發光物質相比較。表5含有氟化之塗有Eu2+之氧正矽酸鍶發光物質以及氟化且塗有SiO2之塗有Eu2+之氧正矽酸鍶發光物質的光學及穩定性數據。表6含有經氟化之塗有SiO2之氧正矽酸鍶發光物質的光學及穩定性數據。
材料之水分穩定性藉由在於85℃溫度及85%空氣濕度下操作之氣氛控制箱(climate-controlled cabinet)中儲存相應發光物質樣品七天來評估。隨後,在150℃下乾燥 發光物質24小時且接著對發光產額(luminescence yield)進行比較量測。
比較發光量測之結果表明,根據本發明例示性實施例之發光物質之發光效率及其溫度依賴性與市售之銪活化型鹼土金屬氧正矽酸鹽或相應正矽酸鹽發光物質相當,或甚至超越後者。其次,如表4、表5及表6中所示,穩定性測試之結果展示,具有氟化表面結構及視情況存在之其他SiO2塗層的根據本發明例示性實施例之發光物質相較於具有相同基質組成之未改變(亦即表面未經氟化)之發光物質而言具有顯著改良之防潮性。
熟習此項技術者將顯而易知,可在本發明中進行各種修改及變化而不悖離本發明之精神或範疇。因此,本發明意欲涵蓋對本發明之修改及變化,限制條件為其屬於隨附申請專利範圍及其等效物之範疇內。
圖1a為參考物質Sr2.9Ba0.01Ca0.05Eu0.04SiO5(指定為「1」)、市售Sr3SiO5:Eu(指定為「2」)發光物質以及根據本發明例示性實施例之氧正矽酸鹽發光物質F-103、F-202、F-202T、F-320及F-TS-600的發射光譜。
圖1b為參考物質Sr0.876Ba1.024Eu0.1SiO4(指定為「1」)及根據本發明例示性實施例之兩種鹼土金屬正矽酸鹽發光物質F-401及F-401TS的發射光譜。
圖2a為未氟化及氟化之鹼土金屬氧正矽酸鹽發光物質的電子顯微照片,左側展示發光物質Sr2.9Ba0.01Ca0.05SiO之未經處理之粒子,且右側展示根據本發明例示性實施例之發光物質F-202之氟化粒子。
圖2b為根據本發明例示性實施例之發光物質F-202表面之放大電子顯微照片。
圖3為基礎晶格組成Sr0.876Ba1.024SiO4:Eu0.1之未經塗佈之鹼土金屬正矽酸鹽發光物質、氟化之鹼土金屬正矽酸鹽發光物質及塗有SiO2之鹼土金屬正矽酸鹽發光物質的電子顯微照片,左側展示未經塗佈之起始物質的掃描電子顯微照片,中間展示氟化之發光物質表面,且右側展示根據本發明之例示性實施例另外塗有SiO2之發光物質樣品。
圖4為根據本發明之例示性實施例具有明顯氟化表面結構的發光物質F-103之能量色散X射線(EDX)光譜影像。
圖5為根據本發明例示性實施例之發光物質F-103之 X射線光電子(XPS)光譜。
圖6為展示不同發光物質樣品之代表性氟XPS峰的圖。曲線1涉及根據工作實例A1具有組成Sr2.9Ba0.01Ca0.05Eu0.04SiO5之發光物質與一定量NH4F的機械混合物,且曲線2涉及根據本發明例示性實施例之氟化發光物質F-103之氟1s峰。

Claims (7)

  1. 一種表面改質矽酸鹽發光物質,包括:矽酸鹽發光物質;以及塗層,包括以下至少一者:氟化塗層包括氟官能化有機矽烷,其包括通式Si(OR)3X,其中R=CH3或C2H5,且X包括氟官能化有機配位體,其中氟化層安置於所述矽酸鹽發光物質上,且包括疏水特性;以及所述氟化塗層與至少一個水分障壁層之組合,其中所述塗層安置於所述矽酸鹽發光物質之表面上。
  2. 如申請專利範圍第1項所述之表面改質矽酸鹽發光物質,其中所述表面改質矽酸鹽發光物質包括粉狀鹼土金屬矽酸鹽發光物質。
  3. 如申請專利範圍第1項所述之表面改質矽酸鹽發光物質,其中所述矽酸鹽發光物質包括通式(Me1+Me2+Me3+)x˙(Si,P,Al,B,V,N,C,Ge)y˙(O,N)z:(A,F,S),其中A為由類鑭系元素及/或錳之族群中選出的活化劑,F為表面固定或交聯之氟或氟化合物,且S為具有未氟化之層形成材料的其他塗層,Me1+為單價金屬,Me2+為二價金屬,且Me3+為由第III族或類鑭系元素中選出的三價金屬,一些Si可由P、Al、B、V、N、Ge或C置換,且0<x<5,0<y<12,0<z<24。
  4. 如申請專利範圍第1項所述之表面改質矽酸鹽發光物質,其中所述矽酸鹽發光物質包括式 Sr3-x-y-zCaxBaySiO5:Euz,F,S,其中F為表面固定或交聯之氟或氟化合物,且S為具有未氟化之層形成材料的其他塗層,且其中0x2,0y2且0<z<0.5。
  5. 如申請專利範圍第1項所述之表面改質矽酸鹽發光物質,其中所述矽酸鹽發光物質包括式Sr3-x-y-zCaxBaySiO5:Euz,F,S,其中F為表面固定或交聯之氟或氟化合物,且S為具有未氟化之層形成材料的其他塗層,且其中0x0.05,0y0.5且0<z<0.25。
  6. 如申請專利範圍第2項所述之表面改質矽酸鹽發光物質,其中所述粉狀鹼土金屬矽酸鹽發光物質更包括一些鹼土金屬由包括Mg、Zn之二價離子、由鹼金屬族及稀土金屬族中選出之單價陽離子以及由稀土金屬族中選出之三價陽離子置換。
  7. 如申請專利範圍第2項所述之表面改質矽酸鹽發光物質,其中所述粉狀鹼土金屬矽酸鹽發光物質更包括一些矽由P、B、V、N、Ge或C置換。
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TW201211209A (en) 2012-03-16
BR112013003417B1 (pt) 2021-10-13
WO2012023714A2 (en) 2012-02-23
EP2603937A2 (en) 2013-06-19
EP2603937B1 (en) 2016-11-23
DE102010034322A1 (de) 2012-02-16
TWI541325B (zh) 2016-07-11
BR112013003416A2 (pt) 2020-10-27
CN103068953A (zh) 2013-04-24
KR20120023495A (ko) 2012-03-13
RU2013111302A (ru) 2014-09-20
KR20120023496A (ko) 2012-03-13
EP2603571A4 (en) 2014-10-22
RU2569167C2 (ru) 2015-11-20
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WO2012023714A3 (en) 2012-05-18
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US8581286B2 (en) 2013-11-12
JP2013536283A (ja) 2013-09-19
BR112013003417A2 (pt) 2020-10-27
KR101752428B1 (ko) 2017-07-05
US20120037850A1 (en) 2012-02-16
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