TWI679233B - 用於照明裝置中過濾色彩的材料及光學組件 - Google Patents

用於照明裝置中過濾色彩的材料及光學組件 Download PDF

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TWI679233B
TWI679233B TW104133077A TW104133077A TWI679233B TW I679233 B TWI679233 B TW I679233B TW 104133077 A TW104133077 A TW 104133077A TW 104133077 A TW104133077 A TW 104133077A TW I679233 B TWI679233 B TW I679233B
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optical component
neodymium
particulate material
compound
visible light
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TW201631046A (zh
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蔡登科
Dengke Cai
湯瑪斯 克里尼
Thomas CLYNNE
健民 何
Jianmin He
馬克 愛德華 卡明斯基
Mark Edward Kaminski
班哲明 李 尤德爾
Benjamin Lee Yoder
任孝軍
Xiaojun REN
周惠升
Huisheng ZHOU
王志勇
Zhiyong Wang
李健
Jian Li
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美商奇異照明解決有限責任公司
GE Lighting Solutions, LLC
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Abstract

本發明係關於適合用於照明裝置中以賦予對可見光之過濾色彩作用的材料及由其所形成的光學組件。該光學組件之至少一部分係由包含聚合基質材料及無機微粒材料之複合材料形成，該無機微粒材料對穿過該複合材料之可見光貢獻過濾色彩作用，且該微粒材料包含含有Nd3+離子之釹化合物。

Description

用於照明裝置中過濾色彩的材料及光學組件
本發明大體上係關於照明系統及相關技術。更特定而言，本發明係關於適於賦予對光源之過濾色彩作用之材料及方法，其非限制性實例包括利用一或多個發光二極體(LED)作為光源的照明裝置。
LED燈提供多種優於較傳統白熾燈及螢光燈的優點，包括(但不限於)較長預期壽命、較高能效及不需升溫時間的全亮度。如此項技術中已知，LED(如本文所用，其亦涵蓋有機LED或OLED)為固態半導體器件，其將電能轉換成包括可見光(波長為約400至750nm)的電磁輻射。LED通常包含摻雜有雜質以形成p-n接面之半導體材料的晶片(晶粒)。將LED晶片電連接至陽極及陰極，以上所有常常安裝在封裝內。因為，相比於其他燈，諸如白熾燈或螢光燈，LED發射呈較窄光束形式較有方向性之可見光，LED傳統上已用於諸如汽車、顯示器、安全/緊急情況及定向區域照明之應用中。然而，LED技術之進步已使基於LED之高效照明系統更廣泛地用於傳統上採用其他類型光源之照明應用，包括先前由白熾燈及螢光燈服務的全向照明應用。因此，LED愈來愈多地用於住宅、商業及市政設置中的區域照明應用。
圖1表示適於區域照明應用之基於LED之照明單元的非限制性商業實例。照明單元(其亦可稱為「照明裝置」)或「燈」)10表示為經組態以提供幾乎全向照明能力的LED燈(ANSI A19類型)。亦已知其他 不同組態之基於LED之照明單元。如圖1中所示，燈10包含透明或半透明罩殼或外罩12、愛迪生型(Edison-type)螺紋基座連接器14、在外罩12與連接器14之間的外殼或基座16及視情況選用之散熱片(heat-dissipating fin)18(增強輻射及對流熱傳遞至周圍環境)。
基於LED之光源(常常為包含多個LED器件的LED陣列)通常位於鄰近基座16之外罩12的下端處。因為LED器件發射在波長之窄帶內的可見光，例如綠色、藍色、紅色等，所以不同LED器件之組合常常在LED燈中組合以產生各種光色彩，包括白光。或者，呈現實質上白色的光可利用來自藍色LED及將至少一些藍色LED之藍光轉換為不同色彩之磷光體(例如，YAG：Ce)之光的組合產生；經轉換之光及藍光之組合可產生呈現白色或實質上白色的光。LED器件可在安裝至基座16或在基座內的載體上安裝，且可在該載體上囊封，例如用保護性罩殼，其常常由指數匹配材料形成以增強自LED器件提取可見光的效率。作為一非限制性實例，圖2表示一種類型之LED器件20之一部分，其包含圓頂22，其用作包圍在印刷電路板(PCB)26上安裝的LED晶片24之光學透明或半透明的包封。磷光體亦可用於發射除由LED產生的色彩光以外的色彩光。出於此目的，圓頂22之內部表面可具有塗層28，該塗層含有磷光體組合物，在此情況下，由LED晶片24發射的電磁輻射(例如，藍色可見光、紫外線(UV)輻射或可見近紫外線(NUV)輻射)可由該磷光體組合物吸收，導致激發該磷光體組合物產生經由圓頂22發射的可見光。作為一替代方案，LED晶片24可在PCB 26上用塗層囊封，且該塗層可視情況含有磷光體組合物以用於其中需要使用LED磊晶(epi)晶圓或晶粒製造的LED-磷光體積體之實施例。
為了促進燈10以幾乎全向方式發射可見光的能力，圖1中之外罩12的形狀表示為實質上球形或橢圓形。促進光分佈(例如，全向光分佈)之其他方法為可能的。為了進一步促進近全向照明能力，外罩12 可由使該外罩12充當光學漫射體之材料形成。作為一非限制性實例，外罩12可為或可包括包含一對半球面漫射體(在其之間可安置內部反射器(圖中未示))的組合件，使得由LED器件產生之可見光導向至外罩12內部，所產生之光的一部分由反射器反射進入更靠近基座16的半球面漫射體，反射光經由該半球面漫射體分佈至燈10周圍的環境。所產生之光的其餘部分穿過反射器中的開口且進入第二半球面漫射體，所穿過之光經由該第二半球面漫射體分佈至燈10周圍的環境。通常用於製造該漫射體之材料可包括聚醯胺(例如，耐綸)、聚碳酸酯(PC)或聚丙烯(PP)或其類似材料。此等聚合材料通常可含有填充劑，例如二氧化鈦(TiO2)，以促進光折射且藉此獲得白色反射外觀。外罩12之內部表面可具有塗層(圖中未示)，例如含有磷光體組合物之塗層。
儘管使用不同LED器件及/或磷光體之組合可用於促進LED燈產生白光作用的能力，但需要其他方法作為替代方案或作為其補充。
本發明提供適合用於照明裝置中以賦予對可見光之過濾色彩作用的材料及由其所形成的光學組件。
根據本發明之一個態樣，光學組件之至少一部分由包含聚合基質材料及無機微粒材料的複合材料形成，該無機微粒材料對穿過該複合材料的可見光貢獻過濾色彩作用，且該微粒材料包含含有Nd3+離子之釹化合物。
本發明之其他態樣涵蓋照明裝置，其包括發射可見光之光源及經組態且經配置使得該光源之至少一部分可見光穿過其的光學組件。該光學組件之部分由包含聚合基質材料及無機微粒材料的複合材料形成，該無機微粒材料對穿過該部分的可見光貢獻過濾色彩作用，且該微粒材料包含含有Nd3+離子之釹化合物。
本發明之額外態樣包括利用上文所述之一種類型的複合材料， 其中該釹化合物可以離散粒子形式(或以該微粒材料中之摻雜劑形式)存在，從而促進微粒材料與聚合基質材料之折射率匹配，足以賦予對由照明裝置發射的可見光之低濁度光學作用。在不受理論限制的情況下，咸信該低濁度光學作用至少部分歸因於使米氏散射(Mie scattering)減至最少。或者，該釹化合物可以離散粒子形式存在，其視情況與微粒材料之第二粒子組合以促進微粒材料與聚合基質材料之折射率失配，足以賦予對由照明單元發射的可見光之漫射光學作用。
上文所述之複合材料、光學組件及照明單元之技術作用較佳包括提供所需過濾色彩作用之能力，且較佳具有使基質材料之折射率有意匹配或失配從而分別最小化或促進經由複合材料及光學組件穿過的光之光學散射的進一步能力。
將自以下【實施方式】更好地理解本發明之其他態樣及優點。
10‧‧‧照明單元/照明裝置/燈
12‧‧‧罩殼/外罩
14‧‧‧愛迪生型螺紋基座連接器
16‧‧‧基座
18‧‧‧散熱片
20‧‧‧LED器件
22‧‧‧圓頂
24‧‧‧LED晶片
26‧‧‧印刷電路板
28‧‧‧塗層
圖1表示能夠自包括根據本發明之非限制性實施例之含有釹組合物的光學組件獲益之類型之基於LED之照明裝置。
圖2表示能夠用於基於LED之照明裝置之類型(例如，圖1中所示之類型)之LED器件的局部截面視圖。
圖3為表示針對NdF3及NaNdF4奈米晶所觀測到的吸收光譜之曲線圖，且圖4為表示當經受800nm之激發頻率(λexc)及240mW之激發功率時，NdF3及NaNdF4奈米晶之上轉換螢光光譜的曲線圖。
圖5為表示分散於聚矽氧基質中的NdF3之光學透射特徵與摻雜Nd2O3之玻璃相比的曲線圖。
以下論述將參考圖1中所示之基於LED之照明裝置10及圖2中所示之LED器件20。然而，應瞭解，各種其他組態之照明單元及LED器件亦在本發明之範疇內。
本發明提供適合用於照明裝置中以賦予對可見光(具體實例為由LED器件產生之可見光)之過濾色彩作用的複合材料及由其所形成的光學組件。如本文所用，光學組件為可見光需要穿過其至少一部分以提供照明效果的組件。複合材料及光學組件含有Nd3+離子來源。經由產生本發明之研究，已確定該來源有效提供過濾色彩作用，尤其為過濾在黃光波長(例如，波長約560nm(奈米)至約600nm)範圍內的可見光。
根據本發明之某些態樣，視複合材料之組成以及複合材料中之Nd3+離子來源之組成及量而定，該等複合材料及光學組件對穿過其之光可具有極小(若存在)的光學散射(漫射)作用或者可引起顯著的光學散射。可基於此等因素選擇所需作用。作為實例，較佳複合材料包含聚合基質材料，其中分散有含有Nd3+離子來源的無機微粒材料。Nd3+離子來源可為釹化合物，該釹化合物以微粒材料中之摻雜劑形式存在，或以釹化合物之離散粒子(其可視情況與其他材料之粒子組合以組成微粒材料)形式存在。含有釹化合物之離散粒子(例如，部分或全部由釹化合物形成)及/或摻雜有釹化合物之另一材料之粒子的微粒材料可與聚合基質材料組合，以達成促進微粒與聚合基質材料之折射率匹配(亦即，使其折射率的差異減至最小)的目的，且足以對穿過複合材料的可見光賦予低濁度(低漫射率)光學作用。或者，微粒材料可僅由釹化合物之離散粒子(例如，部分或全部由釹化合物形成)組成及/或由釹化合物之離散粒子(例如，部分或全部由釹化合物形成)與由至少一種其他不同材料形成之粒子的混合物組成，使得該微粒材料具有充分不同於聚合基質材料之折射率的折射率，從而獲得微粒與聚合基質材料之間的折射率失配(亦即，增加其折射率的差異)，以對穿過複合材料的可見光賦予漫射光學作用。
鑒於此調適複合材料之光學散射作用的能力，由複合材料形成 之光學組件可具有多種功能。舉例而言，一種此類功能可為提供過濾色彩作用，諸如在用於形成LED器件之圓頂(諸如在例如圖2中)時。另一例示性功能可為額外提供(亦即，除過濾色彩作用以外)光學散射作用，諸如在用於形成圖1之照明裝置10之外罩/漫射體12時。
一種Nd3+離子來源可為包含Nd-F化合物之材料。如本文所用，「Nd-F化合物」應廣泛地解釋為包括包含釹及氟及視情況選用之其他元素的化合物。該等包含釹及氟之化合物可包含氟化釹、或氧氟化釹(例如，NdOxFy，其中2x+y=3)、或包含外來水及/或氧的氟化釹、或氟化氫氧化釹(例如，Nd(OH)aFb，其中a+b=3)或包含釹及氟的諸多其他化合物(其將自以下描述變得易於顯而易見)。在一些應用中，Nd-F化合物可具有相對較低的折射率，諸如與所選擇之聚合材料匹配以提供低濁度光學組件的折射率。一種適用之Nd3+離子來源咸信為氟化釹(NdF3)，其折射率為約1.6，提供適當較低折射率以便與某些聚合基質材料指數匹配以使散射損失減至最少。其他Nd3+離子來源為可能的，例如其他含有Nd-F之化合物，其非限制性實例包括Nd-X-F化合物，其中X為至少一種與釹形成化合物之元素，例如，氧、氮、硫、氯等；或至少一種與氟形成化合物之金屬元素(除Nd以外)，例如，金屬元素，諸如Na、K、Al、Mg、Li、Ca、Sr、Ba及Y或該等元素之組合。Nd-X-F化合物之特定實例可包括：氧氟化釹(Nd-O-F)化合物；Nd-X-F化合物，其中X可為Mg及Ca或可為Mg、Ca及O；以及其他含有Nd-F之化合物，包括摻雜有釹之鈣鈦礦結構。某些Nd-X-F化合物可在約580nm之波長下有利地實現廣泛吸收。因為氧氟化釹化合物可包含不同量之O及F(因為氧氟化釹化合物通常衍生自不同量之氧化釹及NdF3)，所以氧氟化釹化合物可具有介於Nd-O化合物之折射率(例如，氧化釹之1.8)與Nd-F化合物之折射率(例如，NdF3之1.60)之間的經選擇之折射率。摻雜有釹之鈣鈦礦結構材料之非限制性實例包括含 有至少一種折射率比釹化合物(例如，NdF3)低之組分的彼等，例如Na、K、Al、Mg、Li、Ca、Sr、Ba及Y之金屬氟化物。該等「主體」化合物在可見光區中具有比NdF3低之折射率，其非限制性實例包括在波長589nm下之NaF(n=1.32)、KF(n=1.36)、AlF3(n=1.36)、MgF2(n=1.38)、LiF(n=1.39)、CaF2(n=1.44)、SrF2(n=1.44)、BaF2(n=1.48)及YF3(n=1.50)。由於摻雜有高折射率Nd-F化合物，例如NdF3，故所得經摻雜之鈣鈦礦結構化合物具有介於主體之折射率(例如，MgF2之1.38)與NdF3之折射率(1.60)之間的折射率。摻雜NdF3之金屬氟化物化合物之折射率將視Nd離子與金屬離子之比率而定。
通常，若基質及微粒材料之折射率在可見光區中在彼此0.1內，則據稱此處獲得低濁度(低漫射率)光學作用，其通常歸因於最低程度之光學散射。若NdF3在聚合基質材料為聚碳酸酯(PC)或聚苯乙烯(PS)之光學組件中用作唯一的無機微粒材料，則當光穿過該組件時，NdF3(約1.60)及PC與PS(約1.586)之折射率使得最低程度之光學散射產生。折射率在NdF3之0.1內之聚合物的另一實例為摻雜氟之聚酯(折射率為約1.607)。在此方面，基於具有類似於釹化合物之折射率來選擇聚合基質材料以便獲得低濁度(低漫射率)光學作用。
對微粒材料進行改質可獲得與在可見光區中折射率與釹化合物相差大於0.1之其他聚合物的折射率匹配。舉例而言，Nd3+離子來源(例如，NdF3)可與一或多種其他材料組合使用，以得到在光學組件中獲得最低程度光學散射的有效折射率，該光學組件之聚合基質材料在可見光區中具有與Nd3+離子來源相差大於0.1之折射率，例如丙烯酸(例如，聚甲基丙烯酸甲酯；PMMA)、聚氟化亞烷基(例如，聚偏二氟乙烯(PVDF))、聚矽氧等。作為一非限制性實例，由金屬氟化物及/或金屬氧化物形成之粒子可摻雜有釹化合物，以具有介於釹化合物之折射率與金屬氟化物及/或金屬氧化物之折射率之間的折射率。適合之 金屬氟化物及金屬氧化物之非限制性實例包括NaF(折射率為約1.32)及MgF2(折射率為約1.38)。藉由選擇釹化合物與金屬氟化物及/或金屬氧化物之適當比率，可調適微粒材料之折射率以允許與PMMA(約1.49)、聚偏二氟乙烯(約1.42)或甲基類型聚矽氧(約1.41)(其常常用於LED封裝中)之折射率匹配或接近匹配。
圖3及圖4為改編自以下出版物之曲線圖：「Controllable Energy Transfer in Fluorescence Upconversion of NdF3 and NaNdF4Nanocrystals」,Li等人，Optics Express，第18卷，第4期，第3364-3369頁，(2010)。曲線圖可表示以相同莫耳濃度分散於水中之NdF3及NaNdF4奈米晶的光學性質。圖3表示針對NdF3及NaNdF4奈米晶所觀測到的吸收光譜，且圖4表示當經受800nm之激發頻率(λexc)及240mW之激發功率時，NdF3及NaNdF4奈米晶之上轉換螢光光譜。如自圖3顯而易見，NdF3及NaNdF4之吸收峰分別為578及583，且因此完全在黃光波長範圍(約560至約600nm)內。圖4證實，NaNdF4之吸收峰相對於NdF3之吸收峰稍微偏移。圖3及圖4指示，NdF3及NaF之組合(得到NaNdF4)沒有根本上改變NdF3之吸收特徵。就此而論，咸信可用含有粒子(其含有除Nd-F以外已摻雜有Nd-F化合物以得到Nd-M-F化合物(其中M為除釹以外的金屬)之化合物)之複合材料獲得所需過濾色彩作用。
若在可見光區中聚合基質與微粒材料之折射率的差值超過0.1，則此處可獲得漫射光學作用(通常歸因於光學散射)。作為一個實例，NdF3(或另一Nd3+離子來源)可在光學組件中用作唯一的無機微粒材料，該光學組件之聚合基質材料具有充分不同於NdF3之折射率，例如PMMA、PVDF或聚矽氧。作為另一實例，可使用由鈣鈦礦結構材料形成之含有金屬氧化物及Nd3+離子來源的微粒材料。該等鈣鈦礦結構材料包括含有Ca、Ba、Al、Y、V、Gd及Sr中之至少兩者之氧化物的 鈣鈦礦結構材料，其可展現大於1.7之折射率，使得可用此等材料在與諸如PC、PS、PMMA、PVDF或聚矽氧之聚合基質材料組合使用時獲得所需過濾色彩作用及光學散射。
增大之折射率失配亦可藉由將NdF3(或另一Nd3+離子來源)之粒子與其他材料之粒子組合來獲得，該等材料之突出實例包括金屬氧化物，諸如金紅石型二氧化鈦(TiO2；折射率為約2.74)及Nd-O化合物(諸如，Nd2O3)或其他含釹金屬氧化物(諸如，含Nd鈣鈦礦結構材料)。用此方法，NdF3之粒子(或另一Nd3+離子來源)可大部分或完全負責過濾色彩作用，且第二粒子可大部分或完全負責獲得顯著程度之光學散射。
在可見光光譜中由Nd3+離子提供之由可見光吸收引起的過濾色彩作用咸信相對於在約560nm至約600nm範圍內之黃光波長優於Nd-O化合物(諸如，Nd2O3)。Nd-F及Nd-X-F化合物優於Nd-O化合物之另一優勢在於折射率愈加接近各種標準光學級透明塑膠(例如，PC、PS、PMMA、PVDF、聚矽氧及聚對苯二甲酸乙二酯(PET))，且可較好地平衡由可歸因於折射率失配之散射所引起的光損失與Nd離子吸收。藉由通過使用Nd-F及/或Nd-X-F化合物來過濾黃光波長，可調整由一或多個白色LED器件發射的光以獲得經增強之演色作用。舉例而言，經增強之演色作用可為經增強之紅-綠色彩對比；或經增強之演色作用可為增加之LED白光CRI(演色指數)或CSI(色彩飽和指數)，或可使色點能夠較接近白色軌跡(「白體線」)。藉由通過使用Nd-F及/或Nd-X-F化合物來過濾黃光波長，可調整由一或多個白色LED器件發射的光以獲得類似於白熾燈泡(可購自GE Lighting)之REVEAL線之照明效果的照明效果。製備具有由摻雜有氧化釹(Nd2O3)的玻璃形成之外部護套的白熾燈泡之REVEAL線，以過濾某些波長之光。圖5為表示分散於聚矽氧基質中的NdF3之光學透射與摻雜Nd2O3之玻璃相比的曲線 圖，且證實其光學透射的相似性，尤其在其過濾黃光波長的能力方面。
咸信複合材料中之Nd3+離子之微粒來源的體積量及粒度會影響複合材料之過濾色彩作用。此外，複合材料中之任何第二材料之相對量及粒度會影響過濾色彩作用。通常，咸信由標準光學級透明塑膠(例如，PC、PS、PMMA、PVDF、聚矽氧或PET)形成之複合材料應含有至少0.1體積%、且更佳約1至約20體積%之NdF3或另一Nd3+離子來源(例如，Nd-F化合物及Nd-X-F化合物，例如摻雜有Nd-F之MgF2)，以獲得所需過濾作用。若存在，則任何第二材料(例如，TiO2、含Nd化合物及相對於NdF3具有較高折射率的含Nd鈣鈦礦結構材料等)可以至多20體積%，更佳約0.01至約2體積%之量存在，視光學漫射體所需的散射概況而定。複合材料中之較佳總微粒負載量咸信為至少0.01至約20體積%，更佳為約0.01至約2體積%。進一步咸信，用於微粒材料之適合粒度為至多約50微米，且較佳為約0.5至約5微米。在此等負載量及粒度下，基質材料為前述標準光學級透明塑膠中之一者的複合材料將通常可易於塑為各種形狀，且在較小粒度及較高負載量情況下可能會遇到困難。
儘管本發明已關於某些實施例描述，但顯而易見，熟習此項技術者可採用其他形式。因此，本發明之範疇應僅由隨附申請專利範圍限制。

Claims (15)

  1. 一種照明裝置之光學組件，該光學組件之至少一部分係由包含聚合基質材料及微粒材料之複合材料形成，該微粒材料對穿過該複合材料之可見光貢獻過濾色彩作用；其中該微粒材料包含含有Nd3+離子之釹化合物，該釹化合物為Nd-X-F化合物，且X為至少一種與釹形成化合物之元素或至少一種與氟形成化合物之除釹以外的金屬元素。
  2. 如請求項1之光學組件，其中該微粒材料對由LED器件產生之可見光貢獻該過濾色彩作用，或其中該微粒材料主要過濾在黃光波長範圍內的波長。
  3. 如請求項1之光學組件，其中該釹化合物係以該微粒材料之離散粒子形式存在。
  4. 如請求項1之光學組件，其中該微粒材料為無機微粒材料，且其中該釹化合物係以該無機微粒材料之粒子中的摻雜劑形式存在。
  5. 如請求項1之光學組件，其中該釹化合物係以至少約0.1體積%之量存在於該複合材料中。
  6. 如請求項1之光學組件，其中該釹化合物係以約1至約20體積%之量存在於該複合材料中。
  7. 如請求項1之光學組件，其中該聚合基質材料係選自由聚碳酸酯、聚苯乙烯、聚丙烯酸酯、聚氟化亞烷基及聚矽氧組成之群。
  8. 如請求項1之光學組件，其中該釹化合物及該聚合基質材料具有在該可見光區中在彼此0.1內的折射率，或其中該微粒材料及該聚合基質材料具有在該可見光區中在彼此0.1內的折射率。
  9. 如請求項8之光學組件，其中該釹化合物係以該微粒材料之離散粒子形式存在，或其中該釹化合物係以該微粒材料之粒子中的摻雜劑形式存在，且該等粒子係由除該釹化合物以外的第二材料形成。
  10. 如請求項9之光學組件，其中該釹化合物為NaNdF4。
  11. 如請求項9之光學組件，其中該等粒子係由至少一種選自具有小於該聚合基質材料之折射率之金屬氟化物或金屬氧化物的材料形成。
  12. 如請求項9之光學組件，其中該等粒子係由至少一種選自由NaF、MgF2、KF、AlF3、LiF、CaF2、SrF2、BaF2及YF3組成之群的材料形成。
  13. 如請求項1之光學組件，其中該光學組件為包圍該照明裝置之LED器件的外罩或圓頂。
  14. 如請求項1之光學組件，其中該釹化合物及該聚合基質材料具有在該可見光區中相差大於0.1的折射率，或其中該微粒材料及該聚合基質材料具有在該可見光區中相差大於0.1的折射率。
  15. 一種照明裝置，其包含發射可見光之光源及經組態且經配置使得該光源之至少一些可見光穿過其的光學組件，該光學組件之一部分係由包含聚合基質材料及無機微粒材料的複合材料形成，該無機微粒材料對穿過該部分的可見光貢獻過濾色彩作用，該無機微粒材料包含Nd-X-F化合物，其中X為至少一種與釹形成化合物之元素或至少一種與氟形成化合物之除釹以外的金屬元素。
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