TW201835305A - Structure of Quantum Dot Ｍaterial, Manufacturing Method thereof, and Light-Emitting Device Using the Same - Google Patents
Structure of Quantum Dot Ｍaterial, Manufacturing Method thereof, and Light-Emitting Device Using the Same Download PDFInfo
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Abstract
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本發明係關於一種量子點材料的結構、製造方法、及發光裝置，尤關於一種包含量子點粒子及矽氧樹脂的製造方法。The present invention relates to a structure, a manufacturing method, and a light-emitting device of a quantum dot material, and more particularly to a method for manufacturing a quantum dot particle and a germanium oxide resin.
量子點材料由於具有量子侷限效應（quantum confined effect），可以藉由調整量子點材料的粒徑大小而改變發光波長。此外，選擇適當的量子點材料也可以改變發光波長。Due to the quantum confined effect, quantum dot materials can change the wavelength of light by adjusting the size of the quantum dot material. In addition, the choice of the appropriate quantum dot material can also change the wavelength of the emission.
量子點材料所發出的光線可具有較小的半高寬（FWHM）。即表示發出的光線更接近單色光（monochromatic light），適合應用於LCD顯示器上，如此可以減少被彩色濾光片濾除的光量。The light emitted by the quantum dot material can have a small full width at half maximum (FWHM). That is to say, the emitted light is closer to monochromatic light, which is suitable for use on an LCD display, so that the amount of light filtered by the color filter can be reduced.
量子點材料應用於發光裝置中的方式之一，是將量子點材料分散於接合劑中形成一膠體，再將此膠體覆蓋在發光元件的表面上。One of the ways in which quantum dot materials are used in light-emitting devices is to disperse a quantum dot material in a bonding agent to form a colloid, and then coat the colloid on the surface of the light-emitting element.
本發明之一實施例係揭露一種波長轉換材料，包含複數個量子點粒子、矽氧樹脂以及複數個含鉑粒子。量子點粒子以及含鉑粒子分散於矽氧樹脂中。量子點粒子包含量子點以及配位基（ligand）。配位基包含可能會與鉑形成錯合物（complex）的第一基團以及包覆第一基團之第二基團，其中，第二基團包含含氮雜環之基團。One embodiment of the present invention discloses a wavelength converting material comprising a plurality of quantum dot particles, a cerium oxide resin, and a plurality of platinum-containing particles. The quantum dot particles and the platinum-containing particles are dispersed in the oxime resin. Quantum dot particles contain quantum dots as well as ligands. The ligand comprises a first group which may form a complex with platinum and a second group which coats the first group, wherein the second group comprises a nitrogen-containing heterocyclic group.
本發明之一另一實施例係揭露一種波長轉換材料的製造方法。包含提供複數個量子點粒子，量子點粒子包含量子點以及可能會與鉑形成錯合物的第一基團之配位基；將複數個量子點粒子與包含第二基團之保護劑混合成第一混合物；將含氫基矽基團（Si-H group），含乙烯基矽基團（Si-vinyl group）以及含鉑粒子與第一混合物混合後，形成第二混合物；以及固化第二混合物，其中，第二基團包含含氮雜環之基團。Another embodiment of the present invention discloses a method of fabricating a wavelength converting material. The invention comprises providing a plurality of quantum dot particles, the quantum dot particles comprising quantum dots and a ligand of a first group which may form a complex with platinum; mixing a plurality of quantum dot particles with a protective agent containing the second group a first mixture; mixing a hydrogen-containing sulfonium group (Si-H group), a vinyl-containing group (Si-vinyl group), and a platinum-containing particle with the first mixture to form a second mixture; and curing the second a mixture wherein the second group comprises a nitrogen-containing heterocyclic group.
於本文中，第二基團包覆第一基團是指第二基團以共價鍵之化學鍵與第一基團結合或是以氫鍵或凡德瓦力（van der Waals forces）的方式形成於第一基團之表面上。包覆的方式可為第一基團的表面完全被第二基團所包覆或是部分的第一基團表面被第二基團所包覆。As used herein, the second group encapsulating the first group means that the second group is bonded to the first group by a chemical bond of a covalent bond or by means of hydrogen bonding or van der Waals forces. Formed on the surface of the first group. The coating may be carried out by completely covering the surface of the first group with the second group or partially covering the surface of the first group with the second group.
於本文中，第一基團及／或第二基團是指具有特定官能基團的化學物質。可能是指一完整的化合物或具有官能基團之化合物的一部分。As used herein, a first group and/or a second group refers to a chemical having a particular functional group. It may refer to a complete compound or a part of a compound having a functional group.
第1圖顯示根據本發明一實施例之波長轉換材料100的示意圖。波長轉換材料100包含複數個量子點粒子120 、矽氧樹脂140及複數個含鉑粒子（粒子中包含鉑元素成分）160。複數個量子點粒子120及多個含鉑粒子160分散於矽氧樹脂140中。此外，量子點粒子120包含量子點122以及量子點122表面的配位基（ligand）124。量子點122表面的配位基（ligand）124包含可能會與鉑形成錯合物（complex）的第一基團124a以及包覆第一基團之第二基團124b，其中，第二基團包含含氮雜環（Nitrogen Heterocyclic Ring）之基團。1 shows a schematic diagram of a wavelength converting material 100 in accordance with an embodiment of the present invention. The wavelength conversion material 100 includes a plurality of quantum dot particles 120, a cerium oxide resin 140, and a plurality of platinum-containing particles (including platinum element components in the particles) 160. A plurality of quantum dot particles 120 and a plurality of platinum-containing particles 160 are dispersed in the epoxy resin 140. Further, the quantum dot particles 120 include quantum dots 122 and a ligand 124 on the surface of the quantum dots 122. The ligand 124 on the surface of the quantum dot 122 contains a first group 124a that may form a complex with platinum and a second group 124b that coats the first group, wherein the second group A group comprising a Nitrogen Heterocyclic Ring.
量子點粒子120可在接受一能量後，以光形態釋放另一能量（通常是光能）。提供給量子點粒子120的能量可以是光能或電能。在一實施例中，量子點粒子120在吸收發光元件，例如：發光二極體（LED）的第一波長後，發出波長較長的第二波長。第二波長的波峰可以是可見光或紅外光。此外，量子點粒子120具有量子侷限（quantum confinement）的特性，藉由改變量子點粒子120的粒徑大小可調整發光波長。關於量子點120的結構及材料可參閱說明書段落[0014]及[0016]。The quantum dot particles 120 can release another energy (usually light energy) in the form of light after receiving an energy. The energy provided to the quantum dot particles 120 can be light energy or electrical energy. In one embodiment, the quantum dot particles 120 emit a second wavelength having a longer wavelength after absorbing a first wavelength of a light emitting element, such as a light emitting diode (LED). The peak of the second wavelength may be visible light or infrared light. In addition, the quantum dot particles 120 have a quantum confinement characteristic, and the emission wavelength can be adjusted by changing the particle size of the quantum dot particles 120. Regarding the structure and material of the quantum dot 120, reference is made to the paragraphs [0014] and [0016] of the specification.
波長轉換材料100可包含單一或多種種類的量子點粒子120。在本案中，單一種類的量子點粒子可指量子點122的材料相同，且量子點122的粒徑也大致相同（即發出相近或相同的色光）。多種的量子點粒子120可指量子點122的材料不同或量子點122的材料相同但粒徑不同。在一實施例中，波長轉換材料100包含可發出藍光之量子點粒子120、可發出綠光之量子點粒子120或可發出紅光之量子點粒子120。另一實施例中，波長轉換材料100包含可發出綠光及紅光之多種量子點粒子120。另一實施例中，波長轉材料100包含可發出藍光，綠光及紅光之多種量子點粒子120。The wavelength converting material 100 can comprise single or multiple types of quantum dot particles 120. In the present case, a single type of quantum dot particle may mean that the material of the quantum dot 122 is the same, and the particle diameter of the quantum dot 122 is also substantially the same (ie, emits a similar or the same color light). The plurality of quantum dot particles 120 may refer to different materials of the quantum dots 122 or the same material of the quantum dots 122 but different particle sizes. In one embodiment, the wavelength converting material 100 comprises quantum dot particles 120 that emit blue light, quantum dot particles 120 that emit green light, or quantum dot particles 120 that emit red light. In another embodiment, the wavelength converting material 100 comprises a plurality of quantum dot particles 120 that emit green and red light. In another embodiment, the wavelength converting material 100 comprises a plurality of quantum dot particles 120 that emit blue, green, and red light.
波長轉換材料100可形成為單層或多層結構。在一實施例中，波長轉換材料100形成為單層結構，其中，單一種類的量子點粒子120或多種的量子點粒子120分散在單一層的矽氧樹脂140中。若多種量子點粒子120分散在單一層的矽氧樹脂140中，不同種類的量子點粒子120間通常並沒有清楚的界線，可能是隨機地散佈在樹脂層中。若是多種量子點粒子12分別位於多層的矽氧樹脂140中，一層材料層中僅包含有一種量子點粒子120，不同種類的量子點粒子120間通常存在清楚的界面。此外，量子點粒子120的分布型態也可能是上述二種方式的組合。舉例而言，存在三種量子點粒子的情況下，第一種量子點粒子與第二種量子點粒子共同分散於同一層的矽氧樹脂140中，第三種量子點粒子則單獨分散於另一層的矽氧樹脂140中，上述兩層的矽樹脂140可彼此堆疊（圖未示）。The wavelength converting material 100 may be formed in a single layer or a multilayer structure. In one embodiment, the wavelength converting material 100 is formed in a single layer structure in which a single kind of quantum dot particles 120 or a plurality of quantum dot particles 120 are dispersed in a single layer of the epoxy resin 140. If the plurality of quantum dot particles 120 are dispersed in the single layer of the oxime resin 140, there is usually no clear boundary between the different kinds of quantum dot particles 120, and may be randomly dispersed in the resin layer. If a plurality of quantum dot particles 12 are respectively located in the multilayer epoxy resin 140, only one quantum dot particle 120 is contained in one material layer, and a clear interface exists between the different kinds of quantum dot particles 120. In addition, the distribution pattern of the quantum dot particles 120 may also be a combination of the above two modes. For example, in the case of three kinds of quantum dot particles, the first quantum dot particle and the second quantum dot particle are co-dispersed in the same layer of the epoxy resin 140, and the third quantum dot particle is separately dispersed in the other layer. In the epoxy resin 140, the above two layers of the ruthenium resin 140 may be stacked on each other (not shown).
參閱第1圖，波長轉換材料100可包含除了量子點粒子120之外的波長轉換物質。於一實施例中，其他種類的螢光粉物質（圖未示）與量子點粒子120同時混合於矽氧樹脂140中。例如：以錳四價為活化中心之氟化物螢光粉（可發出紅光），與綠光之量子點粒子120同時混合於矽氧樹脂140中。於另一實施例中，其他種類的螢光粉物質（圖未示）與量子點粒子120以分層方式混合於矽氧樹脂140中。例如：可發綠光之氮氧化物螢光粉分散於一矽氧樹脂中，形成為靠近光源處的一層螢光粉層，發紅光之量子點粒子120分散於另一矽氧樹脂140中並覆蓋在此螢光粉層之上。在另一實施例中，波長轉換材料形成為一包含第一波長轉換層（圖未示）及第二波長轉換層（圖未示）之結構，且第一波長轉換層堆疊在第二波長轉換層之上。第一波長轉換層包含分散在矽氧樹脂中的發紅光之量子點粒子。第二波長轉換層包含分散在矽氧樹脂中的發綠光之量子點粒子。光源（圖未示），例如：發光二極體，所發出的光線可由第一波長轉換層進入後，再射向第二波長轉換層。光源的短波長光線在通過第一波長轉換層時被部分轉換成紅光，通過第二波長轉換層時再被部分轉換為綠光。藉由此多層結構及疊層順序，可減少綠光被發紅光之量子點粒子再吸收的機會。Referring to FIG. 1, the wavelength converting material 100 may include a wavelength converting substance other than the quantum dot particles 120. In one embodiment, other types of phosphor material (not shown) are mixed with the quantum dot particles 120 in the epoxy resin 140. For example, a fluoride phosphor (which emits red light) having a manganese tetravalent activation center is mixed with the green light quantum dot particles 120 in the epoxy resin 140. In another embodiment, other types of phosphor material (not shown) and quantum dot particles 120 are mixed in a layered manner in the epoxy resin 140. For example, the oxynitride fluorescing powder that emits green light is dispersed in a cerium oxide resin to form a layer of phosphor powder near the light source, and the reddish quantum dot particles 120 are dispersed in the other oxime resin 140. And over the layer of phosphor powder. In another embodiment, the wavelength converting material is formed into a structure including a first wavelength converting layer (not shown) and a second wavelength converting layer (not shown), and the first wavelength converting layer is stacked at the second wavelength conversion. Above the layer. The first wavelength converting layer contains reddish-emitting quantum dot particles dispersed in a cerium oxide resin. The second wavelength conversion layer contains green-emitting quantum dot particles dispersed in the oxime resin. A light source (not shown), such as a light-emitting diode, emits light from the first wavelength conversion layer and then to the second wavelength conversion layer. The short-wavelength light of the light source is partially converted into red light when passing through the first wavelength conversion layer, and partially converted to green light when passing through the second wavelength conversion layer. By virtue of the multilayer structure and the lamination sequence, the chance of green light being re-absorbed by the reddish quantum dot particles can be reduced.
波長轉換材料100還可包含光散射粒子（圖未示）。於一實施例中，多顆光散射粒子分散於矽氧樹脂140中。光散射粒子可散射進入波長轉換材料100的的光線（第一波長光線，例如LED的光線），增加第一波長光線於波長轉換材料100內移動的路徑，進而提高第一波長光線被波長轉換物質吸收的機率。光散射粒子的材料可包含氧化矽或氧化鈦粒子。The wavelength converting material 100 may also include light scattering particles (not shown). In one embodiment, a plurality of light scattering particles are dispersed in the epoxy resin 140. The light scattering particles can scatter light entering the wavelength conversion material 100 (light of the first wavelength, such as light of the LED), increase the path of the first wavelength light moving within the wavelength conversion material 100, thereby increasing the wavelength of the first wavelength light by the wavelength conversion material. The probability of absorption. The material of the light scattering particles may comprise cerium oxide or titanium oxide particles.
在一實施例中，量子點粒子120在吸收發光元件，例如：發光二極體（LED），的入射光（第一波長光）後，發射（轉換成）波長較長的第二波長光。在一實施例中，第一波長光及第二波長光皆為可見光。例如：第一波長光為藍光，第二波長光為綠光或／及紅光。在另一實施例中，第一波長光為紫外光，第二波長光為可見光。於另一實施例中，第一波長光為可見光但第二波長光為紅外光。在一實施例中，量子點粒子120於波長轉換材料100中的重量百分比在0.5%以上。在另一實施例中，量子點粒子120於波長轉換材料100中的重量百分比在1%至10%之間。在另一實施例中，量子點粒子120於波長轉換材料100中的重量百分比在5%至20%之間。In one embodiment, the quantum dot particles 120 emit (convert) into a second wavelength of light having a longer wavelength after absorbing the incident light (first wavelength light) of the light emitting element, such as a light emitting diode (LED). In an embodiment, the first wavelength light and the second wavelength light are both visible light. For example, the first wavelength light is blue light, and the second wavelength light is green light and/or red light. In another embodiment, the first wavelength of light is ultraviolet light and the second wavelength of light is visible light. In another embodiment, the first wavelength of light is visible light but the second wavelength of light is infrared light. In one embodiment, the weight percentage of quantum dot particles 120 in the wavelength converting material 100 is above 0.5%. In another embodiment, the weight percentage of quantum dot particles 120 in the wavelength converting material 100 is between 1% and 10%. In another embodiment, the weight percentage of quantum dot particles 120 in the wavelength converting material 100 is between 5% and 20%.
量子點122可由半導體材料所構成，且其粒徑小於100 奈米（nm）。量子點122的半導體材料包含II-VI族半導體化合物、III-V族半導體化合物、IV-VI族半導體化合物、或上述材料的組合。量子點122的結構可包含主要發光的核心區（core）以及包覆核心區的殼（shell）。核心區的材料可選自於由硫化鋅（ZnS）、硒化鋅（ZnSe）、碲化鋅（ZnTe）、氧化鋅（ZnO）、硫化鎘（CdS）、硒化鎘（CdSe）、碲化鎘（CdTe）、氮化鎵（GaN）、磷化鎵（GaP）、硒化鎵（GaSe）、銻化鎵（GaSb）、砷化鎵（GaAs）、氮化鋁（AlN）、磷化鋁（AlP）、砷化鋁（AlAs）、磷化銦（InP）、砷化銦（InAs）、碲（Te）、硫化鉛（PbS）、銻化銦（InSb）、碲化鉛（PbTe）、硒化鉛（PbSe）、碲化銻（SbTe） 、硒化鋅鎘（ZnCdSe）、硫化鋅鎘硒（ZnCdSeS）、及硫化銅銦（CuInS）所組成之群組。殼的材料與核心區的材料必須相互搭配（例如核心區與殼的材料的晶格常數需要匹配）。具體而言，殼的材料組成之選擇，除了與核心區的材料的晶格常數需匹配外，尚能在核心區的外圍形成一個高能障區域，以提升量子產率（quantum yield）。藉由殼的結構及／或組成的改變，可減少核心區與殼的應力，並拉高能障。殼的結構可以是單層、多層或者材料組成漸變的結構。在一實施例中，核心區為硒化鎘，殼為單層的硫化鋅。在另一實施例中，核心區為硒化鎘，殼包含內層的（鎘, 鋅）（硫, 硒）及外層的硫化鋅。在另一實施例中，核心區為硒化鎘，殼包含內層的硫化鎘，中間漸變層的Zn0.25 Cd0.75 S/Zn0.5 Cd0.5 S/Zn0.75 Cd0.25 S，外層的硫化鋅。Quantum dots 122 may be composed of a semiconductor material and have a particle size of less than 100 nanometers (nm). The semiconductor material of the quantum dot 122 comprises a II-VI semiconductor compound, a III-V semiconductor compound, an IV-VI semiconductor compound, or a combination thereof. The structure of the quantum dots 122 may comprise a core that primarily illuminates and a shell that covers the core region. The material of the core region may be selected from zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), zinc oxide (ZnO), cadmium sulfide (CdS), cadmium selenide (CdSe), and bismuth. Cadmium (CdTe), GaN, GaP, GaSe, GaSb, GaAs, AlN, Aluminium Phosphide (AlP), AlGaAs, InP, InAs, Te, Lead (PbS), InSb, PbTe, A group consisting of lead selenide (PbSe), antimony telluride (SbTe), zinc cadmium selenide (ZnCdSe), zinc cadmium selenide (ZnCdSeS), and copper indium sulfide (CuInS). The material of the shell and the material of the core must match each other (for example, the lattice constants of the core and shell materials need to match). Specifically, the choice of the material composition of the shell, in addition to matching the lattice constant of the material of the core region, can form a high energy barrier region on the periphery of the core region to enhance the quantum yield. By changing the structure and/or composition of the shell, the stress in the core region and the shell can be reduced and the energy barrier can be increased. The structure of the shell may be a single layer, a multilayer or a material with a gradual structure. In one embodiment, the core region is cadmium selenide and the shell is a single layer of zinc sulfide. In another embodiment, the core region is cadmium selenide and the shell comprises an inner layer of (cadmium, zinc) (sulfur, selenium) and an outer layer of zinc sulfide. In another embodiment, the core region is cadmium selenide, the shell comprises an inner layer of cadmium sulfide, and the intermediate grade layer is Zn 0.25 Cd 0.75 S/Zn 0.5 Cd 0.5 S/Zn 0.75 Cd 0.25 S, and the outer layer is zinc sulfide.
其他種類（非量子點）的螢光粉材料可選自於由Y3 Al5 O12 ：Ce、Gd3 Ga5 O12 ：Ce、Lu3 Al5 O12 ：Ce、（Lu、Y）3 Al5 O12 ：Ce、Tb3 Al5 O12 ：Ce、SrS：Eu、SrGa2 S4 ：Eu、（Sr、Ca、Ba）（Al、Ga）2 S4 ：Eu、（Ca、Sr）S：（Eu、Mn）、（Ca、Sr）S：Ce、（Ba、Sr、Ca）2 SiO4 ：Eu、（Ca、Sr、Ba）Si2 O2 N2 ：Eu 、（Sr、Ba、Ca）2 Si5 N8 ：Eu、（Sr、Ba、Ca）（Al、Ga）Si N3 ：Eu、CaAlmSi12−m OnN16−n ：Eu、SrLiAl3 N4 ：Eu、Ba2 LiSi7 AlN12 ：Eu、K2 SiF6 ：Mn、K2 TiF6 ：Mn、及K2 SnF6 ：Mn 所組成之群組。Other kinds of (non-quantum dots) phosphor materials may be selected from Y 3 Al 5 O 12 :Ce, Gd 3 Ga 5 O 12 :Ce, Lu 3 Al 5 O 12 :Ce, (Lu, Y) 3 Al 5 O 12 :Ce, Tb 3 Al 5 O 12 :Ce, SrS:Eu, SrGa 2 S 4 :Eu, (Sr,Ca,Ba)(Al,Ga) 2 S 4 :Eu, (Ca,Sr) S: (Eu, Mn), (Ca, Sr) S: Ce, (Ba, Sr, Ca) 2 SiO 4 : Eu, (Ca, Sr, Ba) Si 2 O 2 N 2 : Eu, (Sr, Ba , Ca) 2 Si 5 N 8 :Eu, (Sr, Ba, Ca)(Al, Ga)Si N 3 :Eu, CaAlmSi 12−m OnN 16−n :Eu, SrLiAl 3 N 4 :Eu, Ba 2 LiSi 7 AlN 12: Eu, K 2 SiF 6: Mn, K 2 TiF 6: Mn, and K 2 SnF 6: the group consisting of Mn.
配位基124具有特定的官能基團（functional group），可用以控制量子點122的尺寸使其維持在奈米尺度。此外，配位基124可提高量子點122分散於矽氧樹脂140的穩定性。在一實施例中，配位基會同時包含可與量子點粒子120之表面產生吸引力的官能基團，例如：胺基（amine group），以及阻止量子點粒子120彼此團聚的官能基團，例如：脂肪族（aliphatic group）。不過，量子點粒子120的配位基124同時也包含可能會與鉑形成錯合物（complex）的第一基團124a。配位基124與鉑形成錯合物（complex）會造成鉑的催化活性降低，此現象也稱作毒化鉑（poisoning Pt ）。Ligand 124 has a specific functional group that can be used to control the size of quantum dots 122 to maintain it at the nanometer scale. In addition, the ligand 124 can improve the stability of the quantum dots 122 dispersed in the silicone resin 140. In one embodiment, the ligand will simultaneously contain functional groups that are attractive to the surface of the quantum dot particles 120, such as an amine group, and functional groups that prevent the quantum dot particles 120 from agglomerating with each other, For example: aliphatic group. However, the ligand 124 of the quantum dot particle 120 also contains a first group 124a that may form a complex with platinum. The complex formation of ligand 124 with platinum causes a decrease in the catalytic activity of platinum, a phenomenon also known as poisoning Pt.
在一實施例中，第一基團124a包含膦（phosphine）或氧化膦（phosphine oxide）。膦之化學式為PRa Rb Rc ，其中Ra 、Rb 、Rc 分別為氫或烷基（alkyl group），且至少一者為烷基。例如：三辛基膦（trioctylphosphine, TOP），化學式為C24 H51 P。氧化膦之化學式為OP Rd Re Rf ，其中Rd 、Re 、Rf 分別為氫或烷基（alkyl group），且至少一者為烷基。例如：三辛基氧膦（trioctylphosphine oxide, TOPO），化學式為C24 H51 PO。此外，配位基124還包含包覆第一基團124a之第二基團124b。在一實施例中，第二基團124b包含含氮雜環（nitrogen heterocyclic ring）之基團。藉由包覆第一基團124a之第二基團124b，可減弱第一基團124a對鉑的作用，進而減低第一基團124a對鉑的毒化效果。於一實施例中，第二基團124b包含4-哌啶乙醇（4-Piperidineethanol），化學式為C7 H15 NO。於一實施例中，第一基團124a為三辛基膦，被第二基團124b 4-哌啶乙醇所包覆。若兩者產生化學反應形成共價鍵，則可能形成化學式Rg Rh ，其中Rg 為三辛基膦（第一基團124a）移除一個氫原子，Rh 為4-哌啶乙醇（第二基團124b）移除一個氫原子。此外，第二基團124b與第一基團124a也可能無化學反應形成，僅以氫鍵或凡德瓦力的方式形成於第一基團124a之表面上，則第一基團124a仍為三辛基膦，第二基團124b仍為4-哌啶乙醇。In one embodiment, the first group 124a comprises phosphine or phosphine oxide. The chemical formula of the phosphine is PR a R b R c , wherein R a , R b , R c are each hydrogen or an alkyl group, and at least one is an alkyl group. For example: trioctylphosphine (TOP), the chemical formula is C 24 H 51 P. The phosphine oxide has the formula OP R d R e R f , wherein R d , R e , R f are each hydrogen or an alkyl group, and at least one is an alkyl group. For example: trioctylphosphine oxide (TOPO), the chemical formula is C 24 H 51 PO. In addition, the ligand 124 further comprises a second group 124b that coats the first group 124a. In one embodiment, the second group 124b comprises a group of a nitrogen heterocyclic ring. By coating the second group 124b of the first group 124a, the effect of the first group 124a on platinum can be weakened, thereby reducing the poisoning effect of the first group 124a on platinum. In one embodiment, the second group 124b comprises 4-piperidineethanol (4-Piperidineethanol), the formula C 7 H 15 NO. In one embodiment, the first group 124a is trioctylphosphine and is coated with a second group 124b 4-piperidineethanol. If the two chemically react to form a covalent bond, a chemical formula R g R h may be formed, wherein R g is trioctylphosphine (first group 124a), one hydrogen atom is removed, and Rh is 4-piperidine ethanol ( The second group 124b) removes one hydrogen atom. In addition, the second group 124b and the first group 124a may also be formed without chemical reaction, and are formed only on the surface of the first group 124a by hydrogen bonding or van der Waals force, and the first group 124a is still Trioctylphosphine, the second group 124b is still 4-piperidineethanol.
第二基團124b的化學組成的資訊可由傅里葉轉換紅外光譜（FT-IR）量測得知。在一實施例中，第二基團124b包含含氮雜環之基團，因此分別在1300~1500 nm之間，1600~1800 nm之間，2800~2950 nm之間，以及3000~3300 nm之間，至少都有一個吸收波長。Information on the chemical composition of the second group 124b can be determined by Fourier Transform Infrared Spectroscopy (FT-IR) measurements. In one embodiment, the second group 124b comprises a nitrogen-containing heterocyclic group, and thus is between 1300 and 1500 nm, between 1600 and 1800 nm, between 2800 and 2950 nm, and between 3,000 and 3,300 nm. There is at least one absorption wavelength.
矽氧樹脂140可固定量子點粒子120，使得量子點粒子120能分散於矽氧樹脂140中。矽氧樹脂140包含以下化學式：R1 R2 R3 SiCH2 CH2 SiR4 R5 R6 ，其中R1 、R2 、R3 、R4 、R5 及R6 為有機基團或含矽基團。於一實施例中，矽氧樹脂140包含矽氧烷化合物（siloxane compound），R1 、R2 、R3 、R4 、R5 及R6 至少其中之一具有O-R7 基團，R7 為有機基團或含矽基團。於一實施例中，矽氧樹脂140具有以下化學式：(CH3)2 (OR8 )Si-CH2 -CH2 Si(CH3 )2 (OR9 )，R8 及R9 為有機基團或含矽基團。The oxime resin 140 can fix the quantum dot particles 120 such that the quantum dot particles 120 can be dispersed in the oxime resin 140. The oxime resin 140 contains the following chemical formula: R 1 R 2 R 3 SiCH 2 CH 2 SiR 4 R 5 R 6 , wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are an organic group or a ruthenium containing group Group. In one embodiment, the oxime resin 140 comprises a siloxane compound, at least one of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 having an OR 7 group, and R 7 is An organic group or a hydrazine-containing group. In one embodiment, the oxime resin 140 has the following chemical formula: (CH3) 2 (OR 8 )Si-CH 2 -CH 2 Si(CH 3 ) 2 (OR 9 ), and R 8 and R 9 are organic groups or Containing a hydrazine group.
含氫基矽基團（Si-H group）及含乙烯基矽基團（Si-vinyl group）可聚合成矽氧樹脂140，此時，含鉑粒子160可作為觸媒之用。因此，形成波長轉換材料100的矽氧樹脂140後，含鉑粒子160也會存在波長轉換材料100中。含鉑粒子160可以純鉑的形式、鉑錯合物（Pt complex）或上述之混合物存在於波長轉換材料100中。鉑錯合物可包含。The hydrogen-containing sulfonium group (Si-H group) and the vinyl group-containing group (Si-vinyl group) can be polymerized into the oxime resin 140. At this time, the platinum-containing particles 160 can be used as a catalyst. Therefore, after the neon resin 140 of the wavelength conversion material 100 is formed, the platinum-containing particles 160 are also present in the wavelength conversion material 100. The platinum-containing particles 160 may be present in the wavelength converting material 100 in the form of pure platinum, a platinum complex (Pt complex), or a mixture thereof. Platinum complexes can be included .
第2圖為製作波長轉換材料100的流程圖。首先，提供多顆量子點粒子120’ （步驟S210），此時量子點粒子120’包含量子點122以及可能會與鉑形成錯合物（complex）的第一基團124a，但還不包含第二基團124b。在一實施例中，多顆量子點粒子120’為粉末狀。在另一實施例中，多顆量子點粒子120’預先分散於溶劑（溶劑1）中。溶劑的種類可依量子點粒子120’的表面性質進行選擇。在一實施例中，溶劑為甲苯。FIG. 2 is a flow chart for fabricating the wavelength converting material 100. First, a plurality of quantum dot particles 120' are provided (step S210), in which case the quantum dot particles 120' comprise quantum dots 122 and a first group 124a which may form a complex with platinum, but does not include the first Two groups 124b. In one embodiment, the plurality of quantum dot particles 120' are in powder form. In another embodiment, a plurality of quantum dot particles 120' are previously dispersed in a solvent (solvent 1). The type of solvent can be selected depending on the surface properties of the quantum dot particles 120'. In one embodiment, the solvent is toluene.
將複數個量子點粒子120’與包含第二基團124b’之保護劑混合成混合物A（步驟S230）。A plurality of quantum dot particles 120' and a protective agent containing the second group 124b' are mixed into a mixture A (step S230).
於一實施例中，複數個量子點粒子120’與包含第二基團124b’之保護劑的重量比例不大於1：8.7。即表示使用1公克的量子點粒子120’，保護劑的用量不大於8.7公克。於一實施例中，包含第二基團124b’之保護劑已預先溶解於溶劑（溶劑2）中形成一溶液，粉末狀之量子點粒子120’加入溶液2並攪拌數小時，使其充分混合。溶劑2的種類需考量易於分散量子點粒子120’以及溶解保護劑。在一實施例中，溶劑2為甲苯。於另一實施例中，則將預先分散於溶劑1的量子點粒子120’與預先溶解於溶劑2的保護劑攪拌混合。In one embodiment, the weight ratio of the plurality of quantum dot particles 120' to the protecting agent comprising the second group 124b' is no greater than 1:8.7. That is, it is indicated that 1 g of the quantum dot particles 120' is used, and the amount of the protective agent is not more than 8.7 g. In one embodiment, the protecting agent comprising the second group 124b' has been previously dissolved in a solvent (solvent 2) to form a solution, and the powdered quantum dot particles 120' are added to the solution 2 and stirred for several hours to be thoroughly mixed. . The type of the solvent 2 is considered to be easy to disperse the quantum dot particles 120' and the dissolution protecting agent. In one embodiment, solvent 2 is toluene. In another embodiment, the quantum dot particles 120' previously dispersed in the solvent 1 are stirred and mixed with a protective agent previously dissolved in the solvent 2.
將另一溶劑（溶劑3）加入混合物A（步驟S250），使量子點粒子120’與保護劑沉澱。溶劑3的種類需選擇量子點粒子120’不能或困難分散其中，以及保護劑不會或困難溶解其中的溶劑。在一實施例中，溶劑3為乙醇。之後，取出沉澱物並加熱。取出沉澱物的方式例如但不限為使用離心方式。加熱可同時移除多於的溶劑以及使得量子點粒子120’與保護劑產生化學反應形成包含包覆第一基團之第二基團124b之量子點粒子120。Another solvent (solvent 3) is added to the mixture A (step S250) to precipitate the quantum dot particles 120' and the protective agent. The type of solvent 3 is such that the quantum dot particles 120' are not selected or difficult to disperse therein, and the solvent in which the protective agent does not or is difficult to dissolve. In one embodiment, solvent 3 is ethanol. After that, the precipitate was taken out and heated. The manner in which the precipitate is taken out is, for example, but not limited to, using a centrifugal method. Heating can simultaneously remove more solvent and chemically react the quantum dot particles 120' with the protecting agent to form quantum dot particles 120 comprising a second group 124b that coats the first group.
將複數個量子點粒子120與含氫基矽基團（Si-H group），含乙烯基矽基團（Si-vinyl group）以及含鉑粒子混合成混合物B（步驟S270）。The plurality of quantum dot particles 120 are mixed with a hydrogen-containing sulfonium group (Si-H group), a vinyl group-containing group (Si-vinyl group), and platinum-containing particles to form a mixture B (step S270).
含氫基矽基團可以是以單體（Monomer）、預聚物（prepolymer）或上述兩者之混合的型態存在。例如：(CH3 )2 (OR10 )Si-H，其中R10 為有機基團或含矽基團。The hydrogen-containing sulfonium group may be present in the form of a monomer, a prepolymer or a mixture of the two. For example: (CH 3 ) 2 (OR 10 )Si-H, wherein R 10 is an organic group or a hydrazine-containing group.
含乙烯基矽基團可以是以單體（Monomer）、預聚物（prepolymer）或上述兩者之混合的型態存在。例如：(CH3 )2 (OR11 )Si-CH=CH2 ，其中R11 為有機基團或含矽基團。The vinyl group-containing group may be present in the form of a monomer, a prepolymer or a mixture of the two. For example: (CH 3 ) 2 (OR 11 )Si-CH=CH 2 , wherein R 11 is an organic group or a hydrazine-containing group.
固化混合物B成矽氧樹脂（步驟S290）。The mixture B is cured to form a silicone resin (step S290).
於一實施例中，固化步驟為加熱方式提供固化所需能量。由於本發明的實施例中已減少或消除量子點粒子120對鉑毒化的影響，因此，固化所需的溫度不會因鉑毒化的問題需升高，也因此，於較高溫度下造成量子點粒子120的量子效率下降的問題也可被改善。於一實施例中，固化溫度不大於150℃。In one embodiment, the curing step provides the energy required for curing in a heating mode. Since the effect of the quantum dot particles 120 on the poisoning of the platinum has been reduced or eliminated in the embodiment of the present invention, the temperature required for curing is not required to be increased due to the problem of platinum poisoning, and therefore, the quantum dots are caused at a higher temperature. The problem of a decrease in the quantum efficiency of the particles 120 can also be improved. In one embodiment, the curing temperature is no greater than 150 °C.
第3圖顯示根據本發明一實施例之發光裝置300。發光裝置300包含一發光元件320、導電元件340、一波長轉換材料360、一環繞發光元件320以及波長轉換材料360的光反射圍欄380。具體而言，發光元件320具有一頂面、底面及多個側面。波長轉換材料360的結構以及製造方法可參閱前述說明。發光元件320的側面位於頂面及底面之間。導電元件340形成在發光元件320之底面上並於發光元件320電性連結。波長轉換元件360覆蓋發光元件320的頂面，且光反射圍欄380環繞發光元件320的側面以及波長轉換材料360。在一實施例中，光反射圍欄380與部分的導電元件340之底面大致為共平面。在另一實施例中，光反射圍欄380與導電元件340之底面可以是不共平面。Figure 3 shows a light emitting device 300 in accordance with an embodiment of the present invention. The light emitting device 300 includes a light emitting element 320, a conductive element 340, a wavelength converting material 360, a surrounding light emitting element 320, and a light reflecting fence 380 of the wavelength converting material 360. Specifically, the light emitting element 320 has a top surface, a bottom surface, and a plurality of side surfaces. The structure and manufacturing method of the wavelength converting material 360 can be referred to the foregoing description. The side surface of the light emitting element 320 is located between the top surface and the bottom surface. The conductive element 340 is formed on the bottom surface of the light emitting element 320 and electrically connected to the light emitting element 320. The wavelength conversion element 360 covers the top surface of the light emitting element 320, and the light reflecting fence 380 surrounds the side of the light emitting element 320 and the wavelength converting material 360. In one embodiment, the light reflecting fence 380 is substantially coplanar with the bottom surface of the portion of the conductive element 340. In another embodiment, the light reflecting fence 380 and the bottom surface of the conductive element 340 may be non-coplanar.
發光元件320可以是一個發光二極體晶粒。在一實施例中，發光二極體晶粒為一覆晶式發光二極體晶粒，發光二極體晶粒包含一透明基板322、發光疊層324形成在透明基板322之一表面上、以及第一電極及第二電極（圖未示）。其中，第一電極及第二電極形成在發光疊層324的另一表面上，並分別與導電元件340之第一導電墊342以及第二導電墊344電性連結。在一實施例中，發光疊層324包含第一型半導體層及第二型半導體層，且第一電極及第二電極分別形成在第一型半導體層及第二型半導體層上。一般而言，發光元件320可發出的波長小於量子點粒子120發出的波長。在一實施例中，發光二極體晶粒是發出藍光波長。在另一實施例中，發光二極體晶粒是發出紫外光波長。The light emitting element 320 can be a light emitting diode die. In one embodiment, the light emitting diode die is a flip chip light emitting diode die, the light emitting diode die includes a transparent substrate 322, and the light emitting stack 324 is formed on a surface of the transparent substrate 322. And a first electrode and a second electrode (not shown). The first electrode and the second electrode are formed on the other surface of the light emitting layer 324 and electrically connected to the first conductive pad 342 and the second conductive pad 344 of the conductive element 340, respectively. In one embodiment, the light emitting stack 324 includes a first type semiconductor layer and a second type semiconductor layer, and the first electrode and the second electrode are respectively formed on the first type semiconductor layer and the second type semiconductor layer. In general, the illuminating element 320 can emit a wavelength that is less than the wavelength emitted by the quantum dot particles 120. In one embodiment, the light emitting diode grains emit blue light wavelengths. In another embodiment, the light emitting diode grains emit a wavelength of ultraviolet light.
光反射圍欄380可將發光元件320以及波長轉換層360發出的光線反射向上。在一實施例中，發光元件320與光反射圍欄380直接接觸。不過，依發光角度以及亮度的整體考量，發光元件320也可與光反射圍欄380不直接接觸。光反射圍欄380可由光反射的不導電材料所組成。在一實施例中，光反射材料例如是氧化鈦（TiO2 ）、氧化鋯（ZrO2 ）、氧化鈮（Nb2 O5 ）、氧化鋁（Al2 O3 ）、氧化矽（SiO2 ）、氟化鎂（MgF2 ）、氮化鋁（Al2 N3 ）。在另一實例中，反射圍欄380是上述光反射材料的顆粒與接著劑混合的膠料固化後所形成，接著劑例如是矽樹脂、壓克力樹脂或環氧樹脂。在一實施例中，可用網版印刷（screen-printing）、點膠（dispensing）或模具成形方式（molding）形成光反射圍欄380。The light reflecting fence 380 can reflect the light emitted by the light emitting element 320 and the wavelength conversion layer 360 upward. In an embodiment, the light emitting element 320 is in direct contact with the light reflecting fence 380. However, depending on the overall illumination angle and brightness, the light-emitting element 320 may not be in direct contact with the light-reflecting fence 380. The light reflecting fence 380 can be composed of a non-conductive material that is reflected by light. In one embodiment, the light reflective material is, for example, titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), cerium oxide (Nb 2 O 5 ), aluminum oxide (Al 2 O 3 ), cerium oxide (SiO 2 ), Magnesium fluoride (MgF 2 ), aluminum nitride (Al 2 N 3 ). In another example, the reflective fence 380 is formed by curing a mixture of particles of the above light-reflecting material and an adhesive, such as a resin, an acrylic resin, or an epoxy resin. In an embodiment, the light reflecting fence 380 may be formed by screen-printing, dispensing, or molding.
以上所述之實施例僅係為說明本發明之技術思想及特點，其目的在使熟習此項技藝之人士能夠瞭解本發明之內容並據以實施，當不能以之限定本發明之專利範圍，即大凡依本發明所揭示之精神所作之均等變化或修飾，仍應涵蓋在本發明之專利範圍內。The embodiments described above are merely illustrative of the technical spirit and the features of the present invention, and the objects of the present invention can be understood by those skilled in the art, and the scope of the present invention cannot be limited thereto. That is, the equivalent variations or modifications made by the spirit of the present invention should still be included in the scope of the present invention.
100、360‧‧‧波長轉換材料100, 360‧‧‧ wavelength conversion materials
120‧‧‧量子點粒子120‧‧‧Quantum point particles
122‧‧‧量子點122‧‧‧ Quantum dots
124‧‧‧配位基124‧‧‧Coordination
124a‧‧‧第一基團124a‧‧‧First Group
124b‧‧‧第二基團124b‧‧‧Second group
140‧‧‧矽氧樹脂140‧‧‧Oxygenated resin
160‧‧‧含鉑粒子160‧‧‧Platinum-containing particles
300‧‧‧發光裝置300‧‧‧Lighting device
320‧‧‧發光元件320‧‧‧Lighting elements
322‧‧‧透明基板322‧‧‧Transparent substrate
324‧‧‧發光疊層324‧‧‧Lighting laminate
340‧‧‧導電元件340‧‧‧Conducting components
342‧‧‧第一導電墊342‧‧‧First conductive pad
344‧‧‧第二導電墊344‧‧‧Second conductive pad
380‧‧‧光反射圍欄380‧‧‧Light Reflective Fence
第1圖係顯示依據本發明一實施例之波長轉換材料的示意圖。1 is a schematic view showing a wavelength converting material according to an embodiment of the present invention.
第2圖顯示依據本發明一實施例之製作波長轉換材料的流程圖。2 is a flow chart showing the fabrication of a wavelength converting material in accordance with an embodiment of the present invention.
第3圖係顯示依據本發明一實施例之發光裝置。Fig. 3 is a view showing a light-emitting device according to an embodiment of the present invention.
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