TWI502047B - Luminescent nanoscale particles with hydrophobic surface finish, process for production thereof and use thereof - Google Patents
Luminescent nanoscale particles with hydrophobic surface finish, process for production thereof and use thereof Download PDFInfo
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Description
本發明係關於新穎之經疏水性表面改質的發光奈米顆粒，關於其之製法及關於其之用途。This invention relates to novel hydrophobic surface-modified luminescent nanoparticles, to processes for their preparation and to their use.
半導體奈米顆粒之新穎的光學性質、磁性質及電性質在近幾年來已受矚目，因為彼能明顯地異於巨結晶變異體之諸性質。因為其良好之性質，通式XY(其中X=Zn、Cd、Hg、Pb且Y=O、S、Se、Te)之奈米顆粒可以是特別令人感興趣的。The novel optical properties, magnetic properties, and electrical properties of semiconductor nanoparticles have received attention in recent years because they are significantly different from the properties of giant crystalline variants. Nanoparticles of the general formula XY (where X = Zn, Cd, Hg, Pb and Y = O, S, Se, Te) may be of particular interest because of their good properties.
特別在用於光學材料及層時，奈米顆粒提供之優點是：因為與顆粒直徑之六次方相關，該等奈米顆粒之發散截面相較於微結晶材料之發散截面是極小的。因此，當加工期間奈米顆粒之附聚可以防止時，可能使用奈米顆粒以製造透明之混合材料。Particularly when used in optical materials and layers, nanoparticle provides the advantage that, due to the sixth power of the particle diameter, the divergent cross section of the nanoparticle is extremely small compared to the divergent cross section of the microcrystalline material. Therefore, when the agglomeration of the nanoparticles is prevented during processing, it is possible to use the nanoparticles to produce a transparent mixed material.
然而，奈米顆粒通常不能以純且未受保護之形式被使用；而是需要保護以不受化學作用的侵襲，例如氧化作用及水解作用。附聚傾向之降低及對化學作用之侵襲安定性的增加係經由適合之配合基殼體或基質之使用而達成。However, nanoparticles are generally not used in pure and unprotected form; rather, they need to be protected from chemical attack, such as oxidation and hydrolysis. The reduction in the tendency to agglomerate and the increase in the aggressiveness of the chemical action are achieved by the use of a suitable mating matrix or matrix.
特別對於光學應用而言，摻雜外來原子之奈米結晶是特別重要的。特別地，摻雜錳之材料代表一種已滲入例如以下應用中以作為發光體之物質類：例如在發光二極體中(Y.Horii et al.,Materials Science and Engineering B,2001,85,92)，在薄層電發光中(EP 1 241 713 A1)，在光生伏打中，在雷射中及在奈米範圍之電子開關中(J.Hu et al.,Science,2001,292,2060)。因為二價錳離子仍然具有強的磁矩，在電子及磁性質之偶合中漸增加之可想到的應用也正被討論(所謂之”自旋電子學”)。Especially for optical applications, nanocrystallization with foreign atoms is particularly important. In particular, the manganese-doped material represents a substance that has penetrated into, for example, the following applications as an illuminant: for example, in a light-emitting diode (Y. Horii et al., Materials Science and Engineering B, 2001, 85, 92). ), in thin-layer electroluminescence (EP 1 241 713 A1), in photovoltaics, in lasers and in electronic switches in the nanometer range (J. Hu et al., Science, 2001, 292, 2060) ). Since divalent manganese ions still have strong magnetic moments, conceivable applications in which electrons and magnetic properties are increasingly added are also being discussed (so-called "spintronics").
摻雜或不摻雜Mn的ZnS奈米顆粒在以前已就其光學激發、其發射及其經由外殼或基質之改質以控制其表面性質，而被描述數次。ZnS nanoparticles doped or undoped with Mn have been described several times before they have been optically excited, their emission and their modification via the outer shell or matrix to control their surface properties.
為要改良其表面，已建議例如以下物質作為配合基：硫代甘油(M.Bredol et al.,Solid State Phenomena,2004,99-100,19)，丙烯酸(T.Toyoda et al.,Thin solid films,2003,438,132；H.Althues et al.,Chem.Mater.,2006,18,1068)，聚乙烯基吡咯烷酮(N.Karara et al.,J.Appl.Phys.,2004,95,656)，3-巰基丙酸(J.Zhuang et al.,J.Mater.Chem.,2003,12,1853)，脫乙醯殼多糖(H.Warad et al.,Microsc.,Microanal.,2005,11,1920)，二辛基硫丁酸鈉(A.Dinsmore et al.,J.Phys.Chem.,2000,88,9)，組胺酸(G.Yi et al.,J.Mater.Chem.,2001,11,2928)，六偏磷酸鈉(H.Warad et al.,Adv.Mater.2005,6,296)，辛硫醇及半胱胺(=2-胺基硫乙醇；S.J.Cho et al.,Langmuir,2007,23,1974)。In order to improve the surface, it has been suggested, for example, as a ligand: thioglycerol (M. Bredol et al., Solid State Phenomena, 2004, 99-100, 19), acrylic acid (T. Toyoda et al., Thin solid) Films, 2003, 438, 132; H. Althues et al., Chem. Mater., 2006, 18, 1068), polyvinylpyrrolidone (N. Karara et al., J. Appl. Phys., 2004, 95, 656), 3 - Mercaptopropionic acid (J. Zhuang et al., J. Mater. Chem., 2003, 12, 1853), quercetin (H. Warad et al., Microsc., Microanal., 2005, 11, 1920) ), sodium dioctyl thiobutyrate (A. Dinsmore et al., J. Phys. Chem., 2000, 88, 9), histidine (G. Yi et al., J. Mater. Chem., 2001) , 11, 2928), sodium hexametaphosphate (H. Warad et al., Adv. Mater. 2005, 6, 296), octyl thiol and cysteamine (= 2-amino thioethanol; SJCho et al., Langmuir , 2007, 23, 1974).
配合基對這些材料之光發射可以具有影響：不適合之配合基吸收來自發光顆粒之所有或部分的激發能量，且因此導致發光之抑制(完全或部分地，所謂之”淬滅”)。此外，配合基可以提供疏水性或親水性基團於新的粒子表面上，而後與周圍基質有交互作用。The ligand can have an effect on the light emission of these materials: an unsuitable ligand absorbs all or part of the excitation energy from the luminescent particles and thus causes inhibition of the luminescence (completely or partially, so-called "quenching"). In addition, the ligand can provide a hydrophobic or hydrophilic group on the surface of the new particle and then interact with the surrounding matrix.
為製造摻雜或不摻雜之親水性顆粒，特別地，半胱胺(2-胺基硫乙醇)及其相對應之鹽類(例如氯化半胱銨)是有利的，因為彼因此可能製造極小顆粒(藉光散射計測量之顆粒直徑小於10mm)，這些顆粒不僅可容易離析的且完全可再分散於水中，但也具有強烈的光致發光。In order to produce doped or undoped hydrophilic particles, in particular, cysteamine (2-aminothioethanol) and its corresponding salts (for example cysteine chloride) are advantageous because they are therefore possible Very small particles (particle diameters measured by light scatterometers of less than 10 mm) are produced, which are not only easily detachable but are completely redispersible in water, but also have strong photoluminescence.
經安定化之奈米顆粒可以藉沉澱而獲得；在合成時原位使用配合基不僅導致相關改良之奈米顆粒，也導致結晶成長之控制及限制。The stabilized nanoparticle can be obtained by precipitation; the use of the ligand in situ during synthesis not only leads to the related modified nanoparticle, but also leads to the control and limitation of crystal growth.
然而，這些經半胱胺改質之親水性顆粒不能分散於有機系統中。However, these cysteamine-modified hydrophilic particles cannot be dispersed in an organic system.
疏水性發光奈米顆粒依照先前技術不能極令人滿意地製造：已知系統顯現出極強的附聚傾向，發射之部分淬滅及僅不令人滿意的配合基黏合。這使合併於疏水性聚合物或其單體的作用複雜化，或使該作用完全被防止。更成功的方法是基於適合單體之吸收/表面反應(H.Althues et al.,Chem.Mater.,2006,18,1068)或基於配合溶劑例如己基癸胺之使用(US 3,780,242)；然而在此二情況中，配合基可以困難地再次除去或改質以供其他目的之用。Hydrophobic luminescent nanoparticles cannot be manufactured very satisfactorily according to the prior art: known systems exhibit a strong tendency to agglomerate, partial quenching of the emission and only unsatisfactory ligand bonding. This complicates the action of the hydrophobic polymer or its monomer, or completely prevents the action. A more successful method is based on the absorption/surface reaction of a suitable monomer (H. Althues et al., Chem. Mater., 2006, 18, 1068) or based on the use of a complexing solvent such as hexylguanamine (US 3,780,242); In both cases, the ligand can be removed or modified again for other purposes with difficulty.
因此本發明之目的是要提供發光奈米顆粒，其已用配合基來疏水性改質，且因此極適合加工成疏水性聚合物或其單體(例如丙烯酸異冰酯)。此外，奈米顆粒應不易於附聚，特別是在用於疏水性系統時，且不顯現出任何明顯的發光淬滅。最後，配合基也應對核心顯現出良好但可逆的黏合性，且在化學上可有效地改質。It is therefore an object of the present invention to provide luminescent nanoparticles which have been hydrophobically modified with a ligand and are therefore highly suitable for processing into hydrophobic polymers or monomers thereof (e.g., isobornyl acrylate). In addition, the nanoparticles should not readily agglomerate, especially when used in hydrophobic systems, and do not exhibit any significant luminescence quenching. Finally, the ligand also exhibits good but reversible adhesion to the core and is chemically effective for upgrading.
此目的藉經改質之奈米顆粒而達成，該奈米顆粒包含式XY之核心及配合基殼體，其中X=Zn、Cd、Hg或Pb，且Y=O、S、Se或Te，其中該配合基殼體包含至少二個配合基L1及L2，其中L1係選自式(1)之胺基烷硫醇This object is achieved by a modified nanoparticle comprising a core of the formula XY and a ligand matrix, wherein X = Zn, Cd, Hg or Pb, and Y = O, S, Se or Te, Wherein the ligand base comprises at least two ligands L1 and L2, wherein the L1 is selected from the group consisting of amino alkanethiols of formula (1)
RR 22 -SO-SO 33 H (2a)H (2a)
本發明之顆粒顯現出強烈的發光(螢光及/或磷光)，特別是具有高的量子產率之螢光。The particles of the invention exhibit intense luminescence (fluorescence and/or phosphorescence), especially fluorescence with a high quantum yield.
本發明之奈米顆粒不僅顯現出所要之正面性質，另外地也特別在於：當配合基L2選自式(2a)及(2b)之未取代或經取代之磺酸類時，彼可以用極簡單之方式在水溶液中製備。The nanoparticle of the present invention not only exhibits the desired positive properties, but also specifically: when the ligand L2 is selected from the unsubstituted or substituted sulfonic acids of the formulae (2a) and (2b), it can be extremely simple The manner is prepared in an aqueous solution.
較佳地，在顆粒中，在配合基殼體中之配合基L1及L2不會互相分開並排地以獨立之配合基形式存在以形成各層(例如單-及/或雙層)，而是至少部分地藉至少一化學鍵來互相連接，以在形式上形成新的L3 配合基。L1及L2配合基較佳形成相對應之磺醯胺鍵或醯胺鍵。Preferably, in the particles, the ligands L1 and L2 in the ligand matrix are not separated from each other side by side in the form of separate ligands to form the layers (for example, single- and/or double-layer), but at least Partially linked to each other by at least one chemical bond to form a new L 3 ligand. The L1 and L2 ligands preferably form a corresponding sulfonamide bond or a guanamine bond.
奈米顆粒更佳是那些具有ZnS核心者，因為這些特徵在於具有比較好的環境相容性與比較好的發光率及低的製造成本。Nanoparticles are preferred for those having a ZnS core because these features are characterized by better environmental compatibility and better luminosity and lower manufacturing costs.
配合基L1較佳是半胱胺(=2-胺基硫乙醇)，因為之後達到特別堅固之配合基對核心的黏合性，且顆粒之發光與不具有殼體之發光相比，幾乎一點也無降低。The ligand L1 is preferably cysteamine (=2-aminothioethanol) because the adhesion of the particularly strong ligand to the core is achieved, and the luminescence of the particles is almost the same as that without the luminescence of the shell. No reduction.
當配合基L2是4-十二烷基苯磺酸時，結果獲得特別適合使用於疏水性介質之奈米顆粒。When the ligand L2 is 4-dodecylbenzenesulfonic acid, as a result, a nanoparticle which is particularly suitable for use in a hydrophobic medium is obtained.
在配合基殼體中之L1：L2配合基的數值比例較佳是>或=0.95，較佳地0.95-1.05。L1：L2配合基之數值比例更佳是1.0。The numerical ratio of the L1:L2 ligand in the mating base shell is preferably > or = 0.95, preferably 0.95-1.05. The numerical ratio of L1:L2 ligand is preferably 1.0.
較佳地，本發明之奈米顆粒在配合基殼體中除了配合基L1及L2以外，不具有另外之配合基。Preferably, the nanoparticles of the present invention have no additional ligands in the ligand matrix other than the ligands L1 and L2.
當本發明之奈米顆粒(包括配合基殼體)，使用Malvern奈米尺寸計且藉由動力光散射而測得具有1至30nm，較佳地5至25nm，更佳地10至15nm尺寸時，彼特別適合光學用途。當顆粒變為大於30nm時，結果是令人不滿意之發光率。在低於此值之範圍內，因此仍可能有利地控制發光性質，特別是激發及最大發射及量子產率。When the nanoparticle of the present invention (including a ligand base) is measured using a Malvern nanometer scale and measured by dynamic light scattering to have a size of 1 to 30 nm, preferably 5 to 25 nm, more preferably 10 to 15 nm He is especially suitable for optical applications. When the particles become larger than 30 nm, the result is an unsatisfactory luminosity. Below this value, it is therefore also possible to advantageously control the luminescent properties, in particular the excitation and maximum emission and quantum yield.
為獲得特別強烈的發光奈米顆粒，且為控制其之上述發光性質，其核心可以摻雜外來原子；在統計平均上，以合金為基準計，對於過渡金屬而言，摻雜最多至10莫耳%的程度，較佳地最多至2莫耳%的程度；對於金屬Au、Ag及Cu而言，摻雜最多至1莫耳%的程度。外來原子可以選自Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Nb、Mo、Tc、Ru、Pd、Ag、Ta、Re、Os、Ir、Pt、Au、Hg、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm及Yb。該金屬較佳是Mn、Fe、Ni、Cu、Ag、Au、Sm、Eu、Tb、Dy、Er、Tm及/或Yb。甚至更佳地，摻雜所用之外來原子是Mn、Cu、Au、Ag、Eu及/或Dy。最適合是Mn。In order to obtain particularly strong luminescent nano-particles, and to control the above-mentioned luminescent properties, the core can be doped with foreign atoms; on a statistical average, based on the alloy, for the transition metal, doping up to 10 The degree of ear %, preferably up to 2 mol%; for metals Au, Ag and Cu, doping up to 1 mol%. The foreign atom may be selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Pd, Ag, Ta, Re, Os, Ir, Pt, Au, Hg, Ce , Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb. The metal is preferably Mn, Fe, Ni, Cu, Ag, Au, Sm, Eu, Tb, Dy, Er, Tm and/or Yb. Even more preferably, the foreign atoms used for doping are Mn, Cu, Au, Ag, Eu and/or Dy. Most suitable is Mn.
本發明之顆粒可以用不同方式來合成。本發明之疏水性奈米顆粒可以在水性介質中製造，是一項大的優點。The particles of the invention can be synthesized in different ways. The hydrophobic nanoparticle of the present invention can be produced in an aqueous medium and is a great advantage.
本發明之奈米顆粒較佳可以藉由在水中或在有機溶劑中之”捕獲沉澱”的方法來製造，其中配合基在其沉澱期間被附加在XY核心之表面上且因此限制核心成長。The nanoparticles of the present invention are preferably produced by a "capture precipitation" method in water or in an organic solvent in which a ligand is attached to the surface of the XY core during its precipitation and thus limits core growth.
藉由在水性介質中之”捕獲沉澱”方法製造之本發明的奈米顆粒，以獲得單分散之奈米顆粒，是特別簡單的：此包含從成分X之鹽的水溶液中，藉添加成分Y之化合物的水溶液，在配合基L1及L2的存在下，沉澱本發明之經配合基改質之奈米顆粒。The nanoparticle of the present invention produced by the "capture precipitation" method in an aqueous medium to obtain monodisperse nanoparticle is particularly simple: this comprises the addition of the component Y from the aqueous solution of the salt of the component X. The aqueous solution of the compound precipitates the ligand-modified nanoparticle of the present invention in the presence of the ligands L1 and L2.
較佳地，在添加成分Y之化合物的水溶液之前，在成分X之鹽的存在或不存在下，配合基L1及L2在溶液中互相反應。Preferably, the ligands L1 and L2 are mutually reacted in solution in the presence or absence of a salt of the component X prior to the addition of the aqueous solution of the compound of the component Y.
在所述之製備方法中可被使用之X的適合鹽類包括X之所有水溶性鹽類。彼較佳是X之可溶的乙酸鹽類、硝酸鹽類、鹵化物、低碳羧酸之羧酸鹽類、及硫酸鹽類。Suitable salts of X which can be used in the preparation process include all water-soluble salts of X. Preferably, it is a soluble acetate, a nitrate, a halide, a carboxylate of a low carbon carboxylic acid, and a sulfate.
Y之較佳化合物包括Y之所有的水溶性化合物或釋出Y的化合物，特別是可溶的硫屬化合物及氫硫屬化合物，H2 Y型之氣態化合物及Y之分解先質，特別是硫醯胺類及硫脲類。特佳者是使用相關之鈉硫屬化合物。Preferred compounds of Y include all water-soluble compounds of Y or compounds which release Y, particularly soluble chalcogenides and hydrogen chalcogenides, gaseous compounds of type H 2 Y and decomposition precursors of Y, especially Thioamines and thioureas. The most preferred is the use of related sodium chalcogenides.
製備經改質之XY奈米顆粒之另外的方法係在逆膠質粒子中進行。這些構成具有固定幾何形狀及量的水性沉澱介質於奈米尺寸之經分散的水滴內。有利的是：顆粒尺寸可以經由親兩性之選擇而反覆地控制，因為膠質粒子之附聚數是一平衡參數。只要顆粒仍然孤立於膠質粒子內部，則另外可能進一步地例如藉由建構用於鈍化之殼體而將顆粒改質。在逆膠質粒子中製造本發明之顆粒的典型的方法使用成分X之鹽的水溶液及成分Y之化合物的水溶液，此二者分別在不與水互溶的有機溶劑中與兩性物質(例如聚氧伸乙基(5)壬基醚於己烷中)摻混，以形成微乳膠，然後二者在激烈攪拌下互相混合，配合基L1及L2在成分X之鹽的水溶液及/或在第三水溶液(其同樣地與該不與水互溶的有機溶劑摻混，以形成微乳膠，且在激烈攪拌下與前二種微乳膠之混合物混合)被離析且之後例如用丙酮來沉澱。An additional method of preparing the modified XY nanoparticles is carried out in reverse colloidal particles. These constitute aqueous precipitation media having a fixed geometry and amount in dispersed droplets of nanometer size. Advantageously, the particle size can be controlled repeatedly by the choice of affinity, since the number of agglomerates of the colloidal particles is an equilibrium parameter. As long as the particles are still isolated inside the colloidal particles, it is additionally possible to further modify the particles, for example by constructing a shell for passivation. A typical method for producing the particles of the present invention in a reverse particle is to use an aqueous solution of a salt of the component X and an aqueous solution of a compound of the component Y, respectively, in an organic solvent which is not miscible with water and an amphoteric substance (for example, polyoxygen extension) Ethyl (5) mercapto ether is blended in hexane to form a microemulsion, and then the two are mixed with each other under vigorous stirring, and the base L1 and L2 are in an aqueous solution of the salt of the component X and/or in the third aqueous solution. (It is likewise blended with the water-immiscible organic solvent to form a microemulsion, and mixed with the mixture of the first two microemulsions under vigorous stirring) is isolated and then precipitated, for example, with acetone.
本發明之奈米顆粒適合很多最終用途。The nanoparticles of the invention are suitable for many end uses.
A.因為其發光性，彼適合多種光致發光應用及適於微光學、光電子及感應器系統中的應用。例如，本發明之顆粒可用於具有或不具有適合配合基改質(這使物質之標記可被偵測)的螢光或磷光研究。也可能使用本發明之顆粒以供製造發光塗層於例如傳導性或非傳導性物質之上，例如於玻璃、膜、箔片或ITO之上，或供製造發光基質(例如塑膠、玻璃等，其在藉由太陽光、UV光、雷射光或類似者激發之後顯出螢光或磷光)，或適合與金屬/半導體聚合物結合用於光生伏打應用中。A. Because of its illuminance, it is suitable for a variety of photoluminescent applications and applications in micro-optics, optoelectronics and sensor systems. For example, the particles of the present invention can be used in fluorescent or phosphorescent studies with or without suitable ligand-based modifications which allow the labeling of the substance to be detected. It is also possible to use the particles of the invention for the manufacture of a luminescent coating on, for example, a conductive or non-conductive material, such as on a glass, film, foil or ITO, or for the manufacture of a luminescent substrate (eg plastic, glass, etc., It exhibits fluorescence or phosphorescence after excitation by sunlight, UV light, laser light or the like, or is suitable for use in photovoltaic applications in combination with metal/semiconductor polymers.
製造此種發光塗層之相關方法可以包含以下步驟：A method of making such a luminescent coating can include the following steps:
(1)提供發光奈米顆粒之分散液，然後(1) providing a dispersion of luminescent nanoparticle, and then
(2)將步驟(1)之後所得之分散液施加至基材上且至少部分地除去溶劑或分散劑，然後(2) applying the dispersion obtained after the step (1) to the substrate and at least partially removing the solvent or dispersant, and then
(3)用光照射在步驟(2)之後所得之塗層，以在光致發光應用中激發光。(3) The coating obtained after the step (2) is irradiated with light to excite the light in the photoluminescence application.
此製造方法也能在生產線中操作，亦即彼可以用在具有以本發明之發光奈米顆粒為底質之層的基材的連續製造方法中，例如用於滾筒對滾筒方法中。This manufacturing method can also be operated in a production line, that is, it can be used in a continuous manufacturing method of a substrate having a layer based on the luminescent nanoparticles of the present invention, for example, in a roll-to-roll method.
本發明因此提供一種藉由依本發明之方法可得之發光層。The invention therefore provides a luminescent layer obtainable by the method according to the invention.
在依本發明之方法的步驟(1)中可以有利地使用含有發光奈米顆粒之分散液。A dispersion containing luminescent nanoparticles can be advantageously used in step (1) of the process according to the invention.
較佳地，在依本發明之方法的步驟(2)中，分散液可以藉噴墨印刷、柔版印刷(flexographic printing)、移印、旋轉塗覆、噴霧、浸漬、刀塗覆、平版印刷、網版印刷、熱轉印刷、凹版印刷、流動塗覆、得自optomec(optomec inc.,Albuquerque,New Mexico)之氣溶膠噴射沉積方法或澆鑄，而施加至基材。Preferably, in step (2) of the method according to the invention, the dispersion can be by inkjet printing, flexographic printing, pad printing, spin coating, spraying, dipping, knife coating, lithography. Screen printing, thermal transfer printing, gravure printing, flow coating, aerosol spray deposition methods or castings from optomec (optomec inc., Albuquerque, New Mexico) are applied to the substrate.
這使基材上有結構或部分結構。此分散液較佳可以施加一次或多於一次及/或連續地施加或分批地施加。周圍條件依照應用之需求而定且因此可以依照如何施加分散液而不同。This gives the structure a structural or partial structure. Preferably, the dispersion can be applied one or more times and/or continuously or in portions. The ambient conditions are dependent on the needs of the application and can therefore vary depending on how the dispersion is applied.
有利地，在依本發明之方法的步驟(2)中，可能使用含有或係為玻璃或塑膠之基材。較佳可能使用(透明及/或傳導性)材料，更佳是石英玻璃、硼矽酸鹽顯示器玻璃、不含鹼之硼矽酸鹽顯示器玻璃、白玻璃、窗玻璃、浮動玻璃、聚酯、聚醯胺、聚醯亞胺、聚丙烯酸酯、聚碳酸酯(PC)、聚醚碸(PES)、聚醚醚酮(PEEK)、聚氯乙烯(PVC)、聚乙烯(PE)、聚丙烯(PP)、聚縮醛(POM)、聚對苯二甲酸乙二酯(PET)、聚萘酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)、聚羥基丁酸酯(PHB)、聚醯胺6、聚醯胺66、聚醯胺11、聚醯胺12、kapton、聚甲基丙烯酸甲酯(PMMA)、或這些材料之組合。極特佳地，可能使用膜型及/或積層材型之這些材料或這些材料之組合。Advantageously, in step (2) of the method according to the invention it is possible to use a substrate comprising or being glass or plastic. It is preferable to use (transparent and/or conductive) materials, more preferably quartz glass, borosilicate display glass, alkali-free borosilicate display glass, white glass, window glass, floating glass, polyester, Polyamide, polyimide, polyacrylate, polycarbonate (PC), polyether oxime (PES), polyetheretherketone (PEEK), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polyacetal (POM), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyhydroxybutyrate (PHB), Polyamide 6, Polyamide 66, Polyamide 11, Polyamide 12, Kapton , polymethyl methacrylate (PMMA), or a combination of these materials. Very preferably, it is possible to use these materials of film type and/or laminate type or a combination of these materials.
在依本發明之方法的步驟(3)之前，另外有利地可以是：藉由在20℃至180℃，較佳地50℃至130℃，更佳地60℃至120℃之溫度下乾燥1秒至60分鐘，以從步驟(2)後所得之塗層中，除去溶劑或分散劑。溶劑及分散劑可以更佳地在120℃溫度下在超過10分鐘之時間內從分散液或溶液中除去。溶劑或分散劑可以例如藉電磁能量的導入或藉基材與熱板之接觸而除去，或在滾筒對滾筒方法中較佳藉由與至少一經加熱之滾筒或壓延機之接觸而除去。另外較佳地，溶劑或分散劑可以藉IR、VIS、或UV光照射，例如藉由在乾燥爐中於IR區中發射之鹵素輻射器或雷射，或藉由使用經加熱之空氣或惰性氣體來清除而除去。更佳地，溶劑或分散劑可以藉由可整合於滾筒對滾筒方法中之至少一方法來除去。特別佳者可以是無接觸方法，極特佳是IR輻射器。最多99%之溶劑或分散劑較佳可以從步驟(2)之後所得的塗層中除去。藉乾燥所除去之溶劑或分散劑的比例可以藉由精於此技藝者已知的測試方法來測定，例如藉測重法。在乾燥後，可以獲得0.05至100μm，較佳地0.1至75μm，另外較佳地0.5至50μm，更佳地1至30μm之層厚度。Before step (3) of the process according to the invention, it may additionally be advantageous to dry by means of a temperature of from 20 ° C to 180 ° C, preferably from 50 ° C to 130 ° C, more preferably from 60 ° C to 120 ° C. The solvent or dispersant is removed from the coating obtained after the step (2) in seconds to 60 minutes. The solvent and dispersant may be more preferably removed from the dispersion or solution over a period of 10 minutes at a temperature of 120 °C. The solvent or dispersant can be removed, for example, by introduction of electromagnetic energy or by contact of the substrate with the hot plate, or preferably by contact with at least one heated roll or calender in a roll-to-roll process. Further preferably, the solvent or dispersant may be irradiated by IR, VIS, or UV light, such as by a halogen radiator or laser that is emitted in the IR zone in a drying oven, or by using heated air or inert The gas is removed and removed. More preferably, the solvent or dispersant can be removed by at least one of the methods that can be integrated into the drum to drum process. A particularly good one can be a contactless method, and an extremely good one is an IR radiator. Up to 99% of the solvent or dispersant is preferably removed from the coating obtained after the step (2). The ratio of solvent or dispersant removed by drying can be determined by a test method known to those skilled in the art, such as by weight measurement. After drying, a layer thickness of from 0.05 to 100 μm, preferably from 0.1 to 75 μm, further preferably from 0.5 to 50 μm, more preferably from 1 to 30 μm, can be obtained.
包含本發明之奈米顆粒的發光基質可以在製造基質前，藉添加本發明之奈米顆粒至相關之單體或基質溶液而製造。本發明之奈米顆粒因此可以在這些本質上是慣用的基質(例如那些以丙烯酸酯、玻璃或塑膠為底質者)的已知製造時被合併於這些基質中，或在其製造過程中被合併於合成的蛋白石中。The luminescent substrate comprising the nanoparticles of the present invention can be made by adding the nanoparticles of the present invention to the relevant monomer or substrate solution prior to the manufacture of the substrate. The nanoparticles of the present invention can thus be incorporated into these matrices in the known manufacture of these essentially conventional matrices (such as those based on acrylate, glass or plastic) or in the manufacture thereof. Merged into the synthetic opal.
B.彼可以有利地被用在奈米材料之慣常應用中，其中基於其小尺寸，奈米顆粒之正面性質，例如其硬度、其光散射性、其對含彼之介質的折射率的影響(特別是為要獲得含彼而具有大的折射率的聚合物)、特別機械性之賦予，在例如製造塗層材料、模製品、合成蛋白石、印刷膏及墨液時是特別重要的。本發明之奈米顆粒更佳在印刷時用於印刷膏，特別是用於網版印刷膏。B. He can be advantageously used in the customary application of nanomaterials, where based on its small size, the positive properties of the nanoparticle, such as its hardness, its light scattering, its effect on the refractive index of the medium containing it. (especially in order to obtain a polymer having a large refractive index), particularly mechanical imparting, is particularly important in, for example, the production of coating materials, molded articles, synthetic opals, printing pastes, and inks. The nanoparticle of the present invention is more preferably used for printing pastes during printing, particularly for screen printing pastes.
C.再者，本發明之奈米顆粒極適於電發光應用。本發明之奈米顆粒可極有效地用在AC及DC電發光領域中。特別是在AC電發光的領域中，本發明奈米顆粒可以用在電發光塗層中，特別是用在供具有高照明強度之膜燈或LED之製造的電發光塗層中。彼特別適於製造具有高輻射強度之屏蔽印刷膜燈。相對於用複雜方式製造以供薄膜電發光應用之層合燈系統(其必須用複雜之CVD技術來製造)，這些燈可以藉相對較簡單及較不昂貴的厚膜技術來製造。C. Further, the nanoparticles of the present invention are highly suitable for electroluminescent applications. The nanoparticle of the present invention can be used extremely effectively in the field of AC and DC electroluminescence. Particularly in the field of AC electroluminescence, the nanoparticles of the invention can be used in electroluminescent coatings, in particular in electroluminescent coatings for the manufacture of membrane lamps or LEDs having high illumination intensity. It is particularly suitable for the manufacture of shielded printed film lamps with high radiation intensity. These lamps can be fabricated by relatively simple and less expensive thick film techniques relative to laminated lamp systems that are fabricated in complex ways for thin film electroluminescent applications, which must be fabricated using complex CVD techniques.
這些電發光塗層可以藉包含以下步驟之方法而製造如下：These electroluminescent coatings can be made by the following steps:
(1)提供發光奈米顆粒之分散液，然後(1) providing a dispersion of luminescent nanoparticle, and then
(2)在步驟(1)之後所得之分散液施加至傳導性基材或施加至塗覆傳導性物質之基材，且至少部分地除去溶劑，然後(2) the dispersion obtained after the step (1) is applied to a conductive substrate or to a substrate coated with a conductive substance, and at least partially removed, and then
(3)隨意地施加介電層，(3) arbitrarily applying a dielectric layer,
(4)施加傳導性相對電極，(4) applying a conductive opposite electrode,
(5)施加電壓至步驟(2)之後所得之塗層，以在電發光應用中獲得發光。(5) Applying a voltage to the coating obtained after the step (2) to obtain luminescence in an electroluminescence application.
此方法也能在生產線中***作，亦即此方法可以用在具有以發光奈米顆粒為底質之層的基材的連續製造方法中，例如用在滾筒對滾筒方法中。This method can also be operated in a production line, i.e., the method can be used in a continuous manufacturing process of a substrate having a layer of light-emitting nanoparticles as a substrate, such as in a roll-to-roll method.
本發明因此同樣地提供一種藉由依本發明之方法所得之電發光層。The invention therefore likewise provides an electroluminescent layer obtained by the process according to the invention.
本發明同樣地提供一種具有本發明之層的電子零組件，及本發明之零組件在電發光模組或顯示器中之用途。The present invention likewise provides an electronic component having the layer of the present invention, and the use of the component of the present invention in an electroluminescent module or display.
較佳地，在依本發明之方法的步驟(2)中，分散液可以藉噴墨印刷、柔版印刷(flexographic printing)、移印、旋轉塗覆、噴霧、浸漬、刀塗覆、平版印刷、網版印刷、熱轉印刷、凹版印刷、流動塗覆、得自optomec(optomec inc.,Albuquerque,New Mexico)之氣溶膠噴射沉積方法或澆鑄，而施加至基材。Preferably, in step (2) of the method according to the invention, the dispersion can be by inkjet printing, flexographic printing, pad printing, spin coating, spraying, dipping, knife coating, lithography. Screen printing, thermal transfer printing, gravure printing, flow coating, aerosol spray deposition methods or castings from optomec (optomec inc., Albuquerque, New Mexico) are applied to the substrate.
這使基材上有結構或部分結構。此分散液較佳可以施加一次或多於一次及/或連續地施加或分批地施加。周圍條件依照應用之需求而定且因此可以依照如何施加分散液而不同。This gives the structure a structural or partial structure. Preferably, the dispersion can be applied one or more times and/or continuously or in portions. The ambient conditions are dependent on the needs of the application and can therefore vary depending on how the dispersion is applied.
有利地，在依本發明之方法的步驟(2)中，可能使用含有或係為玻璃或塑膠之基材。較佳可能使用(透明及傳導性)材料，更佳是石英玻璃、硼矽酸鹽顯示器玻璃、不含鹼之硼矽酸鹽顯示器玻璃、白玻璃、窗玻璃、浮動玻璃、聚酯、聚醯胺、聚醯亞胺、聚丙烯酸酯、聚碳酸酯(PC)、聚醚碸(PES)、聚醚醚酮(PEEK)、聚氯乙烯(PVC)、聚乙烯(PE)、聚丙烯(PP)、聚縮醛(POM)、聚對苯二甲酸乙二酯(PET)、聚萘酸乙二酯(PEN)、聚對苯二甲酸丁二酯(PBT)、聚羥基丁酸酯(PHB)、聚醯胺6、聚醯胺66、聚醯胺11、聚醯胺12、kapton、聚甲基丙烯酸甲酯(PMMA)、或這些材料之組合。極特佳地，可能使用膜型及/或積層材型之這些材料或這些材料之組合。Advantageously, in step (2) of the method according to the invention it is possible to use a substrate comprising or being glass or plastic. It is preferable to use (transparent and conductive) materials, more preferably quartz glass, borosilicate display glass, alkali-free borosilicate display glass, white glass, window glass, floating glass, polyester, polyfluorene Amine, polyimine, polyacrylate, polycarbonate (PC), polyether oxime (PES), polyetheretherketone (PEEK), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP) ), polyacetal (POM), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyhydroxybutyrate (PHB) ), polyamine 6, polyamine 66, polyamine 11, polyamide 12, kapton , polymethyl methacrylate (PMMA), or a combination of these materials. Very preferably, it is possible to use these materials of film type and/or laminate type or a combination of these materials.
在依本發明之方法的步驟(3)之前，另外有利地可以是：藉由在20℃至180℃，較佳地50℃至130℃，更佳地60℃至120℃之溫度下乾燥1秒至60分鐘，以從步驟(2)後所得之塗層中，除去溶劑或分散劑。溶劑及分散劑可以更佳地在120℃溫度下在超過10分鐘之時間內從分散液或溶液中除去。溶劑或分散劑可以例如藉電磁能量的導入或藉基材與熱板之接觸而除去，或在滾筒對滾筒方法中較佳藉由與至少一經加熱之滾筒或壓延機之接觸而除去。另外較佳地，溶劑或分散劑可以藉IR、VIS、或UV光照射，例如藉由在乾燥爐中於IR區中發射之鹵素輻射器或雷射，或藉由使用經加熱之空氣或惰性氣體來清除而除去。更佳地，溶劑或分散劑可以藉由可整合於滾筒對滾筒方法中之至少一方法來除去。特別佳者可以是無接觸方法，極特佳是IR輻射器。最多99%之溶劑或分散劑較佳可以從步驟(2)之後所得的塗層中除去。藉乾燥所除去之溶劑或分散劑的比例可以藉由精於此技藝者已知的測試方法來測定，例如藉測重法。在乾燥後，可以獲得0.05至100μm，較佳地0.1至75μm，另外較佳地0.5至50μm，更佳地1至30μm之層厚度。Before step (3) of the process according to the invention, it may additionally be advantageous to dry by means of a temperature of from 20 ° C to 180 ° C, preferably from 50 ° C to 130 ° C, more preferably from 60 ° C to 120 ° C. The solvent or dispersant is removed from the coating obtained after the step (2) in seconds to 60 minutes. The solvent and dispersant may be more preferably removed from the dispersion or solution over a period of 10 minutes at a temperature of 120 °C. The solvent or dispersant can be removed, for example, by introduction of electromagnetic energy or by contact of the substrate with the hot plate, or preferably by contact with at least one heated roll or calender in a roll-to-roll process. Further preferably, the solvent or dispersant may be irradiated by IR, VIS, or UV light, such as by a halogen radiator or laser that is emitted in the IR zone in a drying oven, or by using heated air or inert The gas is removed and removed. More preferably, the solvent or dispersant can be removed by at least one of the methods that can be integrated into the drum to drum process. A particularly good one can be a contactless method, and an extremely good one is an IR radiator. Up to 99% of the solvent or dispersant is preferably removed from the coating obtained after the step (2). The ratio of solvent or dispersant removed by drying can be determined by a test method known to those skilled in the art, such as by weight measurement. After drying, a layer thickness of from 0.05 to 100 μm, preferably from 0.1 to 75 μm, further preferably from 0.5 to 50 μm, more preferably from 1 to 30 μm, can be obtained.
藉以下合成法，將說明所提出之從半胱胺及十二烷基苯磺酸(DBS)原位產生雙官能配合基的方法：合成：10mmol(2.254g)乙酸鋅二水合物，1.9mmol(0.478g)乙酸錳(II)四水合物及7.0mmol(0.859g)氯化半胱銨被溶在125ml H2 O中(溶液I)。7.0mmol(2.42g)之硫化鈉溶在25ml H2 O中(溶液II)。The following synthesis method will be used to illustrate the proposed method for the in situ generation of a bifunctional ligand from cysteamine and dodecylbenzenesulfonic acid (DBS): synthesis: 10 mmol (2.254 g) of zinc acetate dihydrate, 1.9 mmol (0.478 g) Manganese (II) acetate tetrahydrate and 7.0 mmol (0.859 g) of cysteammonium chloride were dissolved in 125 ml of H 2 O (solution I). 7.0 mmol (2.42 g) of sodium sulfide was dissolved in 25 ml of H 2 O (solution II).
溶液I而後在攪拌下緩慢而逐滴地與4-十二烷基苯磺酸摻混(整個超過1.5小時，0.025ml/分鐘)。為沉澱奈米顆粒，溶液II而後以0.083ml/分鐘之速率在超過5小時之時間內緩慢地添加。所形成之分散液在95℃下迴流加熱3.5小時，以完成結晶且孤立奈米顆粒。Solution I was then slowly and dropwise blended with 4-dodecylbenzenesulfonic acid with stirring (entire over 1.5 hours, 0.025 ml/min). To precipitate the nanoparticles, solution II was then slowly added over a period of more than 5 hours at a rate of 0.083 ml/min. The resulting dispersion was heated under reflux at 95 ° C for 3.5 hours to complete crystallization and to isolate the nanoparticles.
形成透明奈米顆粒。為分離顆粒，添加乙醇且藉離心除去沉澱物。在60℃及低壓下進行顆粒之最終乾燥。Transparent nanoparticle is formed. To separate the particles, ethanol was added and the precipitate was removed by centrifugation. The final drying of the granules was carried out at 60 ° C and at a low pressure.
FTIR研究清楚地顯示：至少部分地已形成(安定)磺醯胺鍵，以致這些配合基可以結合半胱胺之優越且簡單之吸附作用與DBS之強的疏水作用。這些效果不能用個別之物質來達成。The FTIR study clearly shows that at least partially (stabilized) sulfonamide bonds have been formed such that these ligands can bind to the superior and simple adsorption of cysteamine and the strong hydrophobic action of DBS. These effects cannot be achieved with individual substances.
由此所得之顆粒可以極容易地以高的質量比例(最高達30重量%)再分散於聚合物溶液、疏水性單體等之中；有效的顆粒尺寸(依照DLS)則是10至20nm。在光致發光中，約30%之量子產率幾乎與經丙烯酸安定化之顆粒之參考值一般高[Althues et al.,Chem.Mater.,2006,18,168]。The particles thus obtained can be easily redispersed in a high mass ratio (up to 30% by weight) in a polymer solution, a hydrophobic monomer or the like; an effective particle size (according to DLS) is 10 to 20 nm. In photoluminescence, a quantum yield of about 30% is almost as high as a reference value for particles stabilized by acrylic acid [Althues et al., Chem. Mater., 2006, 18, 168].
經乾燥之疏水化奈米顆粒以粉末形式自發地分散於丙烯酸異冰片酯中，成30質量%之比例。為要固化，添加光起始劑(Irgacure 369)之後用UV光來照射。The dried hydrophobized nanoparticle was spontaneously dispersed in a powder form in isobornyl acrylate to a ratio of 30% by mass. To be cured, a photoinitiator (Irgacure 369) was added and then irradiated with UV light.
經固化之奈米複合材料是透明的，雖然有高的奈米顆粒含量。The cured nanocomposite is transparent, albeit with a high nanoparticle content.
從所得顆粒之繞射作圖顯明：存在閃鋅礦改質(在約29grd之最大散射對應於閃鋅礦之[111]反射，在約47grd之譜帶對應於[220]反射)。極寬之繞射線顯示：包含極小的一級結晶。Diffraction mapping from the resulting particles revealed that there was a sphalerite modification (the maximum scattering at about 29 grd corresponds to [111] reflection of sphalerite, and the band at about 47 grd corresponds to [220] reflection). Extremely wide ray display: Contains minimal primary crystals.
(使用Philips X-ray粉末繞射計PW 1130/00來記錄)(recorded using the Philips X-ray powder diffractometer PW 1130/00)
由顆粒在紫外線激發下的激發及發射光譜顯明：顆粒尺寸已導致激發譜帶移向較高之能量(與微結晶材料相比)，此外，由於Mn摻雜，實際上全部在發射中(約590nm)。由ZnS中之缺陷所引起之發射(約450nm)扮演有限的角色，且因此可以假設及良好之結晶品質。The excitation and emission spectra of the particles under UV excitation show that the particle size has caused the excitation band to shift to a higher energy (compared to the microcrystalline material) and, in addition, due to Mn doping, is actually all in the emission (about 590nm). Emissions (about 450 nm) caused by defects in ZnS play a limited role, and thus can be assumed and good crystal quality.
(使用UV-Vis螢光分光光度計RF-5301 PC Shimadzu)(Using UV-Vis Fluorescence Spectrophotometer RF-5301 PC Shimadzu)
從經離析之粉末的IR光譜顯明新的配合基的本質，其中半胱胺之特徵線(例如在3045cm-1 及832cm-1 之胺基)及十二烷基磺酸之特徵線(例如在1180cm-1 之碸基及在2956cm-1 之芳族CH)是可見的。一些新的譜帶指明磺醯胺鍵之形成。The IR spectrum of the isolated powder reveals the nature of the new ligand, in which the characteristic line of cysteamine (for example, the amine group at 3045 cm -1 and 832 cm -1 ) and the characteristic line of dodecyl sulfonic acid (for example, 1180cm -1 2956cm -1, and the sulfone group of the aromatic CH) is visible. Some new bands indicate the formation of sulfonamide bonds.
(使用Perkin-Elmer FTIR分光計)(using a Perkin-Elmer FTIR spectrometer)
在再分散之後，藉由動力光散射所測得之顆粒尺寸分布顯示：在分散於THF之後，顆粒僅稍微大於10nm。After redispersion, the particle size distribution measured by dynamic light scattering showed that the particles were only slightly larger than 10 nm after dispersion in THF.
(高效顆粒尺寸計(動力光散射)，Malvern)(Efficient particle size meter (power light scattering), Malvern)
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