TWI706025B - Preparation method of manganese-titanium co-activated magnesium stannate spinel fluorescent powder - Google Patents

Preparation method of manganese-titanium co-activated magnesium stannate spinel fluorescent powder Download PDF

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TWI706025B
TWI706025B TW108129906A TW108129906A TWI706025B TW I706025 B TWI706025 B TW I706025B TW 108129906 A TW108129906 A TW 108129906A TW 108129906 A TW108129906 A TW 108129906A TW I706025 B TWI706025 B TW I706025B
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titanium
manganese
activated magnesium
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TW202108744A (en
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蔡木村
潘柏宇
蔡宏哲
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國立虎尾科技大學
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Abstract

一種錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，包含：(1)製備前驅液，該前驅液含有鎂(II)醇鹽、錫(IV)鹽及溶劑；(2)於該前驅液中加入含錳(II)活化劑、含鈦(IV)活化劑及尿素並進行水解反應，以獲得透明溶膠，其中，尿素與錫(IV)鹽的莫耳數比值不大於5；(3)使該透明溶膠進行縮聚合反應，以獲得透明凝膠；(4)乾燥該透明凝膠，並在不低於1000℃的溫度下進行退火，以獲得該錳鈦共活化錫酸鎂尖晶石螢光粉體，且該錳鈦共活化錫酸鎂尖晶石螢光粉體的實驗式為Mg2(1-x)MnxSn1-yTiyO4，0.001≦x≦0.01，0.005≦y≦0.1。 A preparation method of manganese-titanium co-activated magnesium stannate spinel fluor powder, comprising: (1) preparing a precursor liquid, the precursor liquid containing magnesium (II) alkoxide, tin (IV) salt and solvent; (2) in the Add manganese (II)-containing activator, titanium (IV)-containing activator and urea to the precursor solution and conduct a hydrolysis reaction to obtain a transparent sol, wherein the molar ratio of urea to tin (IV) salt is not more than 5; 3) Perform polycondensation reaction of the transparent sol to obtain a transparent gel; (4) Dry the transparent gel and anneal at a temperature not lower than 1000° C. to obtain the manganese-titanium co-activated magnesium stannate tip Spar phosphor powder, and the experimental formula of the manganese-titanium co-activated magnesium stannate spinel phosphor powder is Mg 2(1-x) Mn x Sn 1-y Ti y O 4 , 0.001≦x≦0.01, 0.005≦y ≦0.1.

Description

錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法 Preparation method of manganese-titanium co-activated magnesium stannate spinel fluorescent powder

本發明是有關於一種錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，特別是指一種利用溶膠-凝膠(sol-gel)法之錳鈦共活化錫酸鎂(Mg2SnO4)尖晶石青色螢光粉體的製備方法。 The present invention relates to a preparation method of manganese-titanium co-activated magnesium stannate spinel phosphor powder, in particular to a sol-gel (sol-gel) method using manganese-titanium co-activated magnesium stannate (Mg 2 SnO 4 ) Preparation method of spinel cyan fluorescent powder.

目前商用的液晶顯示器(liquid crystal display,LCD)因液晶分子無法自行發光，需依賴背光源設計組裝，除有視角受限之問題，其內容物亦會造成環境負荷及製程耗能的問題。相對地，應用螢光材料之電漿顯示器(plasma display panel,PDP)及場發射顯示器(field emission display,FED)則具有主動發光特性且兼具廣視角及高對比等優點，尤其在發展新世代的場發射顯示器，企需開發具有低電壓特性，且在高真空受電子束衝擊後，仍具有良好化學安定性與高發光效率之螢光材料。 At present, commercial liquid crystal displays (LCDs) cannot emit light on their own because liquid crystal molecules cannot emit light on their own, and need to rely on backlight design and assembly. In addition to the problem of limited viewing angles, its contents will also cause environmental load and process energy consumption problems. In contrast, plasma display panels (PDP) and field emission displays (FED) using fluorescent materials have active luminescence characteristics and have the advantages of wide viewing angle and high contrast, especially in the development of new generations For field emission displays, companies need to develop fluorescent materials that have low voltage characteristics and still have good chemical stability and high luminous efficiency even after being impacted by electron beams in high vacuum.

傳統應用於平面顯示器之螢光材料，其主體是以硫化物螢光粉為主，雖然具有低電壓及高亮度特性，但是硫化物系螢光粉受到電子束撞擊後易釋放出硫蒸氣，容易導致螢光層剝蝕與發光特性衰退的狀況發生。此外，由於硫化物系螢光粉的化學穩定性較差，且對於環境溼度敏感，也不適合以化學蝕刻或光學平板印刷的方法製作圖案，故研究逐漸往非硫化物螢光材料發展。場發射顯示器具有優異的顯示特性與應用前景，被認為是取代傳統CRT顯示器，且可能超越目前LCD液晶顯示器的前瞻性產品，其中尚待克服 的關鍵性技術之一，即是開發具有化學安定性、熱穩定性、及高發光效率的螢光材料。 The fluorescent materials traditionally used in flat-panel displays are mainly based on sulfide phosphors. Although they have low voltage and high brightness, the sulfide phosphors easily release sulfur vapor after being hit by electron beams. Causes the phosphor layer to be eroded and the luminescence characteristics decline. In addition, because sulfide phosphors have poor chemical stability and are sensitive to environmental humidity, they are not suitable for patterning by chemical etching or optical lithography. Therefore, research has gradually developed toward non-sulfide phosphors. Field emission displays have excellent display characteristics and application prospects, and are considered to replace traditional CRT displays, and may surpass the current LCD liquid crystal display prospective products, which have yet to be overcome One of the key technologies is the development of fluorescent materials with chemical stability, thermal stability, and high luminous efficiency.

此外，白光發光二極體(light emitting diode,LED)由於具有高效率、壽命長、節能與環保等特性，已逐漸取代傳統燈泡成為照明設備發展的主流。 In addition, white light emitting diodes (LEDs) have gradually replaced traditional light bulbs as the mainstream of lighting equipment development due to their high efficiency, long life, energy saving and environmental protection.

現有商用的白光LED主要是由GaN系藍光與摻雜鈰(Ce)的釔鋁石榴石(Y3Al5O12：Ce3+，即YAG：Ce3+)黃光螢光粉混合而成，由於缺少綠光與紅光的成分，故存在演色性(color rendering)低的缺點，不適合應用於室內與醫療照明。雖然近期已有以紫外光或紫外光晶片與RGB三原色螢光粉體組合形成具有高演色性的白光，但其發光效率偏低。 The existing commercial white LEDs are mainly composed of GaN-based blue light and cerium (Ce) doped yttrium aluminum garnet (Y 3 Al 5 O 12 : Ce 3+ , that is, YAG: Ce 3+ ) yellow phosphor. It lacks the components of green light and red light, so it has the disadvantage of low color rendering, which is not suitable for indoor and medical lighting. Although the combination of ultraviolet light or ultraviolet light chip and RGB three primary color phosphor powder has been used recently to form white light with high color rendering, its luminous efficiency is low.

場發射顯示器或白光LED之螢光粉的色域是由其CIE色度座標的位置決定，即是由RGB三原色的座標點包圍成的三角形區域，例如商用的紅光螢光粉Y2O2S：Eu3+(0.647,0.343)或Y2O3：Eu3+(0.64,0.34)，綠光螢光粉ZnS：Cu,Al(0.298,0.619)或Zn2SiO4：Mn2+(0.222,0.706)及藍光螢光粉ZnS：Ag,Al(0.146,0.056)或BaMgAl10O17：Eu2+(即BAM：Eu2+)(0.139,0.078)。 The color gamut of the phosphor of a field emission display or a white LED is determined by the position of its CIE chromaticity coordinates, which is a triangular area surrounded by the coordinate points of the three primary colors of RGB, such as the commercial red phosphor Y 2 O 2 S: Eu 3+ (0.647, 0.343) or Y 2 O 3 : Eu 3+ (0.64, 0.34), green phosphor ZnS: Cu, Al (0.298, 0.619) or Zn 2 SiO 4 : Mn 2+ ( 0.222, 0.706) and blue phosphor ZnS: Ag, Al (0.146, 0.056) or BaMgAl 10 O 17 : Eu 2+ (ie BAM: Eu 2+ ) (0.139, 0.078).

因此，若能開發新式的螢光材料使其CIE色度座標位於上述三角形色域之外，將有利於擴大CIE之RGB三原色的色域，進而可增強全彩顯示器及改善白光LED的演色性。 Therefore, if new fluorescent materials can be developed to have CIE chromaticity coordinates outside the above-mentioned triangular color gamut, it will help expand the color gamut of CIE's RGB three primary colors, thereby enhancing full-color displays and improving the color rendering properties of white LEDs.

錫酸鎂(Mg2SnO4)尖晶石(spinel)具有穩定的電容與介電常數溫度係數、低損耗因子、高品質因子、高功率密度、化學安定性、對於可見光呈透明性且具有發光性，因而被廣泛應用於手 機與高速電腦的介電板、氣體與溼度感測器、鋰電池陽極材料、透明導電薄膜、太陽能電池、核廢料惰性載體及發光材料等。 Magnesium stannate (Mg 2 SnO 4 ) spinel (spinel) has stable capacitance and temperature coefficient of dielectric constant, low loss factor, high quality factor, high power density, chemical stability, transparency to visible light and luminescence Therefore, it is widely used in the dielectric panels of mobile phones and high-speed computers, gas and humidity sensors, lithium battery anode materials, transparent conductive films, solar cells, inert carriers of nuclear waste, and luminescent materials.

現有的錫酸鎂尖晶石螢光粉體主要是以固態法(solid state method)製備。例如Journal of Luminescence,vol.99(2002),p.169-173公開以固態法製備出能放射綠光的錳活化錫酸鎂尖晶石螢光粉體(Mg2SnO4：Mn)；又例如Journal of Materials Chemistry,vol.21(2011),p.6477-6479公開以固態法製備出共摻錳鈦的錫酸鎂螢光粉體，其經低電壓電子束激發後陰極射線致發光光譜(cathodoluminescence,CL)能放射出青光，其中Mn與Ti的臨界添加量分別為0.1mol%及2.0mol%，超過所述添加量之螢光粉體的發光效率顯著下降。此外，前述的固態法需依賴長時間的高溫熱處理，屬於高耗能的高成本製程，且具有容易造成粉體粗化、寬粒徑分布及產生大量MgO與SnO2偏析相的缺點，若將前述的螢光粉體應用於薄層螢光屏幕，難以增進其填充密度且發光性能仍顯不足。 The existing magnesium stannate spinel phosphor powder is mainly prepared by the solid state method. For example, Journal of Luminescence , vol.99 (2002), p.169-173 discloses the preparation of green light-emitting manganese activated magnesium stannate spinel fluor powder (Mg 2 SnO 4 : Mn) by solid-state method; another example is Journal of Materials Chemistry , vol.21 (2011), p.6477-6479 discloses the preparation of magnesium stannate phosphors co-doped with manganese-titanium by a solid-state method, which is excited by low-voltage electron beams and cathodoluminescence spectroscopy. , CL) can emit cyan light, wherein the critical addition amounts of Mn and Ti are 0.1 mol% and 2.0 mol%, respectively, and the luminous efficiency of the phosphor powder exceeding the addition amount is significantly reduced. In addition, the aforementioned solid-state method requires long-term high-temperature heat treatment, which is a high-energy and high-cost process, and has the disadvantages of easily causing powder coarsening, wide particle size distribution, and large amounts of MgO and SnO 2 segregation phases. The aforementioned phosphor powder is applied to a thin-layer fluorescent screen, it is difficult to increase its filling density and the luminous performance is still insufficient.

中華民國第I658005號專利案揭示一種利用氯化鎂及氯化錫為前趨物經膠粒溶膠-凝膠法製備鈦活化錫酸鎂尖晶石螢光粉體的方法，能合成具有窄粒徑分布及藍色發光特性的錫酸鎂尖晶石螢光粉體，可解決前述粉體粗化及寬粒徑分布的問題，且鈦鹽的臨界添加量為3.5mol%，顯示設備成本低的溶膠-凝膠法具有提高活化劑濃度作用及製備窄粒徑分布粉體的優點。然而，該方法的產物中含有大量偏析SnO2。 The Republic of China Patent No. I658005 discloses a method for preparing titanium activated magnesium stannate spinel fluors powder by colloidal particle sol-gel method using magnesium chloride and tin chloride as precursors, which can synthesize a narrow particle size distribution and blue Magnesium stannate spinel fluorescent powder with color luminescence characteristics can solve the aforementioned problems of powder coarsening and wide particle size distribution, and the critical addition amount of titanium salt is 3.5 mol%, which shows a sol-gel method with low equipment cost It has the advantages of increasing the concentration of activator and preparing powder with narrow particle size distribution. However, the product of this method contains a large amount of segregated SnO 2 .

因此，如何改良現有之錫酸鎂尖晶石螢光粉體的製備方法，能製備出具有均質性、窄粒徑分布及青光放射特性的錫酸鎂尖晶石青光螢光粉體，成為目前致力研究的方向。 Therefore, how to improve the existing preparation method of magnesium stannate spinel fluorescein powder, can prepare magnesium stannate spinel cyanoluminescence fluorescent powder with homogeneity, narrow particle size distribution and cyan light emission characteristics, has become the current research Direction.

因此，本發明之目的，即在提供一種錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法。本發明製備方法可自然形成凝膠化、能降低粉體結團狀態且所製得的錳鈦共活化錫酸鎂尖晶石螢光粉體具有均質性、窄粒徑分布、結晶性佳、低結團及青光放射特性，可以克服上述先前技術的缺點。 Therefore, the object of the present invention is to provide a method for preparing manganese-titanium co-activated magnesium stannate spinel phosphor powder. The preparation method of the invention can naturally form gelation, can reduce the state of powder agglomeration, and the prepared manganese-titanium co-activated magnesium stannate spinel fluor powder has homogeneity, narrow particle size distribution, good crystallinity, and low structure. The radiation characteristics of group and cyan light can overcome the above-mentioned shortcomings of the prior art.

於是，本發明錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，包含下列步驟：(1)製備前驅液，該前驅液含有鎂(II)醇鹽、錫(IV)鹽及溶劑；(2)於該前驅液中加入含錳(II)活化劑、含鈦(IV)活化劑及尿素並進行水解反應，以獲得透明溶膠，其中，尿素與錫(IV)鹽的莫耳數比值不大於5；(3)使該透明溶膠進行縮聚合反應，以獲得透明凝膠；及(4)乾燥該透明凝膠，並在不低於1000℃的溫度下進行退火，以獲得該錳鈦共活化錫酸鎂尖晶石螢光粉體，且該錳鈦共活化錫酸鎂尖晶石螢光粉體的實驗式為Mg2(1-x)MnxSn1-yTiyO4，其中，0.001≦x≦0.01，0.005≦y≦0.1。 Therefore, the method for preparing manganese-titanium co-activated magnesium stannate spinel phosphor powder of the present invention includes the following steps: (1) preparing a precursor solution containing magnesium (II) alkoxide, tin (IV) salt and a solvent; (2) Add manganese (II)-containing activator, titanium (IV)-containing activator, and urea to the precursor solution and perform a hydrolysis reaction to obtain a transparent sol, wherein the molar ratio of urea to tin (IV) salt Not more than 5; (3) subjecting the transparent sol to a condensation polymerization reaction to obtain a transparent gel; and (4) drying the transparent gel and annealing at a temperature not lower than 1000°C to obtain the manganese titanium Co-activated magnesium stannate spinel fluorescent powder, and the empirical formula of the manganese-titanium co-activated magnesium stannate spinel fluorescent powder is Mg 2(1-x) Mn x Sn 1-y Ti y O 4 , where 0.001 ≦x≦0.01, 0.005≦y≦0.1.

本發明之功效在於：本發明製備方法是以該鎂(II)醇鹽及該錫(IV)鹽分別作為鎂源及錫源，可藉由縮聚合反應自然形成凝膠化，能保持組成分子的緊密均勻分布，故可增進錫酸鎂尖晶石的結晶性，且在製程中添加特定量作為水解助劑的尿素(尿素與錫(IV)鹽的莫耳數比值不大於5)，因而能促進水解反應以大幅改善所生成溶膠的分散性與均質性，所製得的錫酸鎂尖晶石結團的情況更少、平均粒徑更小，且共同添加含錳(II)活化劑及含鈦(IV)活化劑以進行水解反應，並在不低於1000℃的溫度下進行退火，可製得具有青光放射特性的錫酸鎂尖晶石螢光粉體，且能提高其放射光強度與穩定性。 The effect of the present invention is that: the preparation method of the present invention uses the magnesium (II) alkoxide and the tin (IV) salt as the magnesium source and the tin source, respectively, which can naturally form gelation through the condensation polymerization reaction, and can maintain the constituent molecules The dense and uniform distribution of the magnesium stannate spinel can improve the crystallinity of the magnesium stannate spinel, and add a specific amount of urea as a hydrolysis aid in the process (the molar ratio of urea to tin(IV) salt is not more than 5), so It can promote the hydrolysis reaction to greatly improve the dispersibility and homogeneity of the resulting sol. The prepared magnesium stannate spinel has less agglomeration and smaller average particle size, and the manganese (II)-containing activator is added together And titanium (IV)-containing activator to carry out the hydrolysis reaction, and annealing at a temperature of not less than 1000 ℃, can produce magnesium stannate spinel phosphor powder with cyan light emission characteristics, and can increase its emission Strength and stability.

以下將就本發明內容進行詳細說明：本發明製備方法的步驟(1)為製備前驅液，該前驅液含有鎂(II)醇鹽、錫(IV)鹽及溶劑。 The content of the present invention will be described in detail below: Step (1) of the preparation method of the present invention is to prepare a precursor liquid, which contains magnesium (II) alkoxide, tin (IV) salt and a solvent.

該鎂(II)醇鹽可單獨一種使用或混合多種使用，其可為但不限於甲醇鎂[Mg(OCH3)2]或乙醇鎂[Mg(OC2H5)2]。在本發明的具體實施例中，該鎂(II)醇鹽是甲醇鎂。 The magnesium(II) alkoxide can be used alone or in combination of multiple types, which can be, but not limited to, magnesium methoxide [Mg(OCH 3 ) 2 ] or magnesium ethoxide [Mg(OC 2 H 5 ) 2 ]. In a specific embodiment of the present invention, the magnesium(II) alkoxide is magnesium methoxide.

該錫(IV)鹽可單獨一種使用或混合多種使用，其可為但不限於四氯化錫[SnCl4]、四甲氧基錫[Sn(OCH3)4]或四乙氧基錫[Sn(OC2H5)4]。在本發明的具體實施例中，該錫(IV)鹽是四氯化錫。 The tin(IV) salt can be used alone or in combination of multiple types, and it can be, but not limited to, tin tetrachloride [SnCl 4 ], tetramethoxytin [Sn(OCH 3 ) 4 ] or tetraethoxytin [ Sn(OC 2 H 5 ) 4 ]. In a specific embodiment of the present invention, the tin(IV) salt is tin tetrachloride.

該溶劑可單獨一種使用或混合多種使用，其可為醇溶劑，具體可為但不限於甲醇或乙醇。在本發明的具體實施例中，該溶劑是乙醇。 The solvent can be used alone or in a mixture of multiple types, and it can be an alcohol solvent, specifically but not limited to methanol or ethanol. In a specific embodiment of the present invention, the solvent is ethanol.

較佳地，該步驟(1)是於25~30℃下攪拌，以形成該前驅液。在本發明的具體實施例中，該步驟(1)是於25℃下攪拌，以形成該前驅液。 Preferably, the step (1) is to stir at 25-30°C to form the precursor liquid. In a specific embodiment of the present invention, the step (1) is to stir at 25°C to form the precursor liquid.

在本發明的具體實施例中，該步驟(1)是將該鎂(II)醇鹽及該錫(IV)鹽溶於該溶劑。 In a specific embodiment of the present invention, the step (1) is to dissolve the magnesium (II) alkoxide and the tin (IV) salt in the solvent.

本發明製備方法的步驟(2)為於該前驅液中加入含錳(II)活化劑、含鈦(IV)活化劑及尿素並進行水解反應，以獲得透明溶膠。 The step (2) of the preparation method of the present invention is to add a manganese (II)-containing activator, a titanium (IV)-containing activator and urea to the precursor solution and perform a hydrolysis reaction to obtain a transparent sol.

較佳地，該含錳(II)活化劑是選自於氯化錳(Ⅱ)、硝酸錳(Ⅱ)或其組合。在本發明的具體實施例中，該含錳(II)活化劑是氯化錳(Ⅱ)。 Preferably, the manganese (II)-containing activator is selected from manganese (II) chloride, manganese (II) nitrate or a combination thereof. In a specific embodiment of the present invention, the manganese (II)-containing activator is manganese (II) chloride.

較佳地，該含鈦(IV)活化劑是選自於異丙醇鈦(Ⅳ)、四氯化鈦或其組合。在本發明的具體實施例中，該含鈦(IV)活化劑是異丙醇鈦(Ⅳ)。 Preferably, the titanium (IV)-containing activator is selected from titanium (IV) isopropoxide, titanium tetrachloride or a combination thereof. In a specific embodiment of the present invention, the titanium (IV)-containing activator is titanium (IV) isopropoxide.

在本發明的具體實施例中，尿素與錫(IV)鹽的莫耳數比值不大於5。若尿素與錫(IV)鹽的莫耳數比值大於5，所得的溶膠或凝膠外觀透明度較低，且所需的凝膠化時間較長。 In a specific embodiment of the present invention, the molar ratio of urea to tin(IV) salt is not more than 5. If the molar ratio of urea to tin (IV) salt is greater than 5, the resulting sol or gel has a lower appearance and transparency, and the required gelation time is longer.

較佳地，尿素與該錫(IV)鹽的莫耳數比值範圍為0.5~5。更佳地，尿素與該錫(IV)鹽的莫耳數比值範圍為1~3。在本發明的部分具體實施例中，尿素與該錫(IV)鹽的莫耳數比值為3。 Preferably, the molar ratio of urea to the tin (IV) salt ranges from 0.5 to 5. More preferably, the molar ratio of urea to the tin (IV) salt ranges from 1 to 3. In some specific embodiments of the present invention, the molar ratio of urea to the tin(IV) salt is 3.

較佳地，該含錳(II)活化劑與該鎂(II)醇鹽的莫耳數比值範圍為0.001~0.005。更佳地，該含錳(II)活化劑與該鎂(II)醇鹽的莫耳數比值範圍為0.001~0.003，在此範圍中，本發明的部分具體實施例所製得的粉體產物具有較高的藍綠光放射強度。 Preferably, the molar ratio of the manganese (II)-containing activator to the magnesium (II) alkoxide ranges from 0.001 to 0.005. More preferably, the molar ratio of the manganese (II)-containing activator to the magnesium (II) alkoxide ranges from 0.001 to 0.003. In this range, the powder product prepared by some specific embodiments of the present invention Has a high intensity of blue and green light emission.

較佳地，該含鈦(IV)活化劑與該錫(IV)鹽的莫耳數比值範圍為0.005~0.100。更佳地，該含鈦(IV)活化劑與該錫(IV)鹽的莫耳數比值範圍為0.010~0.050。又更佳地，該含鈦(IV)活化劑與該錫(IV)鹽的莫耳數比值範圍為0.010~0.030，在此範圍中，本發明的部分具體實施例所製得的粉體產物具有較高的藍綠光放射強度。 Preferably, the molar ratio of the titanium (IV)-containing activator to the tin (IV) salt ranges from 0.005 to 0.100. More preferably, the molar ratio of the titanium (IV)-containing activator to the tin (IV) salt ranges from 0.010 to 0.050. More preferably, the molar ratio of the titanium (IV)-containing activator to the tin (IV) salt ranges from 0.010 to 0.030, and in this range, the powder product prepared by some specific embodiments of the present invention Has a high intensity of blue and green light emission.

較佳地，該步驟(2)是於25~30℃下進行水解反應，以獲得該透明溶膠。在本發明的具體實施例中，該步驟(2)是於25℃下進行水解反應，以獲得該透明溶膠。 Preferably, the step (2) is to perform a hydrolysis reaction at 25-30°C to obtain the transparent sol. In a specific embodiment of the present invention, the step (2) is to conduct a hydrolysis reaction at 25° C. to obtain the transparent sol.

本發明製備方法的步驟(3)為使該透明溶膠進行縮聚合反應，以獲得透明凝膠。 Step (3) of the preparation method of the present invention is to subject the transparent sol to a condensation polymerization reaction to obtain a transparent gel.

較佳地，該步驟(3)是於25~30℃下進行縮聚合反應，以獲得該透明凝膠。在本發明的具體實施例中，該步驟(3)是於25℃下進行縮聚合反應，以獲得該透明凝膠。 Preferably, the step (3) is to perform a condensation polymerization reaction at 25-30°C to obtain the transparent gel. In a specific embodiment of the present invention, the step (3) is to perform a condensation polymerization reaction at 25°C to obtain the transparent gel.

較佳地，該步驟(3)是於相對溼度55~85%下進行縮聚合反應。在本發明的具體實施例中，該步驟(3)是於相對溼度85%下進行縮聚合反應。 Preferably, this step (3) is to carry out the condensation polymerization reaction at a relative humidity of 55-85%. In a specific embodiment of the present invention, this step (3) is to carry out the condensation polymerization reaction at a relative humidity of 85%.

在本發明的具體實施例中，該步驟(3)是進行縮聚合反應30~42h。 In the specific embodiment of the present invention, this step (3) is to carry out the condensation polymerization reaction for 30 to 42 hours.

本發明製備方法的步驟(4)為乾燥該透明凝膠，並在不低於1000℃的溫度下進行退火，以獲得該錳鈦共活化錫酸鎂尖晶石螢光粉體。 The step (4) of the preparation method of the present invention is to dry the transparent gel and anneal at a temperature not lower than 1000° C. to obtain the manganese-titanium co-activated magnesium stannate spinel fluor powder.

在本發明的具體實施例中，該步驟(4)是於150℃下乾燥該透明凝膠。 In a specific embodiment of the present invention, the step (4) is to dry the transparent gel at 150°C.

較佳地，該步驟(4)是於1000~1200℃的溫度下進行退火。在本發明的部分具體實施例中，該步驟(4)是於1200℃的溫度下進行退火。 Preferably, this step (4) is annealing at a temperature of 1000-1200°C. In some specific embodiments of the present invention, the step (4) is annealing at a temperature of 1200°C.

較佳地，該步驟(4)是進行退火2~6小時。 Preferably, this step (4) is annealing for 2-6 hours.

在本發明的部分具體實施例中，該步驟(4)是於1200℃的溫度下空氣環境中進行退火後，再於800℃下氮氫混合氣體中進行退火，可增加綠光強度並增進青光飽和度。 In some specific embodiments of the present invention, the step (4) is to perform annealing in an air environment at a temperature of 1200°C, and then annealing in a nitrogen-hydrogen mixed gas at 800°C, which can increase the intensity of green light and enhance the green light. Light saturation.

在本發明的部分具體實施例中，該錳鈦共活化錫酸鎂尖晶石螢光粉體經波長268nm的紫外光激發後，產生的放射光為CIE色度座標之x座標值於0.1026~0.1995範圍間及y座標值於0.2183~0.3128範圍間的青色光。 In some specific embodiments of the present invention, after the manganese-titanium co-activated magnesium stannate spinel phosphor powder is excited by ultraviolet light with a wavelength of 268nm, the emitted light is the x-coordinate value of the CIE chromaticity coordinate in the range of 0.1026~0.1995 Cyan light with y-coordinate value in the range of 0.2183~0.3128.

本發明之其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中：〔圖1〕是實施例1~2與比較例2所製得的粉體產物的X-光繞射圖；〔圖2〕是比較例3~5所製得的粉體產物的X-光繞射圖；〔圖3〕是實施例2~5與比較例5~6所製得的粉體產物的X-光繞射圖；〔圖4〕是實施例2、實施例6~13與比較例7所製得的粉體產物的X-光繞射圖；〔圖5〕是實施例2、實施例14~17與比較例8所製得的粉體產物的X-光繞射圖； 〔圖6〕是實施例1~2與比較例2所製得的粉體產物的紅外光光譜圖；〔圖7至9〕分別是實施例1~2與比較例5所製得的粉體產物的SEM相片；〔圖10及11〕分別是實施例14及比較例9所製得的粉體產物的X-光光電子能譜圖；〔圖12及13〕分別是實施例2及比較例5所製得的粉體產物的電子順磁共振光譜圖；〔圖14〕是實施例7所製得的粉體產物之光致發光的激發光譜及放射光譜；〔圖15〕是實施例2、實施例18及比較例5所製得的粉體產物之光致發光的放射光譜；及〔圖16〕是顯示有商用Y2O3：Eu3+、Zn2SiO4：Mn2+、BAM：Eu2+與比較例7、8及實施例2、7、18、19、21、22、24的粉體產物的放射光位置的CIE色度圖。 The other features and effects of the present invention will be clearly presented in the embodiments with reference to the drawings, in which: [Figure 1] is the X-ray winding of the powder products prepared in Examples 1 to 2 and Comparative Example 2. [Figure 2] is the X-ray diffraction diagram of the powder product prepared in Comparative Examples 3 to 5; [Figure 3] is the powder prepared in Examples 2 to 5 and Comparative Examples 5 to 6 X-ray diffraction diagram of the product; [Figure 4] is the X-ray diffraction diagram of the powder products prepared in Example 2, Examples 6 to 13 and Comparative Example 7; [Figure 5] is Example 2 , X-ray diffraction diagrams of the powder products prepared in Examples 14-17 and Comparative Example 8; [Figure 6] is the infrared spectrum of the powder products prepared in Examples 1 to 2 and Comparative Example 2 Figures; [Figures 7 to 9] are SEM photographs of the powder products prepared in Examples 1 to 2 and Comparative Example 5; [Figures 10 and 11] are the powders obtained in Example 14 and Comparative Example 9, respectively X-ray photoelectron spectroscopy of the bulk product; [Figures 12 and 13] are the electron paramagnetic resonance spectra of the powder products prepared in Example 2 and Comparative Example 5, respectively; [Figure 14] is shown in Example 7 The photoluminescence excitation spectrum and emission spectrum of the powder product obtained; [Figure 15] is the photoluminescence emission spectrum of the powder product obtained in Example 2, Example 18 and Comparative Example 5; and [ Figure 16] It shows that there are commercial Y 2 O 3 : Eu 3+ , Zn 2 SiO 4 : Mn 2+ , BAM: Eu 2+ and comparative examples 7, 8 and examples 2 , 7, 18, 19, 21, 22 , 24 CIE chromaticity diagram of the emission position of the powder product.

本發明將就以下實施例來作進一步說明，但應瞭解的是，該等實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。 The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.

〈實施例1~24及比較例1~9〉 < Examples 1 to 24 and Comparative Examples 1 to 9 >

實施例1~24及比較例1~9的粉體產物是依據下列步驟所製得，其中，實施例1~24及比較例1~9的尿素與四氯化錫的莫耳數比值(U/Sn)、氯化錳(Ⅱ)與甲醇鎂的莫耳數比值(Mn/Mg)、異 丙醇鈦(Ⅳ)與四氯化錫的莫耳數比值(Ti/Sn)、退火溫度(環境)、退火時間分別如下表1所示。 The powder products of Examples 1-24 and Comparative Examples 1-9 were prepared according to the following steps. Among them, the molar ratio of urea to tin tetrachloride (U) of Examples 1-24 and Comparative Examples 1-9 /Sn), the molar ratio of manganese chloride (Ⅱ) to magnesium methoxide (Mn/Mg), different The molar ratio (Ti/Sn), annealing temperature (environment) and annealing time of titanium (IV) propoxide to tin tetrachloride are shown in Table 1 below.

步驟(1)：將0.4mol甲醇鎂及0.2mol四氯化錫溶於乙醇(溶劑)中，並於25℃下攪拌1h後，以形成前驅液。 Step (1): Dissolve 0.4 mol magnesium methoxide and 0.2 mol tin tetrachloride in ethanol (solvent), and stir at 25° C. for 1 hour to form a precursor solution.

步驟(2)：於該前驅液中加入氯化錳(Ⅱ)、異丙醇鈦(Ⅳ)及尿素[比較例1、8、9無添加氯化錳(Ⅱ)；比較例1、7、9無添加異丙醇鈦(Ⅳ)；比較例1、4、5無添加尿素]，並於25℃下進行水解反應1~2h後，以獲得溶膠。 Step (2): Add manganese chloride (II), titanium isopropoxide (IV) and urea to the precursor solution [Comparative Examples 1, 8, and 9 without adding manganese chloride (II); Comparative Examples 1, 7, and 9 No titanium isopropoxide (IV) is added; Comparative Examples 1, 4, and 5 are not added urea], and the hydrolysis reaction is performed at 25° C. for 1 to 2 hours to obtain a sol.

步驟(3)：將該溶膠於25℃及相對溼度為85%下進行縮聚合反應28~47h後，以獲得凝膠。 Step (3): the sol is subjected to a condensation polymerization reaction at 25° C. and a relative humidity of 85% for 28 to 47 hours to obtain a gel.

步驟(4)：將該透明凝膠於150℃下進行乾燥，並細化成膠體粉末。接著，使該膠體粉末進行退火2~6h後，冷卻至室溫，即可獲得實施例1~24與比較例1~9的粉體產物。 Step (4): Dry the transparent gel at 150°C and refine it into colloidal powder. Then, the colloidal powder was annealed for 2-6 hours and then cooled to room temperature to obtain the powder products of Examples 1-24 and Comparative Examples 1-9.

Figure 108129906-A0305-02-0011-1
Figure 108129906-A0305-02-0011-1
Figure 108129906-A0305-02-0012-2
Figure 108129906-A0305-02-0012-2

[縮聚合反應(凝膠化)時間與溶膠及凝膠的外觀比較][Comparison of polycondensation reaction (gelation) time with the appearance of sol and gel]

依據上述實施例1之步驟(1)至(3)及下表2中所列之尿素與四氯化錫)的莫耳數比值(U/Sn)製得溶膠與凝膠。接著，觀察不同條件下所製得溶膠與凝膠的外觀，並記錄步驟(3)所需的縮聚合反應時間(即凝膠化時間)，所得結果整理於下表2中。 The sol and gel were prepared according to the steps (1) to (3) of the above embodiment 1 and the molar ratio (U/Sn) of urea and tin tetrachloride listed in Table 2 below. Next, observe the appearance of the sol and gel prepared under different conditions, and record the polycondensation reaction time (ie gelation time) required in step (3). The results are summarized in Table 2 below.

Figure 108129906-A0305-02-0012-3
Figure 108129906-A0305-02-0012-3
Figure 108129906-A0305-02-0013-4
Figure 108129906-A0305-02-0013-4

由表2結果可知，製程中無添加尿素所得的溶膠外觀雖為清澈，但其凝膠外觀卻呈半透明。又，製程中有添加尿素且尿素與四氯化錫的莫耳數比值(U/Sn)不大於5所得的溶膠與凝膠，其外觀皆為清澈與透明。然而，製程中雖有添加尿素但U/Sn大於5所得的溶膠外觀皆為混濁，且其凝膠外觀呈現半透明(U/Sn=7)或白色不透明(U/Sn=10)。 From the results in Table 2, it can be seen that although the appearance of the sol obtained without adding urea during the process is clear, the appearance of the gel is translucent. In addition, the sol and gel obtained by adding urea and the molar ratio (U/Sn) of urea to tin tetrachloride not greater than 5 during the manufacturing process are all clear and transparent in appearance. However, although urea is added in the process, the appearance of the sol obtained with U/Sn greater than 5 is turbid, and the gel appearance is translucent (U/Sn=7) or white and opaque (U/Sn=10).

由上述說明可知，本發明製程中有添加尿素且U/Sn不大於5的製備方法，可製成外觀為清澈與透明的溶膠與凝膠，說明適量尿素能促進水解反應的分散性(即能均勻水解)，進而後續能得到清澈溶膠與透明凝膠。 It can be seen from the above description that there is a preparation method in which urea is added and U/Sn is not greater than 5 in the process of the present invention, which can be made into sol and gel with a clear and transparent appearance. Uniform hydrolysis), and then a clear sol and transparent gel can be obtained later.

[X-光繞射(X-ray diffraction,XRD)分析][X-ray diffraction (XRD) analysis]

將實施例1~2與比較例2所製得的粉體產物以X-光繞射儀(廠商：Bruker；型號：D8 Advance)分別進行X-光繞射分析，所得的X-光繞射圖如圖1所示。將比較例3~5所製得的粉體產物進行X-光繞射分析，所得的X-光繞射圖如圖2所示。將實施例2~5與比較例5~6所製得的粉體產物分別進行X-光繞射分析，所得的X-光繞射圖如圖3所示。將實施例2、實施例6~13與比較例7所製得的粉體產物分別進行X-光繞射分析，所得的X-光繞射圖如圖4所示。將實施例2、實施例14~17與比較例8所製得的粉體產物分別進行X-光繞射分析，所得的X-光繞射圖如圖5所示。 The powder products prepared in Examples 1 to 2 and Comparative Example 2 were analyzed by X-ray diffraction with an X-ray diffractometer (manufacturer: Bruker; model: D8 Advance), and the obtained X-ray diffraction The figure is shown in Figure 1. The powder products prepared in Comparative Examples 3 to 5 were subjected to X-ray diffraction analysis, and the obtained X-ray diffraction diagram was shown in FIG. 2. The powder products prepared in Examples 2 to 5 and Comparative Examples 5 to 6 were subjected to X-ray diffraction analysis, and the obtained X-ray diffraction diagrams are shown in FIG. 3. The powder products prepared in Example 2, Examples 6 to 13 and Comparative Example 7 were respectively subjected to X-ray diffraction analysis, and the obtained X-ray diffraction diagram was shown in FIG. 4. The powder products prepared in Example 2, Examples 14 to 17 and Comparative Example 8 were respectively subjected to X-ray diffraction analysis, and the obtained X-ray diffraction diagram is shown in FIG. 5.

由圖1可以發現，製程中有添加尿素所得的膠體粉末，經800℃退火後(比較例2)主要為MgO(氧化鎂；JCPDS Card no.45-0946)及SnO2(二氧化錫；JCPDS Card no.41-1445)的雙相 結構，只有相當微量的MgSnO3(偏錫酸鎂；JCPDS Card no.30-0798)及Mg2SnO4尖晶石(錫酸鎂尖晶石；JCPDS Card no.24-0723)結晶相，直到退火溫度為1000~1200℃(實施例1~2)，才轉變成主要為Mg2SnO4尖晶石結構。此外，退火溫度為1200℃的製備方法所製得的粉體產物(實施例2)，其Mg2SnO4尖晶石的結晶相繞射峰強度較退火溫度為1000℃的製備方法所製得的粉體產物(實施例1)更高，顯示實施例2所製得的粉體產物的結晶性較高。 It can be found from Figure 1 that there is colloidal powder obtained by adding urea in the process. After annealing at 800°C (Comparative Example 2), it is mainly MgO (magnesium oxide; JCPDS Card no.45-0946) and SnO 2 (tin dioxide; JCPDS) Card no. 41-1445) of the dual-phase structure, only a very small amount of MgSnO 3 (magnesium metastannate; JCPDS Card no. 30-0798) and Mg 2 SnO 4 spinel (magnesium stannate spinel; JCPDS Card no.24-0723) The crystalline phase is not transformed into a Mg 2 SnO 4 spinel structure until the annealing temperature is 1000~1200°C (Examples 1~2). In addition, the powder product obtained by the preparation method with an annealing temperature of 1200°C (Example 2) has a Mg 2 SnO 4 spinel whose crystal phase diffraction peak intensity is higher than that of the preparation method with an annealing temperature of 1000°C. The powder product (Example 1) is higher, indicating that the powder product prepared in Example 2 has higher crystallinity.

由圖2可以發現，製程中無添加尿素所得的膠體粉末，經800~1200℃退火後(比較例3~5)皆明顯含有MgO及SnO2偏析相，顯示其無法製得高結晶性的Mg2SnO4尖晶石結構。 It can be seen from Figure 2 that the colloidal powder obtained without adding urea in the process, after annealing at 800~1200℃ (Comparative Examples 3~5), all obviously contain MgO and SnO 2 segregation phases, which shows that it is impossible to obtain high crystallinity Mg. 2 SnO 4 spinel structure.

由圖3可以發現，製程中無添加尿素(比較例5)及有添加尿素且U/Sn=10(比較例6)所得的膠體粉末，經1200℃退火後皆明顯含有SnO2偏析相，顯示其無法製得高結晶性的Mg2SnO4尖晶石結構。而製程中有添加尿素且U/Sn=0.5~5(實施例2~5)所得的膠體粉末，經1200℃退火後的Mg2SnO4尖晶石結晶的均質性較高。 It can be found from Figure 3 that the colloidal powder obtained without adding urea (Comparative Example 5) and adding urea and U/Sn=10 (Comparative Example 6) in the process obviously contains SnO 2 segregation phase after annealing at 1200°C. It cannot produce a highly crystalline Mg 2 SnO 4 spinel structure. For the colloidal powder obtained by adding urea and U/Sn=0.5~5 (Examples 2-5) during the manufacturing process, the Mg 2 SnO 4 spinel crystals after annealing at 1200° C. have higher homogeneity.

此外，將實施例2~5、比較例5~6的結果依據Scherrer方程式計算可以得到Mg2SnO4的平均晶粒大小，分別如下表3所示。 In addition, by calculating the results of Examples 2 to 5 and Comparative Examples 5 to 6 according to the Scherrer equation, the average grain size of Mg 2 SnO 4 can be obtained, as shown in Table 3 below.

Figure 108129906-A0305-02-0014-5
Figure 108129906-A0305-02-0014-5

表3結果顯示製程中U/Sn=0~5所得的Mg2SnO4平均晶粒大小，隨著尿素與四氯化錫的莫耳數比值(U/Sn)增大而逐漸縮小，顯示添加較多的尿素可以製得較細小的晶粒。此外，製程中雖有添加尿素但U/Sn大於5所得的Mg2SnO4平均晶粒大小與U/Sn=5所得的Mg2SnO4平均晶粒大小並無明顯差異。 The results in Table 3 show that the average grain size of Mg 2 SnO 4 obtained from U/Sn=0~5 in the process gradually shrinks as the molar ratio (U/Sn) of urea to tin tetrachloride increases. More urea can produce finer grains. In addition, although urea is added in the process, the average grain size of Mg 2 SnO 4 obtained with U/Sn greater than 5 is not significantly different from the average grain size of Mg 2 SnO 4 obtained with U/Sn=5.

由圖4~5可以發現，於製程中添加尿素並共同添加氯化錳(Ⅱ)及異丙醇鈦(Ⅳ)的實施例2、6~17，所製得的粉體產物主要皆為Mg2SnO4尖晶石，且皆不產生氧化錳(Ⅱ)或氧化鈦(Ⅳ)第二相，說明氯化錳(Ⅱ)中Mn2+離子或異丙醇鈦(Ⅳ)中Ti4+離子會分別取代部分Mg2+離子或Sn4+離子而固溶於Mg2SnO4主體晶格中。 It can be found from Figures 4 to 5 that in the process of adding urea and co-adding manganese chloride (II) and titanium isopropoxide (IV) in Examples 2, 6 to 17, the powder products produced are mainly Mg 2 SnO 4 spinel, and there is no second phase of manganese oxide (Ⅱ) or titanium oxide (Ⅳ), indicating that Mn 2+ ions in manganese chloride (Ⅱ) or Ti 4+ in titanium isopropoxide (Ⅳ) The ions will replace part of the Mg 2+ ions or Sn 4+ ions respectively and dissolve in the Mg 2 SnO 4 host lattice.

此外，將實施例2、實施例6~17、比較例7~8的結果依據Scherrer方程式計算可以得到Mg2SnO4的平均晶粒大小，分別如下表4所示。 In addition, calculating the results of Example 2, Examples 6-17, and Comparative Examples 7-8 according to the Scherrer equation, the average crystal grain size of Mg 2 SnO 4 can be obtained, as shown in Table 4 below.

Figure 108129906-A0305-02-0015-6
Figure 108129906-A0305-02-0015-6

表4結果顯示，當固定氯化錳(Ⅱ)添加量時，Mg2SnO4晶粒大小隨著異丙醇鈦(Ⅳ)添加量增加而縮小；而當固定異丙醇鈦 (Ⅳ)添加量時，Mg2SnO4晶粒大小則隨著氯化錳(Ⅱ)添加量增加而增大。 The results in Table 4 show that when the addition amount of manganese chloride (II) is fixed, the Mg 2 SnO 4 grain size decreases as the addition amount of titanium isopropoxide (IV) increases; and when the addition amount of titanium isopropoxide (IV) is fixed The crystallite size of Mg 2 SnO 4 increases with the addition of manganese (II) chloride.

[傅立葉轉換紅外光光譜(Fourier transform infrared spectroscopy,FT-IR)分析][Fourier transform infrared spectroscopy (FT-IR) analysis]

將實施例1~2與比較例2所製得的粉體產物與KBr共同研磨壓片後，以傅立葉轉換紅外光光譜儀(廠商：Varian；型號：2000 FT-IR)量測波數範圍為400~4000cm-1的穿透度，所得光譜圖如圖6所示。 After the powder products prepared in Examples 1 to 2 and Comparative Example 2 were ground and pressed together with KBr, the wavenumber range was 400 measured by a Fourier transform infrared spectrometer (manufacturer: Varian; model: 2000 FT-IR) The transmittance of ~4000cm -1 , the resulting spectrum is shown in Figure 6.

由圖6可以發現，製程中有添加尿素所得的膠體粉末，經1000~1200℃退火後(實施例1~2)的樣品，可以觀察到680、599及443cm-1的特徵峰，其分別對應Mg-O、Sn-O-Sn及八面體格隙的MgO6，顯示其具有Mg2SnO4尖晶石結構。而經800℃退火後(比較例2)的樣品在波數範圍為400~700cm-1內沒有觀察到特徵峰，顯示其Mg2SnO4尖晶石的結晶性非常低。 It can be found from Figure 6 that there is colloidal powder obtained by adding urea in the process. After annealing at 1000~1200℃ (Examples 1~2), characteristic peaks of 680, 599 and 443 cm -1 can be observed, which correspond to Mg-O, Sn-O-Sn and MgO 6 with octahedral lattice gaps show that they have a Mg 2 SnO 4 spinel structure. After annealing at 800°C (Comparative Example 2), no characteristic peaks were observed in the wave number range of 400-700 cm -1 , indicating that the crystallinity of the Mg 2 SnO 4 spinel was very low.

[掃描式電子顯微術(Scanning electron microscopy,SEM)分析][Scanning electron microscopy (SEM) analysis]

將實施例1~2與比較例5所製得的粉體產物以掃描式電子顯微鏡(廠商：Hitachi；型號：S-4800-I)進行拍照，所得SEM相片分別如圖7~9所示。由圖7~9中所得的一次粒子平均粒徑結果整理於下表5中。 The powder products prepared in Examples 1 to 2 and Comparative Example 5 were photographed with a scanning electron microscope (manufacturer: Hitachi; model: S-4800-I), and the obtained SEM photos are shown in Figures 7 to 9 respectively. The results of the average particle size of primary particles obtained from FIGS. 7 to 9 are summarized in Table 5 below.

Figure 108129906-A0305-02-0016-7
Figure 108129906-A0305-02-0016-7

由圖7~9及表5結果可知，於相同退火溫度下，相較於製程中無添加尿素的方法(比較例5)，製程中添加尿素的方法(實施例1、2)所得的粉體產物之一次粒子平均粒徑較小，且具有窄粒徑分布，說明本發明製程中添加尿素並共同添加氯化錳(Ⅱ)及異丙醇鈦(Ⅳ)的方法能減少粉體產物結團的情況且能減小其平均粒徑大小。 From the results of Figures 7-9 and Table 5, it can be seen that at the same annealing temperature, compared to the method without adding urea in the process (Comparative Example 5), the powder obtained by the method of adding urea in the process (Examples 1 and 2) The average particle size of the primary particles of the product is small and has a narrow particle size distribution, which shows that the method of adding urea and co-adding manganese chloride (II) and titanium isopropoxide (IV) in the process of the present invention can reduce agglomeration of powder products Circumstances and can reduce the average particle size.

[X-光光電子能譜(X-ray photoelectron spectroscopy,XPS)分析][X-ray photoelectron spectroscopy (XPS) analysis]

將實施例14及比較例9的粉體產物以X-光光電子能譜儀(廠商：ULVAC-PHI；型號：PHI 5000 VersaProbe)量測O 1s電子的束縛能及強度，結果分別如圖10及圖11所示。 The powder products of Example 14 and Comparative Example 9 were measured with an X-photoelectron spectrometer (manufacturer: ULVAC-PHI; model: PHI 5000 VersaProbe) to measure the binding energy and intensity of O 1s electrons. The results are shown in Figure 10 and Shown in Figure 11.

在圖10及圖11中曲線I(晶格氧)與曲線Ⅱ(氧空缺)下的面積比值AI/AⅡ分別為3.51及3.63，顯示製程中添加尿素並共同添加氯化錳(Ⅱ)及異丙醇鈦(Ⅳ)(實施例14)所得的粉體產物的氧空缺濃度高於製程中添加尿素而無共同添加氯化錳(Ⅱ)及異丙醇鈦(Ⅳ)(比較例9)所得的粉體產物的氧空缺濃度。 In Figure 10 and Figure 11, the area ratio A I /A Ⅱ under curve I (lattice oxygen) and curve II (oxygen vacancy) is 3.51 and 3.63, respectively, indicating that urea is added in the process and manganese chloride (II) is added together. The oxygen vacancy concentration of the powder product obtained from titanium and titanium isopropoxide (IV) (Example 14) is higher than the addition of urea in the process without the co-addition of manganese chloride (II) and titanium isopropoxide (IV) (Comparative Example 9) ) The oxygen vacancy concentration of the obtained powder product.

[電子順磁共振(Electron paramagnetic resonance,EPR)光譜分析][Electron paramagnetic resonance (EPR) spectrum analysis]

將實施例2及比較例5的粉體產物以電子順磁共振光譜儀(廠商：Bruker；型號：ELEXSYS E580)量測Mn2+離子的吸收訊號，其一次微分的結果分別如圖12及圖13所示。 The powder products of Example 2 and Comparative Example 5 were measured with an electron paramagnetic resonance spectrometer (manufacturer: Bruker; model: ELEXSYS E580) to measure the absorption signal of Mn 2+ ions. The first-order differential results are shown in Figure 12 and Figure 13, respectively. Shown.

雖然EPR光譜測得實施例2及比較例5的粉體產物的g因子(g factor)皆約為2.02，顯示Mn2+離子主要是固溶於主體四面體晶格，但製程中添加尿素的粉體產物(實施例2)顯然具有較高分 辨性的超精細六重峰譜線，此為Mn2+離子的特性共振訊號，表示較多孤立的Mn2+離子是均勻分布在Mg2SnO4主體晶格中；而製程中無添加尿素的粉體產物(比較例5)則因局部結團而大幅降低分辨率，顯示製程中添加尿素有助於降低粉體產物結團的情況。 Although the g factor of the powder products of Example 2 and Comparative Example 5 measured by EPR spectroscopy is about 2.02, it shows that Mn 2+ ions are mainly solid-dissolved in the main tetrahedral lattice, but urea is added during the process. the product powder (Example 2) clearly has a higher resolution of the hyperfine spectral sextet, Mn 2+ ions characteristic of this resonance signal, represented more isolated Mn 2+ ions are uniformly distributed in the Mg 2 SnO 4 In the main crystal lattice; the powder product without adding urea in the process (Comparative Example 5) greatly reduces the resolution due to local agglomeration, which shows that the addition of urea in the process helps reduce the agglomeration of the powder product.

[光致發光(Photoluminescence,PL)分析][Photoluminescence (PL) analysis]

將實施例7的粉體產物以螢光光譜儀(廠商：Hitachi；型號：F-7000)量測波長範圍為200~650nm之光致發光的激發光譜及放射光譜，結果如圖14所示。將實施例2、實施例18及比較例5的粉體產物以螢光光譜儀量測波長範圍為300~650nm之光致發光的放射光譜(以波長為268nm的激發光激發)，結果如圖15所示。 The powder product of Example 7 was measured with a fluorescence spectrometer (manufacturer: Hitachi; model: F-7000) to measure the excitation spectrum and emission spectrum of the photoluminescence in the wavelength range of 200 to 650 nm, and the result is shown in FIG. 14. The powder products of Example 2, Example 18 and Comparative Example 5 were measured with a fluorescence spectrometer to measure the emission spectra of photoluminescence in the wavelength range of 300 to 650 nm (excited by excitation light with a wavelength of 268 nm), and the results are shown in Figure 15. Shown.

由圖14可以發現，實施例7的粉體產物的最大吸收峰的波長為268nm。以波長為268nm的激發光激發實施例7的粉體產物，得到的螢光放射峰波長為445nm及498nm，由此可知本發明共同添加含錳(II)活化劑及含鈦(IV)活化劑所製得的粉體產物具有同時放射藍光與綠光的特性。 It can be found from FIG. 14 that the wavelength of the maximum absorption peak of the powder product of Example 7 is 268 nm. The powder product of Example 7 was excited by excitation light with a wavelength of 268nm, and the obtained fluorescence emission peak wavelengths were 445nm and 498nm. It can be seen that the present invention jointly adds manganese (II)-containing activator and titanium (IV)-containing activator The prepared powder product has the characteristic of simultaneously emitting blue and green light.

另外，當固定含錳(II)活化劑添加量時，增加含鈦(IV)活化劑添加量可提高藍光放射強度但會降低綠光放射強度；而當固定含鈦(IV)活化劑添加量時，增加含錳(II)活化劑添加量可提高綠光放射強度並使藍光放射強度略為降低，推論是因Mn2+離子及Ti4+離子在主體晶格的交互作用所導致。當固定含錳(II)活化劑與鎂(II)醇鹽的莫耳數比值(Mn/Mg)為0.003時，若含鈦(IV)活化劑與錫(IV)鹽的莫耳數比值(Ti/Sn)範圍為0.01~0.03可測得較高的藍綠光放射強度；而當固定Ti/Sn為0.03時，若Mn/Mg範圍為0.001~0.003可測得較高的藍綠光放射強度。 In addition, when the addition amount of manganese (II)-containing activator is fixed, increasing the addition amount of titanium (IV)-containing activator can increase the intensity of blue light radiation but reduce the intensity of green light radiation; and when the addition amount of titanium (IV)-containing activator is fixed At this time, increasing the amount of manganese (II)-containing activator can increase the intensity of green light emission and slightly reduce the intensity of blue light emission. It is inferred that it is caused by the interaction of Mn 2+ ions and Ti 4+ ions in the host lattice. When the molar ratio (Mn/Mg) of the manganese (II)-containing activator and the magnesium (II) alkoxide is fixed as 0.003, if the molar ratio of the titanium (IV)-containing activator and the tin (IV) salt is ( Ti/Sn) range of 0.01~0.03 can measure higher blue-green light emission intensity; when fixed Ti/Sn is 0.03, if Mn/Mg range is 0.001~0.003, higher blue-green light emission can be measured strength.

由圖15可以發現，在相同退火溫度及環境的條件下，相較於製程中無添加尿素的方法(比較例5)，製程中添加尿素的方法(實施例2)所得的粉體產物的放射光強度明顯高出許多，且再進一步在氮氫混合氣體(還原氣氛)中進行退火(實施例18)所得的粉體產物的放射光會增加綠光強度。 It can be found from Figure 15 that under the same annealing temperature and environment conditions, compared with the method without adding urea in the process (Comparative Example 5), the radiation of the powder product obtained by the method of adding urea in the process (Example 2) The light intensity is significantly higher, and the emitted light of the powder product obtained by further annealing in a nitrogen-hydrogen mixed gas (reducing atmosphere) (Example 18) will increase the green light intensity.

[CIE色度圖(CIE chromaticity diagram)分析][CIE chromaticity diagram (CIE chromaticity diagram) analysis]

比較例1、7、8及實施例2、7、8、14、18~24的粉體產物以波長λex為268nm的激發光激發後所得的放射光色及CIE色度座標(x,y)如下表6所示。其中，CIE色度座標是依照國際照明組織(International Commission on Illumination，法文縮寫為CIE)所制定的標準三原色(RGB)與三色刺激值(X、Y、Z)進行運算，將螢光光譜儀所測得的放射光譜轉換成色度座標值。另外，商用紅光螢光粉Y2O3：Eu3+、綠光螢光粉Zn2SiO4：Mn2+、藍光螢光粉BAM：Eu2+與比較例7、8及實施例2、7、18、19、21、22、24的粉體產物的放射光在CIE色度圖上的位置如圖16所示。 The powder products of Comparative Examples 1, 7, 8, and Examples 2, 7, 8, 14, 18~24 were excited by excitation light with a wavelength of λ ex of 268 nm and the resulting emission color and CIE chromaticity coordinates (x, y ) As shown in Table 6 below. Among them, the CIE chromaticity coordinates are calculated in accordance with the standard three primary colors (RGB) and tristimulus values (X, Y, Z) established by the International Commission on Illumination (CIE). The measured emission spectrum is converted into chromaticity coordinate values. In addition, commercial red phosphor Y 2 O 3 : Eu 3+ , green phosphor Zn 2 SiO 4 : Mn 2+ , blue phosphor BAM: Eu 2+ and Comparative Examples 7, 8 and Example 2. The positions of the radiated light of the powder products of, 7, 18, 19, 21, 22, and 24 on the CIE chromaticity diagram are shown in Figure 16.

Figure 108129906-A0305-02-0019-8
Figure 108129906-A0305-02-0019-8
Figure 108129906-A0305-02-0020-9
Figure 108129906-A0305-02-0020-9

由表6及圖16可以得知，實施例2、7、8、14、18~24的粉體產物的放射光色皆為青光，且CIE色度座標之x座標值落在0.1026~0.1995範圍間，y座標值落在0.2183~0.3128範圍間，也就是說，本發明於製程中添加尿素並共同添加含錳(II)活化劑及含鈦(IV)活化劑所製得的錫酸鎂尖晶石螢光粉體具有青光放射的特性。另外，退火時間較長的實施例22可提高放射光強度並增進青光的演色性。特別值得一提的是，再進一步在還原氣氛中進行退火的實施例18、19所製得的錫酸鎂尖晶石螢光粉體，其青光放射光具有更佳的飽合度。因此，由前述說明可知，本發明錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法可製得具有青光放射特性的粉體產物，有助於擴大CIE色度圖中三原色(RGB)的色域，進而可增強全彩顯示器及白光LED的演色性。 It can be seen from Table 6 and Figure 16 that the emitted light color of the powder products of Examples 2, 7, 8, 14, 18 to 24 are all cyan light, and the x-coordinate value of the CIE chromaticity coordinates is between 0.1026 and 0.1995 In the range, the y-coordinate value falls within the range of 0.2183~0.3128, that is to say, the magnesium stannate prepared by adding urea and co-adding manganese (II)-containing activator and titanium (IV)-containing activator in the process of the present invention Spinel phosphor powder has the characteristic of cyan light emission. In addition, Example 22 with a longer annealing time can increase the intensity of emitted light and enhance the color rendering of cyan light. It is particularly worth mentioning that the magnesium stannate spinel phosphor powders prepared in Examples 18 and 19, which are further annealed in a reducing atmosphere, have better saturation of the cyan light emission. Therefore, it can be seen from the foregoing description that the preparation method of the manganese-titanium co-activated magnesium stannate spinel fluorescent powder of the present invention can produce a powder product with cyan light emission characteristics, which is helpful to expand the three primary colors (RGB) in the CIE chromaticity diagram The color gamut can enhance the color rendering of full-color displays and white LEDs.

綜上所述，由於本發明製備方法是以該鎂(II)醇鹽及該錫(IV)鹽分別作為鎂源及錫源，可藉由縮聚合反應自然形成凝膠化，能保持組成分子的緊密均勻分布，故可增進錫酸鎂尖晶石的結晶性，且在製程中添加特定量作為水解助劑的尿素(尿素與錫(IV)鹽的莫耳數比值不大於5)，因而能促進水解反應以大幅改善所生成溶膠的分散性與均質性，所製得的錫酸鎂尖晶石結團的情況更少、平均粒徑更小，且共同添加含錳(II)活化劑及含鈦(IV)活化劑以進行水解反應，並在不低於1000℃的溫度下進行退火，可製得具有青光放射特性的錫酸鎂尖晶石螢光粉體，且能提高其放射光強度與穩定性，故確實能達成本發明之目的。 In summary, since the preparation method of the present invention uses the magnesium (II) alkoxide and the tin (IV) salt as the magnesium source and the tin source, respectively, gelation can be formed naturally by the condensation polymerization reaction, and the constituent molecules can be maintained The dense and uniform distribution of the magnesium stannate spinel can improve the crystallinity of the magnesium stannate spinel, and add a specific amount of urea as a hydrolysis aid in the process (the molar ratio of urea to tin(IV) salt is not more than 5), so It can promote the hydrolysis reaction to greatly improve the dispersibility and homogeneity of the resulting sol. The prepared magnesium stannate spinel has less agglomeration and smaller average particle size, and the manganese (II)-containing activator is added together And titanium (IV)-containing activator to carry out the hydrolysis reaction, and annealing at a temperature of not less than 1000 ℃, can produce magnesium stannate spinel phosphor powder with cyan light emission characteristics, and can increase its emission Strength and stability, it can indeed achieve the purpose of the invention.

惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。 However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the patent specification still belong to This invention patent covers the scope.

Claims (10)

一種錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，包含下列步驟：(1)製備前驅液，該前驅液含有鎂(II)醇鹽、錫(IV)鹽及溶劑；(2)於該前驅液中加入含錳(II)活化劑、含鈦(IV)活化劑及尿素並進行水解反應，以獲得透明溶膠，其中，尿素與錫(IV)鹽的莫耳數比值範圍為0.5~5；(3)使該透明溶膠進行縮聚合反應，以獲得透明凝膠；及(4)乾燥該透明凝膠，並在不低於1000℃的溫度下進行退火，以獲得該錳鈦共活化錫酸鎂尖晶石螢光粉體，且該錳鈦共活化錫酸鎂尖晶石螢光粉體的實驗式為Mg2(1-x)MnxSn1-yTiyO4，其中，0.001≦x≦0.01，0.005≦y≦0.1。 A method for preparing manganese-titanium co-activated magnesium stannate spinel fluor powder, comprising the following steps: (1) preparing a precursor liquid, the precursor liquid containing magnesium (II) alkoxide, tin (IV) salt and solvent; (2) Add manganese (II)-containing activator, titanium (IV)-containing activator, and urea to the precursor solution and perform a hydrolysis reaction to obtain a transparent sol, wherein the molar ratio of urea to tin (IV) salt ranges from 0.5 ~5; (3) subjecting the transparent sol to polycondensation reaction to obtain a transparent gel; and (4) drying the transparent gel and annealing at a temperature not lower than 1000°C to obtain the manganese-titanium copolymer Activated magnesium stannate spinel phosphor powder, and the empirical formula of the manganese-titanium co-activated magnesium stannate spinel phosphor powder is Mg 2(1-x) Mn x Sn 1-y Ti y O 4 , where 0.001≦ x≦0.01, 0.005≦y≦0.1. 如請求項1所述的錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，其中，該含錳(II)活化劑是選自於氯化錳(Ⅱ)、硝酸錳(Ⅱ)或其組合。 The method for preparing manganese-titanium co-activated magnesium stannate spinel fluor powder according to claim 1, wherein the manganese (II)-containing activator is selected from manganese chloride (II), manganese nitrate (II) or Its combination. 如請求項1所述的錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，其中，該含鈦(IV)活化劑是選自於異丙醇鈦(Ⅳ)、四氯化鈦或其組合。 The method for preparing manganese-titanium co-activated magnesium stannate spinel fluor powder according to claim 1, wherein the titanium (IV)-containing activator is selected from titanium (IV) isopropoxide, titanium tetrachloride or Its combination. 如請求項1所述的錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，其中，尿素與該錫(IV)鹽的莫耳數比值範圍為1~5。 The method for preparing manganese-titanium co-activated magnesium stannate spinel fluorescer powder according to claim 1, wherein the molar ratio of urea to the tin(IV) salt ranges from 1 to 5. 如請求項1所述的錳鈦共活化錫酸鎂尖晶石螢光粉體的製 備方法，其中，該鎂(II)醇鹽是選自於甲醇鎂、乙醇鎂或其組合。 Preparation of manganese-titanium co-activated magnesium stannate spinel phosphor powder as described in claim 1 The preparation method, wherein the magnesium (II) alkoxide is selected from magnesium methoxide, magnesium ethoxide or a combination thereof. 如請求項1所述的錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，其中，該錫(IV)鹽是選自於四氯化錫、四甲氧基錫、四乙氧基錫或其組合。 The method for preparing manganese-titanium co-activated magnesium stannate spinel fluorescent powder according to claim 1, wherein the tin(IV) salt is selected from tin tetrachloride, tetramethoxytin, and tetraethoxy Tin or a combination. 如請求項1所述的錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，其中，該含錳(II)活化劑與該鎂(II)醇鹽的莫耳數比值範圍為0.001~0.005。 The method for preparing manganese-titanium co-activated magnesium stannate spinel fluorescer powder according to claim 1, wherein the molar ratio of the manganese (II)-containing activator to the magnesium (II) alkoxide ranges from 0.001 to 0.005. 如請求項1所述的錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，其中，該含鈦(IV)活化劑與該錫(IV)鹽的莫耳數比值範圍為0.005~0.100。 The preparation method of manganese-titanium co-activated magnesium stannate spinel fluor powder according to claim 1, wherein the molar ratio of the titanium (IV)-containing activator to the tin (IV) salt ranges from 0.005 to 0.100 . 如請求項1所述的錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，其中，該步驟(4)是於1000~1200℃的溫度下進行退火。 The method for preparing manganese-titanium co-activated magnesium stannate spinel phosphor powder according to claim 1, wherein the step (4) is annealing at a temperature of 1000 to 1200°C. 如請求項1所述的錳鈦共活化錫酸鎂尖晶石螢光粉體的製備方法，其中，該錳鈦共活化錫酸鎂尖晶石螢光粉體經波長268nm的紫外光激發後，產生的放射光為CIE色度座標之x座標值於0.1026~0.1995範圍間及y座標值於0.2183~0.3128範圍間的青色光。 The method for preparing manganese-titanium co-activated magnesium stannate spinel fluor powder according to claim 1, wherein the manganese-titanium co-activated magnesium stannate spinel fluor powder is excited by ultraviolet light with a wavelength of 268 nm, and the radiation generated The light is cyan light with the x-coordinate value of the CIE chromaticity coordinate in the range of 0.1026~0.1995 and the y-coordinate value in the range of 0.2183~0.3128.
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* Cited by examiner, † Cited by third party
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TWI658005B (en) * 2017-12-25 2019-05-01 國立虎尾科技大學 Method for preparing titanium activated magnesium stannate spinel fluorescent powder

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Premkumar V.K, "Facile hydrothermally synthesized mesoporous manganous stannate (Mn2SnO4) nanoparticles and its electrochemical properties.", Materials Research Express, Vol. 4, No. 12,5 Dec. 2017.
Premkumar V.K, "Facile hydrothermally synthesized mesoporous manganous stannate (Mn2SnO4) nanoparticles and its electrochemical properties.", Materials Research Express, Vol. 4, No. 12,5 Dec. 2017. Tsega, Moges, and F. B. Dejene., "Photoluminescence and Thermoluminescence Properties of Sol-Gel Auto-Combustion Driven Mg2SnO4 Nanophosphor.", ECS Journal of Solid State Science and Technology, Vol. 7, No. 11, 31 Oct. 2018, pages R183-R189. Xu, Hongwei, et al., "Exploring the self-redox reaction mechanism of Mn-doped Mg2 (Ti/Sn) O4 with its precise dopant position.", Materials Research Bulletin, Vol.110, Feb 2019, pages 112-119. *
Tsega, Moges, and F. B. Dejene., "Photoluminescence and Thermoluminescence Properties of Sol-Gel Auto-Combustion Driven Mg2SnO4 Nanophosphor.", ECS Journal of Solid State Science and Technology, Vol. 7, No. 11, 31 Oct. 2018, pages R183-R189.
Xu, Hongwei, et al., "Exploring the self-redox reaction mechanism of Mn-doped Mg2 (Ti/Sn) O4 with its precise dopant position.", Materials Research Bulletin, Vol.110, Feb 2019, pages 112-119.

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