CN111864023B - 一种钨酸钇钠薄膜材料及其制备方法和应用 - Google Patents
一种钨酸钇钠薄膜材料及其制备方法和应用 Download PDFInfo
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 59
- APLRNZFSUMKULK-UHFFFAOYSA-N sodium yttrium Chemical compound [Na].[Y] APLRNZFSUMKULK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000009501 film coating Methods 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 140
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 69
- -1 europium ion Chemical class 0.000 claims description 59
- 238000001035 drying Methods 0.000 claims description 45
- 239000012153 distilled water Substances 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052727 yttrium Inorganic materials 0.000 claims description 30
- 239000013067 intermediate product Substances 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
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- 150000003388 sodium compounds Chemical class 0.000 claims description 18
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- 238000002156 mixing Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 8
- 229910052693 Europium Inorganic materials 0.000 claims description 7
- 229910052772 Samarium Inorganic materials 0.000 claims description 7
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- ZTMNUNZAFAQOMQ-UHFFFAOYSA-N nitric acid oxygen(2-) yttrium(3+) Chemical compound [N+](=O)(O)[O-].[O-2].[Y+3].[O-2].[O-2].[Y+3] ZTMNUNZAFAQOMQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 description 7
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
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- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
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- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
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- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于无机光电功能材料制备技术领域,公开了一种钨酸钇钠薄膜材料及其制备方法和应用。本发明以FTO导电玻璃为基底,利用层层浸渍提拉法交替镀膜制备了一种四方晶系的NaY(WO4)2薄膜材料,通过表面活性剂与前驱体膜层交替镀膜有效改善膜的致密度及晶体生长取向。本发明工艺烧结温度在350~550°之间,具有较好的节能效果,可以显著、大幅度降低生产能耗和生产成本、拓展薄膜的应用领域。
Description
技术领域
本发明属于无机光电功能材料制备技术领域,具体涉及一种钨酸钇钠薄膜材料及其制备方法和应用。
背景技术
薄膜材料的厚度较薄,表面积同体积之比很大,容易产生尺寸效应,表面效应很显著,是现代信息技术的核心要素之一。其与器件结合后成为电子、信息、传感器、光学、太阳能等技术的核心基础。其中的发光薄膜由于在对比度、分辨率、热传导、均匀性、与基底的附着性以及释气速率等方面都显示出较强的优越性,使得在工业上应用更为广泛。
发明内容
基于上述技术问题,本发明的目的在于提供一种钨酸钇钠薄膜及其制备方法。本发明提供的钨酸钇钠薄膜致密度高、光谱宽,发射强度高;制备工艺简单、成本低,具有良好的导热性质,在光催化领域具有广泛的应用前景。
为了实现以上目的,本发明采用的技术方案是:
本发明提供了一种钨酸钇钠薄膜材料,所述钨酸钇钠薄膜材料包含有结构通式为NaY1-x(Rx)(WO4)2的颗粒;其中,R为铕离子、铽离子或钐离子中的任一种,x为R掺杂的摩尔百分数,0≤x<0.5;所述颗粒为四方晶系,形态不规则,晶面平直、棱角分明,平均粒度在110~180nm之间。
本发明还提供了一种钨酸钇钠薄膜的制备方法,包括以下步骤:
(1)配制前驱体溶液:在钨酸盐溶液、钇化合物溶液、R化合物溶液和钠化合物溶液中分别加入柠檬酸后混合为混合液,搅拌均匀后调节混合液的pH值,加入乙二醇,继续搅拌得到前驱体溶液;
(2)取洁净的基片放入步骤(1)所制备的前驱体溶液中,采用浸渍提拉法进行镀膜,取出后干燥得中间产物;或取洁净的基片放入表面活性剂溶液中初次镀膜、干燥后放入步骤(1)所制备的前驱体溶液中再次镀膜干燥后得中间产物;
(3)将中间产物热处理后得到钨酸钇钠薄膜。
步骤(1)中所述钨酸盐溶液为(NH4)10W12O41或(NH4)10H2(W2O7)6溶液;所述钇化合物溶液为硝酸钇水溶液或氧化钇硝酸溶液,所述R化合物溶液为R2O3溶液或R (NO3)3溶液,所述R为铕离子(Eu3+)、铽离子(Tb3+)或钐离子(Sm3+)中任一种;所述钠化合物溶液为NaOH溶液或NaNO3溶液。
步骤(1)中所述混合液中所含的钨酸根离子、钇离子、R离子和钠离子的摩尔比为2:1-x:x:1,其中,0≤x<0.5。
步骤(1)中所述混合液的pH值为3~9。
步骤(1)中所述柠檬酸的质量为钨酸根离子、钇离子和钠离子的1~1.5倍;所述步骤(1)中所述乙二醇与所述柠檬酸的摩尔总量相同。
步骤(2)中所述基片为FTO导电玻璃基片,所述洁净为将基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗后干燥。
步骤(2)所述表面活性剂为十二烷基苯磺酸钠或十六烷基三甲基溴化铵,所述表面活性剂溶液浓度为1.65~15mmol/L。
步骤(2)中所述浸渍提拉法的提拉速度0.3~0.7cm/s,所述干燥的温度为110~130℃,干燥时间为15~30min。
步骤(3)中所述热处理温度为350~550℃,时间为3~6小时。
与现有技术相比,本发明的有益效果是:
本发明以FTO导电玻璃为基底,利用层层浸渍提拉法交替镀膜制备了一种四方晶系的NaY(WO4)2薄膜材料,通过表面活性剂与前驱体膜层交替镀膜有效改善膜的致密度及晶体生长取向。另外,本发明工艺烧结温度在350~550°之间,具有较好的节能效果,可以显著、大幅度降低生产能耗和生产成本,拓展薄膜的应用领域。发明人发现当制备的 NaY(WO4)2薄膜材料掺稀土元素时对膜吸收峰具有意外的影响。当掺杂有铕或钐时,在紫外光区和绿光区均有吸收峰,有显著蓝绿荧光增效作用,发射对光合作用有意义的红橙光;其发射波长在570-650nm范围光谱宽,发射强度高。当掺杂铽时,发射近紫光、可见紫光和蓝绿光荧光,可做为蓝绿光LED激发光源及显示屏荧光材料。所制备的薄膜在智慧农业、微型固态激光器、高清显示设备、光催化等领域均具有广泛的应用前景。
附图说明
图1是实施例1制备的钨酸钇钠薄膜的扫描电子显微镜图;
图2是实施例1制备的钨酸钇钠薄膜的X射线衍射图;
图3是实施例1制备的钨酸钇钠薄膜的Mapping元素图;
图4是实施例2制备的钨酸钇钠薄膜的扫描电子显微镜图;
图5是实施例3制备的钨酸钇钠薄膜的扫描电子显微镜图;
图6是实施例7制备的NaY0.8(Eu0.2)(WO4)2薄膜荧光光谱分析结果图;
图7是实施例8制备的NaY0.85(Tb0.15)(WO4)2薄膜荧光光谱分析结果图;
图8是实施例9制备的NaY0.9(Sm 0.1)(WO4)2薄膜的荧光光谱分析结果图。
具体实施方式
通过下面的实施例可以对本发明进行进一步的描述,然而,本发明的范围并不限于下述实施例。本发明对试验中所使用到的材料以及试验方法进行一般性和/或具体的描述。下列实施例中未注明具体条件的实验方法,通常按照常规条件或按照厂商所建议的条件实施检测。
实施例1
(1)分别将1/3mol的 (NH4)10H2(W2O7)6、2mol的Y(NO3)3和2mol的 NaNO3溶解于蒸馏水中,配置成钨酸盐溶液、钇化合物溶液和钠化合物溶液;称量4.8mol、2.4mol和2.4mol的柠檬酸依次加入上述的钨酸盐溶液、钇化合物溶液和钠化合物溶液中,将上述三种溶液混合均匀后得混合液,混合液中钨离子、钇离子和钠离子的摩尔比为2:1:1;调节混合液的pH值为3,加入9.6mol的乙二醇溶液,搅拌至形成稳定透明液体即得到前驱体溶液;
(2)将FTO导电玻璃基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗15min,干燥后放入步骤(1)制备的前驱体溶液中,采用浸渍提拉法(提拉速度0.3cm/s)在FTO导电玻璃基片上镀膜后在干燥箱中120℃干燥15min得中间产物;对中间产物进行热处理,热处理温度为550℃,保温时间为3小时,最终获得钨酸钇钠薄膜。图1是制备的钨酸钇钠薄膜的扫描电子显微镜图;如图1所示,薄膜表面布满NaY(WO4)2颗粒,颗粒形态棱角分明,致密度高,平均粒径约为180 nm。图2是制备的钨酸钇钠薄膜的X射线衍射图;由图2可见,制备的钨酸钇钠薄膜既包含钨酸钇钠的衍射峰又包括FTO衬底的衍射峰,钨酸钇钠的主峰分别位于2θ=18.729°,29.375°, 31.750°,34.439°,分别对应四方晶系NaY(WO4)2晶体的(101),(103),(004)和(200)晶面,与NYW晶体标准PDF卡主峰相符合,且峰强而尖,晶体结晶性良好。图3是制备的钨酸钇钠薄膜的Mapping元素图;由图3可见,FTO导电玻璃基片表面均匀布满NaY(WO4)2颗粒。
实施例2
取FTO导电玻璃基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗15min,干燥后放入实施例1中制备的前驱体溶液中,采用浸渍提拉法(提拉速度0.7cm/s)在FTO导电玻璃基片上镀膜后在干燥箱中110℃干燥30min得中间产物;对中间产物进行热处理,热处理温度为400℃,保温时间为5小时,获得钨酸钇钠薄膜。图4是本实施例制备的钨酸钇钠薄膜的扫描电子显微镜图;如图4所示,制备的钨酸钇钠薄膜的平均粒径约为118 nm,棱角分明,致密度高。
实施例3
(1)将1/3mol的(NH4)10W12O41溶解于蒸馏水中配置成钨酸盐溶液,2mol的Y2O3溶解于硝酸中配置成钇化合物溶液、2mol的NaOH溶解于蒸馏水中配置成钠化合物溶液;称量4.8mol、2.4mol和2.4mol的柠檬酸依次加入上述的钨酸盐溶液、钇化合物溶液和钠化合物溶液中,将上述三种溶液混合均匀后得混合液,混合液中钨离子、钇离子和钠离子的摩尔比为2:1:1;调节混合液的pH值为7,加入9.6mol的乙二醇溶液,搅拌至形成稳定透明液体即得到前驱体溶液;
(2)将FTO导电玻璃基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗15min,干燥后放入步骤(1)制备的前驱体溶液中,采用浸渍提拉法(提拉速度0.7cm/s)在FTO导电玻璃基片上镀膜后在干燥箱中130℃干燥20min得中间产物;对中间产物进行热处理,热处理温度为550℃,保温时间为4小时,最终获得钨酸钇钠薄膜。图5是制备的钨酸钇钠薄膜的扫描电子显微镜图;由图5可见,颗粒平均粒度约为175 nm,棱角分明,致密度高。
实施例4
(1)分别将1/3mol的 (NH4)10H2(W2O7)6、2mol的Y(NO3)3和2mol的 NaNO3溶解于蒸馏水中,配置成钨酸盐溶液、钇化合物溶液和钠化合物溶液;称量4.8mol、2.4mol和2.4mol的柠檬酸依次加入上述的钨酸盐溶液、钇化合物溶液和钠化合物溶液中,将上述三种溶液混合均匀后得到混合液,混合液中钨离子、钇离子和钠离子的摩尔比为2:1:1;调节混合液的pH值为9,加入9.6mol的乙二醇溶液,搅拌至形成稳定透明液体即得到前驱体溶液;
(2)将FTO导电玻璃基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗15min,干燥后放入浓度为15mmol/L的表面活性剂十二烷基苯磺酸钠(SDBS)溶液中,采用浸渍提拉法(提拉速度0.5cm/s)镀一层薄膜后干燥,再放入步骤(1)制备的前驱体溶液中镀膜后在干燥箱中120℃干燥15min得中间产物;对中间产物进行热处理,热处理温度为550℃,保温时间为4小时,最终获得钨酸钇钠薄膜。颗粒平均粒度约为165 nm,棱角较分明,致密度高。
实施例5
(1)分别将1/3mol的 (NH4)10H2(W2O7)6、2mol的Y(NO3)3和2mol的 NaNO3溶解于蒸馏水中,配置成钨酸盐溶液、钇化合物溶液和钠化合物溶液;称量4.8mol、2.4mol和2.4mol的柠檬酸依次加入上述的钨酸盐溶液、钇化合物溶液和钠化合物溶液中,将上述三种溶液混合均匀后得混合液,混合液中钨离子、钇离子和钠离子的摩尔比为2:1:1;调节混合液的pH值为3,加入9.6mol的乙二醇溶液,搅拌至形成稳定透明液体即得到前驱体溶液;
(2)将FTO导电玻璃基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗15min,干燥后放入浓度为1.72mmol/L的表面活性剂十二烷基苯磺酸钠(SDBS)溶液中,采用浸渍提拉法镀一层薄膜后干燥,再放入步骤(1)制备的前驱体溶液中镀膜后在干燥箱中120℃干燥15min得中间产物;对中间产物进行热处理,热处理温度为450℃,保温时间为4小时,制备得到钨酸钇钠薄膜,通过扫描电子显微镜可得制备的薄膜粒晶平均粒度约为150 nm,棱角较分明,致密度高。
实施例6
将FTO导电玻璃基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗15min,干燥后放入浓度为1.65mmol/L的表面活性剂十六烷基三甲基溴化铵(CTAB)溶液中,采用浸渍提拉法镀一层薄膜后干燥,再放入实施例5步骤(1)所制备的前驱体溶液中第二次镀膜,放入干燥箱中120℃干燥15min得中间产物;对中间产物进行热处理,热处理温度为550℃,保温时间为4小时,最终获得平均粒度约为160 nm的钨酸钇钠薄膜。
实施例7
(1)分别将1/3mol的 (NH4)10H2(W2O7)6溶解于蒸馏水中配置成钨酸盐溶液,1.6mol的Y2O3、0.4mol Eu2O3分别溶解于硝酸中配置成钇化合物溶液和铕化合物溶液,2mol的NaOH溶解于蒸馏水中配置成钠化合物溶液;称量4.8mol、1.92mol、0.48mol和2.4mol的柠檬酸依次加入上述的钨酸盐溶液、钇化合物溶液、铕化合物溶液和钠化合物溶液中,搅拌均匀后将上述四种溶液混合得到混合液,混合液中钨离子、钇离子、铕离子和钠离子的摩尔比为2:0.8:0.2:1;用柠檬酸调节混合液的pH值为5,加入9.6mol的乙二醇溶液,搅拌至形成稳定透明液体即得到前驱体溶液;
(2)将FTO导电玻璃基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗15min,干燥后放入步骤(1)制备的前驱体溶液中,采用浸渍提拉法在FTO导电玻璃基片上镀膜后在干燥箱中120℃干燥30min得中间产物;对中间产物进行热处理,热处理温度为350℃,保温时间为6小时,最终获得致密度高的NaY0.8(Eu0.2)(WO4)2薄膜。薄膜由NaY0.8(Eu0.2)(WO4)2颗粒组成,其晶系与实施例1相同,其粒晶平均粒度为110 nm。图6是制备的NaY0.8(Eu0.2)(WO4)2薄膜荧光光谱分析结果图;如图6所示,制备的薄膜具有显著的荧光强度,同时具有明显的蓝绿荧光增强效果。
实施例8
(1)分别将1/3mol的 (NH4)10H2(W2O7)6、1.7mol的Y(NO3)3、0.3mol Tb (NO3)3和2mol的 NaNO3溶解于蒸馏水中,配置成钨酸盐溶液、钇化合物溶液、铽化合物溶液和钠化合物溶液;称量4.8mol、2.04mol、0.36mol和2.4mol的柠檬酸依次加入上述各化合物溶液中,搅拌均匀后将上述四种溶液混合得到混合液,混合液中钨离子、钇离子、离子和钠离子的摩尔比为2:0.85:0.15:1;用柠檬酸调节混合液的pH值为3,搅拌均匀后加入9.6mol的乙二醇溶液,搅拌至形成稳定透明液体即得到前驱体溶液;
(2)将FTO导电玻璃基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗15min,干燥后放入步骤(1)制备的前驱体溶液中,采用浸渍提拉法在FTO导电玻璃基片上镀膜后在干燥箱中120℃干燥15min得中间产物;对中间产物进行热处理,热处理温度为550℃,保温时间为4小时,最终获得致密度高的NaY0.85(Tb0.15)(WO4)2薄膜。薄膜由NaY0.85(Tb0.15)(WO4)2颗粒组成,其晶系与实施例1相同,粒晶平均粒度为140 nm。图7是制备的NaY0.85(Tb0.15)(WO4)2薄膜荧光光谱分析结果图;如图7所示,荧光光谱分析结果表明,加入Tb3+的量为15%时,发出近紫外和可见紫光和和蓝绿光,其中以最高峰位于545nm的537-554nm绿光区域强度最强。
实施例9
(1)分别将1/3mol的 (NH4)10H2(W2O7)6、1.8mol的Y(NO3)3、0.2mol Sm (NO3)3和2mol的 NaNO3溶解于蒸馏水中,配置成钨酸盐溶液、钇化合物溶液、钐化合物溶液和钠化合物溶液;称量4.8mol、2.16mol、0.24mol和2.4mol的柠檬酸依次加入上述各化合物溶液中,搅拌均匀后将上述四种溶液混合得到混合液,混合液中钨离子、钇离子、钐离子和钠离子的摩尔比为2:0.9:0.1:1;用柠檬酸调节混合液的pH值为3,搅拌均匀后加入9.6mol的乙二醇溶液,搅拌至形成稳定透明液体即得到前驱体溶液;
(2)将FTO导电玻璃基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗15min,再放入步骤(1)制备的前驱体溶液中,采用浸渍提拉法在FTO导电玻璃基片上镀膜后在干燥箱中120℃干燥15min得中间产物;对中间产物进行热处理,热处理温度为550℃,保温时间为4小时,最终获得NaY0.9(Sm 0.1)(WO4)2薄膜。其由NaY0.9(Sm 0.1)(WO4)2颗粒组成,其晶系与实施例1相同,粒晶平均粒度为145 nm。图8是制备的NaY0.9(Sm 0.1)(WO4)2薄膜荧光光谱分析结果图;如图8所示,荧光光谱分析结果表明,当加入Sm 3+的量为10%时,在404nm激发下的发射光谱,主要包含4个发射峰,位于565nm对应黄绿光,600nm对应黄橙光,652nm和700nm对应橙红光。发射光谱表明掺杂Sm3+离子的样品具有将紫外光转化为较强的黄、橙、红光及其过渡色调的能力,与叶绿素吸收光谱匹配。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本领域的技术人员在本发明所揭露的技术范围内,可不经过创造性劳动想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书所限定的保护范围为准。
Claims (6)
1.一种钨酸钇钠薄膜材料,其特征在于,所述钨酸钇钠薄膜材料包含有结构通式为NaY1-x(Rx)(WO4)2的颗粒;其中,R为铕离子、铽离子或钐离子中的任一种,x为R掺杂的摩尔百分数,0≤x<0.5;所述颗粒为四方晶系,形态不规则,晶面平直、棱角分明,平均粒度在110~180nm之间;所述钨酸钇钠薄膜材料的制备方法包括以下步骤:
(1)配制前驱体溶液:在钨酸盐溶液、钇化合物溶液、R化合物溶液和钠化合物溶液中分别加入柠檬酸后混合为混合液,搅拌均匀后调节混合液的pH值,加入乙二醇,继续搅拌得到前驱体溶液;
(2)取洁净的基片放入步骤(1)所制备的前驱体溶液中,采用浸渍提拉法进行镀膜,取出后干燥得中间产物;或取洁净的基片放入表面活性剂溶液中初次镀膜、干燥后放入步骤(1)所制备的前驱体溶液中再次镀膜干燥后得中间产物;
(3)将中间产物热处理后得到钨酸钇钠薄膜;步骤(1)中所述钨酸盐溶液为(NH4)10W12O41或(NH4)10H2(W2O7)6溶液;所述钇化合物溶液为硝酸钇水溶液或氧化钇硝酸溶液;所述R化合物溶液为R2O3溶液或R (NO3)3溶液,所述R为铕离子、铽离子或钐离子中任一种;所述钠化合物溶液为NaOH溶液或NaNO3溶液;步骤(1)中所述混合液中所含的钨酸根离子、钇离子、R离子和钠离子的摩尔比为2:1-x:x:1,其中,0≤x<0.5;步骤(1)中所述混合液的pH值为3~9;步骤(2)中所述基片为FTO导电玻璃基片,所述洁净为将基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗后干燥。
2.一种钨酸钇钠薄膜材料的制备方法,其特征在于,包括以下步骤:
(1)配制前驱体溶液:在钨酸盐溶液、钇化合物溶液、R化合物溶液和钠化合物溶液中分别加入柠檬酸后混合为混合液,搅拌均匀后调节混合液的pH值,加入乙二醇,继续搅拌得到前驱体溶液;
(2)取洁净的基片放入步骤(1)所制备的前驱体溶液中,采用浸渍提拉法进行镀膜,取出后干燥得中间产物;或取洁净的基片放入表面活性剂溶液中初次镀膜、干燥后放入步骤(1)所制备的前驱体溶液中再次镀膜干燥后得中间产物;
(3)将中间产物热处理后得到钨酸钇钠薄膜;步骤(1)中所述钨酸盐溶液为(NH4)10W12O41或(NH4)10H2(W2O7)6溶液;所述钇化合物溶液为硝酸钇水溶液或氧化钇硝酸溶液;所述R化合物溶液为R2O3溶液或R (NO3)3溶液,所述R为铕离子、铽离子或钐离子中任一种;所述钠化合物溶液为NaOH溶液或NaNO3溶液;步骤(1)中所述混合液中所含的钨酸根离子、钇离子、R离子和钠离子的摩尔比为2:1-x:x:1,其中,0≤x<0.5;步骤(1)中所述混合液的pH值为3~9;步骤(2)中所述基片为FTO导电玻璃基片,所述洁净为将基片依次放入丙酮、蒸馏水、酒精、蒸馏水中超声震荡清洗后干燥。
3.根据权利要求2所述的钨酸钇钠薄膜材料的制备方法,其特征在于,步骤(1)中所述柠檬酸的加入量分别为各溶液中钨酸根离子、钇离子或钠离子的1~1.5倍;所述步骤(1)中乙二醇的加入量与各个溶液中柠檬酸的摩尔总量相同。
4.根据权利要求2所述的钨酸钇钠薄膜材料的制备方法,其特征在于,步骤(2)所述表面活性剂为十二烷基苯磺酸钠或十六烷基三甲基溴化铵,所述表面活性剂溶液浓度为1.72~15mmol/L。
5.根据权利要求2所述的钨酸钇钠薄膜材料的制备方法,其特征在于,步骤(2)中所述浸渍提拉法的提拉速度0.3~0.7cm/s,所述干燥的温度为120℃,干燥时间为20min。
6.根据权利要求2所述的钨酸钇钠薄膜材料的制备方法,其特征在于,步骤(3)中所述热处理的温度为350~550℃,时间为3~6小时。
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