磷酸鋯基藍(lán)綠色長(zhǎng)余輝發(fā)光材料制備及其發(fā)光機(jī)理
本文選題:長(zhǎng)余輝發(fā)光材料 + 摻雜 ; 參考:《閩南師范大學(xué)》2017年碩士論文
【摘要】:長(zhǎng)余輝發(fā)光材料是一種蓄光節(jié)能的綠色環(huán)保材料,在標(biāo)識(shí)物、日用工藝品等廣泛應(yīng)用。發(fā)光性能優(yōu)異、化學(xué)性能穩(wěn)定、綠色環(huán)保、制造成本低成為衡量長(zhǎng)于輝發(fā)光材料的重要指標(biāo)。磷酸鹽長(zhǎng)余輝發(fā)光材料具有綠色環(huán)保、化學(xué)性能穩(wěn)定、且易制作等優(yōu)點(diǎn)。本研究首次報(bào)道新型藍(lán)綠色長(zhǎng)余輝發(fā)光材料ZrP_2O_7:Mn~(2+)的制備。采用高溫固相合成法制備以ZrP_2O_7為主體材料,以Zr4+作為發(fā)光中心制備藍(lán)綠色長(zhǎng)余輝發(fā)光材料。通過摻雜低價(jià)態(tài)的金屬離子以及稀土敏化離子以提高材料的發(fā)光性能。對(duì)材料進(jìn)行XRD測(cè)試并對(duì)其物相進(jìn)行分析,所制備的各種摻雜材料ZrP_2O_7:Mn~(2+),M均歸屬于標(biāo)號(hào)為PDF:49-1079的標(biāo)準(zhǔn)圖譜,摻雜未造成物相的改變但引起晶胞的微小收縮并對(duì)材料的結(jié)構(gòu)性能有所改善;對(duì)材料進(jìn)行激發(fā)發(fā)射光譜測(cè)試,并對(duì)激發(fā)峰及發(fā)射峰所對(duì)應(yīng)的微觀能級(jí)躍遷進(jìn)行歸屬,其中位于412 nm、400 nm、382 nm、369 nm及332 nm及附近的激發(fā)峰分別歸屬于Mn~(2+)的6A1→4T1(4G)、6A1→4T2(4G)、6A1→4E、4A1(4G)、6A1→4T2(4D)及6A1→4E(4D)能級(jí)躍遷,493 nm附近的發(fā)射峰來自于Zr4+,屬于藍(lán)光范疇,在545 nm處有一個(gè)很弱的發(fā)射峰,屬于綠光范圍,歸屬于Mn~(2+)離子4T1g→6A1g的能級(jí)躍遷,與所觀察的藍(lán)綠光一致;對(duì)材料的余輝衰減性能進(jìn)行測(cè)試,材料的目測(cè)余輝時(shí)間可以達(dá)到3小時(shí)以上;對(duì)材料進(jìn)行熱釋光譜的測(cè)試,并計(jì)算其能級(jí)陷阱,陷阱深度介于0.2-0.5 eV,深度較合適。通過對(duì)材料進(jìn)行低價(jià)離子(Na+、K+、Sr~(2+))摻雜,替代Zr4+以制造材料的內(nèi)部氧空位缺陷,增加氧缺陷濃度。氧缺陷濃度的增加有利于材料發(fā)光性能的改善;此外,摻雜離子的引入也有利于制造深度更加合適的能級(jí)陷阱,從而改善材料的發(fā)光性能;引入稀土離子(Dy3+、Pr3+、Sm3+)作為敏化離子,利用敏化離子的發(fā)射峰能級(jí)與發(fā)光中心離子能級(jí)的交錯(cuò)以達(dá)到把敏化離子吸收的光能轉(zhuǎn)移給發(fā)光中心從而改善材料的發(fā)光性能。材料被光照射后其電子將由基態(tài)躍遷到激發(fā)態(tài)并在材料內(nèi)部中產(chǎn)生電子空穴對(duì)。處于激發(fā)態(tài)的電子會(huì)弛豫到比較低的能級(jí)狀態(tài),其中大部分直接返回到基態(tài)發(fā)光,而少部分會(huì)被陷阱所捕獲并在熱擾動(dòng)下被釋放出來躍遷回基態(tài)發(fā)出光而起到余輝作用。此外因光激發(fā)而產(chǎn)生的電子空穴對(duì)會(huì)在晶格中遷移并在遷移過程中發(fā)生相遇而覆滅發(fā)光,電子空穴對(duì)的壽命影響材料的余輝性能。
[Abstract]:Long afterglow luminescent material is a kind of green environmental protection material, which is widely used in marking, daily handicraft and so on. Luminescence performance, chemical stability, green environmental protection, low manufacturing cost have become an important index to measure the length of luminescent materials. Phosphates long afterglow luminescent materials have the advantages of green environment, stable chemical properties and easy to manufacture. The preparation of a novel blue-green long afterglow phosphor (ZrP_2O_7:Mn~(2) is reported for the first time. The blue-green long afterglow phosphors were prepared by high temperature solid state synthesis with ZrP_2O_7 as the main material and Zr4 as the luminous center. The luminescence properties of the materials were improved by doping metal ions and rare earth sensitized ions. The materials were tested by XRD and their phases were analyzed. All kinds of doped materials, ZrP_2O_7:Mn~(2 + M, were assigned to the standard spectrum of PDF:49-1079. Doping did not change the phase, but caused the tiny shrinkage of the unit cell and improved the structure and properties of the material. The excitation emission spectrum of the material was measured, and the microscopic energy level transition corresponding to the excitation peak and the emission peak was assigned. The emission peaks near 369nm, 332nm and 332nm of 412Nm ~ (1) ~ (4nm) ~ (3 ~ (2) ~ (3) ~ (2) and ~ (3) ~ (32) nm) belong to Zr4 and belong to the category of blue light, respectively, and the emission peaks of 4A1 ~ (4A ~ (1) ~ (4A ~ (1) ~ (4A ~ (1) ~ (4T _ (2) ~ (4D) and 6A1 _ (4E) ~ (4D) are from Zr4 and belong to the category of blue light, and the emission peaks near the excitation peaks are located at 412nm and 332nm, respectively. There is a very weak emission peak at 545nm, which belongs to the green light range and belongs to the energy level transition of Mn~(2) ion 4T1g 6A1g, which is consistent with the observed blue-green light, and the decay performance of the afterglow of the material is measured. The visual luminescence time of the material can reach more than 3 hours, and the pyrorelease spectrum of the material is measured, and its energy level trap is calculated. The depth of the trap is between 0.2-0.5 EV, and the depth is more suitable. In order to make the internal oxygen vacancy defects and increase the concentration of oxygen defects, the Zr4 was replaced by the doping of Na ~ (2 +) -K ~ (2 +) ~ (2 +) ~ (2 +) in the materials. The increase of oxygen defect concentration is beneficial to the improvement of the luminescence performance of the material, in addition, the introduction of doping ions is also beneficial to the fabrication of energy level traps with more suitable depth, thus improving the luminescent properties of the materials. Rare earth ion (Dy3 + Pr3 + Sm 3) was introduced as sensitized ion. The luminescent properties of the sensitized ion were improved by the interleaving of the emission peak energy level of the sensitized ion and the ion level of the luminous center to transfer the light energy absorbed by the sensitized ion to the luminescent center. When the material is irradiated by light, the electrons will transition from ground state to excited state and the electron hole pair will be generated in the material. The electrons in the excited state will relax to the lower energy level state, most of them will return directly to the ground state to emit light, while a few will be trapped by the trap and released under the thermal disturbance to transfer back to the ground state to emit light, which will play an afterglow effect. In addition, the electron hole pair generated by light excitation will migrate in the lattice and meet during the migration process, and the lifetime of the electron hole pair will affect the afterglow properties of the material.
【學(xué)位授予單位】:閩南師范大學(xué)
【學(xué)位級(jí)別】:碩士
【學(xué)位授予年份】:2017
【分類號(hào)】:O482.31
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