【摘要】：隨著能源短缺和環(huán)境問(wèn)題的日益嚴(yán)峻,可再生無(wú)污染的天然能源太陽(yáng)能受到普遍關(guān)注。晶體硅太陽(yáng)能電池占據(jù)著太陽(yáng)能電池市場(chǎng)絕大部分份額,廣泛應(yīng)用于航天、工業(yè)、農(nóng)業(yè)、軍事、民用等領(lǐng)域。然而,太陽(yáng)光分布(300-2500 nm, AM 1.5G)和硅太陽(yáng)能電池響應(yīng)曲線(xiàn)(Eg≈1.12 eV,λ≈1100 nm)的光譜失配導(dǎo)致太陽(yáng)能電池的光電轉(zhuǎn)換效率比較低。于是,如何通過(guò)光譜調(diào)制(Spectral Modulation)增加硅基太陽(yáng)能電池的光電轉(zhuǎn)換效率成為當(dāng)前學(xué)術(shù)界和產(chǎn)業(yè)界研究的熱點(diǎn)問(wèn)題之一。鑒于此,可以通過(guò)能量傳遞過(guò)程將紫外-可見(jiàn)光(300～500 nm)轉(zhuǎn)換為長(zhǎng)波長(zhǎng)的近紅外光(900～1100 nm)或可見(jiàn)光,從而減小能量損失,提高硅基太陽(yáng)能電池的光電轉(zhuǎn)換效率。本文主要以性質(zhì)穩(wěn)定的鋁酸鹽、氯硼酸鹽、硼酸鹽和釩酸鹽作為基質(zhì)材料,稀土離子為摻雜劑,采用溶膠-凝膠法和固相法合成了硅基太陽(yáng)能電池用稀土摻雜下轉(zhuǎn)換發(fā)光材料。主要包括四部分的內(nèi)容：(1)以Dy~(3+)離子與Dy~(3+)-Yb~(3+)、Pr~(3+)-Yb~(3+)、Tb~(3+)-Yb~(3+)雙摻離子對(duì)為摻雜劑,制備了稀土摻雜Li_8Bi_2(MoO_4)_7體系熒光粉。利用X-射線(xiàn)衍射儀、熒光光譜儀等對(duì)樣品的合成條件、結(jié)構(gòu)物相、摻雜濃度、下轉(zhuǎn)換發(fā)光性質(zhì)等進(jìn)行了研究。依據(jù)發(fā)射光譜確定了Dy~(3+)離子在Li_8Bi_2(MoO_4)_7基質(zhì)中發(fā)光的黃藍(lán)比,實(shí)現(xiàn)了白光發(fā)射。通過(guò)計(jì)算得到了Dy~(3+)-Yb~(3+)、Pr~(3+)-Yb~(3+)、Tb~(3+)-Yb3雙摻體系的能量傳遞效率,并分析了下轉(zhuǎn)換能量傳遞機(jī)理。比較了Dy~(3+)、Pr~(3+)、Tb~(3+)不同窄帶吸收(f-f)敏化劑離子對(duì)Yb~(3+)離子近紅外發(fā)光的影響,最終獲得有效的近紅外發(fā)射,并探討了這些熒光粉在硅基太陽(yáng)能電池上的潛在應(yīng)用。(2)采用傳統(tǒng)的高溫固相法合成了RE~(3+)-Yb~(3+)(RE= Tb, Pr, Nd)雙摻、Ce~(3+)-Tb~(3+)-Yb~(3+)三摻雜的Ba_2Y(BO_3)_2Cl下轉(zhuǎn)換熒光粉。首先,對(duì)雙摻體系中Tb~(3+)/Pr~(3+)/Nd~(3+)到Y(jié)b~(3+)的能量傳遞過(guò)程進(jìn)行了研究。然后,系統(tǒng)地對(duì)比了Ce~(3+)-Tb~(3+)-Yb~(3+)三摻與對(duì)應(yīng)的Ce~(3+)-Yb~(3+)和Tb~(3+)-Yb~(3+)雙摻最佳摻雜樣品的下轉(zhuǎn)換發(fā)光性質(zhì)。探索了Tb~(3+)-Yb~(3+)三摻雜體系中的下轉(zhuǎn)換機(jī)理,詳細(xì)分析了可能存在的Ce~(3+)→Tb~(3+), Ce~(3+)→Tb~(3+),Tb~(3+)→Yb~(3+)+和Ce~(3+)→Tb~(3+)→Yb~(3+)四種能量傳遞過(guò)程。闡明了在能量傳遞過(guò)程中Tb~(3+)起橋梁作用,具有f-d躍遷特征的Ce~(3+)離子是一種高效的敏化劑,可以擴(kuò)大紫外-可見(jiàn)波段吸收截面積并增強(qiáng)了近紅外發(fā)射強(qiáng)度。表明Ba_2Y(BO3)2Cl:Ce~(3+),lT~(3+),Yb~(3+)寬譜吸收近紅外熒光粉是一種有潛力的硅基太陽(yáng)能電池用下轉(zhuǎn)換層材料。(3)合成了Ba_3Y(BO_3)_3:Ce~(3+),Nd3'硼酸鹽基近紅外下轉(zhuǎn)換發(fā)光材料,利用Ce~(3+)到Nd~(3+)的能量傳遞將近紫外光轉(zhuǎn)換為近紅外光。在356nm激發(fā)下,不僅能產(chǎn)生Ce~(3+)離子的特征藍(lán)紫光寬譜發(fā)射,還可以發(fā)射出Nd~(3+)離子的近紅外光。討論了Nd~(3+)離子摻雜濃度對(duì)近紅外發(fā)光強(qiáng)度的影響。充分表明,Ce~(3+)-Nd~(3+)雙摻Ba_3Y(BO_3)_3熒光粉可以產(chǎn)生位于900-1100 nm波段的近紅外光,能夠提高硅基太陽(yáng)能電池的光電轉(zhuǎn)換效率。(4)采用溶膠-凝膠法合成了以Ba_2RV_3O_(11)(R=La,Y,Gd,Bi)釩酸鹽為基質(zhì)的下轉(zhuǎn)換發(fā)光材料。對(duì)Ba_2RV_3O_(11):Eu~(3+)熒光粉的下轉(zhuǎn)換發(fā)光性質(zhì)進(jìn)行了分析。著重研究了基質(zhì)敏化型近紅外下轉(zhuǎn)換發(fā)光材料Ba_2LaV_3O_(11):Yb~(3+)和Ba_2YV_3O_(11):Nd~(3+)/HO~(3+)/Yb~(3+)的近紅外發(fā)光性質(zhì)以及相應(yīng)的下轉(zhuǎn)換發(fā)光機(jī)理。證實(shí)了存在釩酸鹽基質(zhì)到Y(jié)b~(3+)的能量傳遞,探索了Ba_2LaV_3O_(11):Yb~(3+)熒光粉中的能量傳遞類(lèi)型。釩酸鹽基熒光粉是一類(lèi)有潛力的硅基太陽(yáng)能電池用下轉(zhuǎn)換光譜調(diào)制材料。
[Abstract]:As the energy shortage and environmental problems become increasingly severe, renewable and non polluting natural energy solar energy is widely concerned. Crystal silicon solar cells occupy most of the market share of solar cells, widely used in space, industry, agriculture, military, civil and other fields. However, the solar distribution (300-2500 nm, AM 1.5G) and silicon sun The spectral mismatch of the cell response curve (Eg 1.12 eV, lambda 1100 nm) leads to the low photoelectric conversion efficiency of the solar cells. Therefore, how to increase the photoelectric conversion efficiency of the silicon based solar cells by spectral modulation (Spectral Modulation) has become one of the hot issues in the current academic and Industry research. The energy transfer process converts ultraviolet visible light (300~500 nm) to long wavelength near infrared light (900~1100 nm) or visible light, thus reducing energy loss and improving the photoelectric conversion efficiency of silicon based solar cells. This paper mainly uses aluminate, borate, borate and vanadate as matrix material, and rare earth ions as admixture. The rare earth doped conversion luminescent materials for silicon based solar cells were synthesized by sol-gel method and solid phase method. The main contents of four parts were as follows: (1) Dy~ (3+) ions and Dy~ (3+) -Yb~ (3+), Pr~ (3+) -Yb~ (3+), Tb~ (3+) doped double ions were used as dopants. The synthesis conditions, structure phase, doping concentration, and down conversion luminescence properties of the samples were studied by - ray diffractometer, fluorescence spectrometer and so on. According to the emission spectra, the yellow and blue ratio of Dy~ (3+) ions in Li_8Bi_2 (MoO_4) _7 matrix was determined, and the Dy~ (3+) -Yb~ (3+), Pr~ (3+) -Yb~ was obtained by calculation. 3 the energy transfer efficiency of the dual doped system and the mechanism of down conversion energy transfer were analyzed. The effects of Dy~ (3+), Pr~ (3+), Tb~ (3+) on the near infrared luminescence of Yb~ (3+) ions by different narrow band absorption (f-f) ions were compared, and the effective near infrared emission was obtained. The potential applications of these phosphors to silicon based solar cells were discussed. (2) the potential application of these phosphors to silicon based solar cells was discussed. The conversion of RE~ (3+) -Yb~ (3+) (RE= Tb, Pr, Nd) and Ce~ (3+) -Tb~ (3+) -Tb~ (3+) three dopants are synthesized by the traditional high temperature solid-phase method. The down conversion luminescence properties of the best doped Ce~ (3+) -Yb~ (3+) and Tb~ (3+) -Yb~ (3+) doped samples are investigated. The mechanism of the down conversion in the Tb~ (3+) -Yb~ (3+) three doping system is explored. The possible existing four energy transfer processes are analyzed in detail. In the process of energy transfer, Tb~ (3+) plays a bridge role, and the Ce~ (3+) ion with the characteristics of F-D transition is a highly efficient sensitizer. It can enlarge the absorption section area of the ultraviolet visible band and enhance the near infrared emission intensity. It shows that Ba_2Y (BO3) 2Cl:Ce~ (3+), lT~ (3+), and broad spectrum absorption near infrared phosphor is a potential silicon based sun. A lower conversion layer material for battery. (3) Ba_3Y (BO_3) _3:Ce~ (3+), Nd3'borate base near infrared light conversion luminescent material, using Ce~ (3+) to Nd~ (3+) energy transfer nearly ultraviolet light to near infrared light. Under 356nm excitation, not only can produce the characteristic blue violet light spectrum emission of Ce~ (3+) ions, but also can emit the ions. Near infrared light. The effect of Nd~ (3+) ion doping concentration on near infrared luminescence intensity is discussed. It is shown that Ce~ (3+) -Nd~ (3+) doped Ba_3Y (BO_3) _3 phosphor can produce near infrared light in 900-1100 nm band, and can improve the photoelectric conversion efficiency of silicon based solar cells. (4) the sol-gel method is used to synthesize Ba_2RV_3O_ (11) (R=La). The lower conversion luminescence properties of Ba_2RV_3O_ (11): Eu~ (3+) phosphor are analyzed in the down conversion luminescence properties of Ba_2RV_3O_ (11): Eu~ (3+) phosphor. The properties of the near infrared luminescence of the matrix sensitized near infrared lower conversion luminescent materials Ba_2LaV_3O_ (11), Yb~ (3+) and Ba_2YV_3O_ (11), and the corresponding down conversion are emphatically studied. Luminescence mechanism. The energy transfer of vanadate matrix to Yb~ (3+) is confirmed and the energy transfer type in Ba_2LaV_3O_ (11): Yb~ (3+) phosphor is explored. Vanadate base phosphor is a kind of potential silicon based solar cell using down conversion spectral modulation material.
【學(xué)位授予單位】：西北大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：O482.31

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