低維無(wú)機(jī)納米材料在有機(jī)光伏與光探測(cè)器件中的應(yīng)用研究
發(fā)布時(shí)間：2018-08-14 14:37
【摘要】：有機(jī)電子學(xué)在過(guò)去的60多年里一直是物理和化學(xué)領(lǐng)域的一大研究熱點(diǎn)。由于具有成本低，質(zhì)量輕和可制備大面積器件等優(yōu)點(diǎn)，有機(jī)半導(dǎo)體非常有潛力成為無(wú)機(jī)半導(dǎo)體的替代材料。近年來(lái)，在有機(jī)半導(dǎo)體材料研究方面所取得的顯著進(jìn)展使有機(jī)光電器件的研制成為了可能，如有機(jī)發(fā)光二極管OLED、有機(jī)光伏器件OPV和有機(jī)光探測(cè)器件OPD等。尤其是OLED，如今已經(jīng)在平板顯示和室內(nèi)照明方面達(dá)到了商業(yè)化應(yīng)用的水平。但是目前OPV和OPD的性能與實(shí)用化的目標(biāo)還有一定的距離，所以對(duì)于OPV和OPD的研究還有很長(zhǎng)一段路要走。基于導(dǎo)電聚合物的光電器件作為有機(jī)光電器件中的一類，由于具有相對(duì)較高的性能和相對(duì)簡(jiǎn)單的溶液制備方法，近幾年得到了非常廣泛的研究。本論文的工作研究了低維無(wú)機(jī)納米材料對(duì)于聚合物太陽(yáng)能電池和有機(jī)/無(wú)機(jī)雜化紫外光探測(cè)器性能的影響。 在聚合物太陽(yáng)能電池方面: 盡管目前新型的窄帶隙聚合物給體材料層出不窮，但由于在450-600nm藍(lán)綠光波段具有良好的吸收和較高的載流子遷移率，P3HT仍然是難以被取代的聚合物給體材料之一。若要從根本上提高P3HT/PCBM共混太陽(yáng)能電池的能量轉(zhuǎn)換效率，除了改善器件對(duì)入射光的利用率之外，必須突破材料自身固有的限制，，進(jìn)一步提高電池器件的開路電壓。 首先，采用NaF、YCl3·xH2O作為前驅(qū)體反應(yīng)物，PVP作為表面活性劑，通過(guò)方法簡(jiǎn)便的溶劑熱法合成了PVP包覆的NaYF4納米顆粒。XRD數(shù)據(jù)顯示，制備的納米顆粒為立方相的β-NaYF4；SEM和TEM的表征結(jié)果表明，納米顆粒的粒徑分布在30-45nm之間。而且，可以清楚的觀察到在納米顆粒表面包覆有一層薄薄的PVP，使得NaYF4納米顆粒能夠溶于P3HT:PCBM的鄰二氯苯混合溶液中。 然后，將制備好的NaYF4納米顆粒按不同質(zhì)量比摻入到P3HT:PCBM（1:1）的鄰二氯苯混合溶液中配制成有源層溶液，并設(shè)計(jì)制作結(jié)構(gòu)為ITO/TiO2/P3HT:PCBM:NaYF4/WO3/Ag的聚合物體異質(zhì)結(jié)太陽(yáng)能電池器件。當(dāng)NaYF4納米顆粒的質(zhì)量分?jǐn)?shù)為0.45wt%時(shí)，器件的性能達(dá)到最優(yōu)，對(duì)應(yīng)的光伏性能參數(shù)為：開路電壓為0.62V，短路電流密度為9.63mA/cm2，填充因子為58.3%，能量轉(zhuǎn)換效率為3.48%，與無(wú)納米顆粒摻雜的器件相比，器件性能得到了明顯的提升。 通過(guò)對(duì)摻入質(zhì)量分?jǐn)?shù)為0.75wt%的PVP且結(jié)構(gòu)為ITO/TiO2/P3HT:PCBM:PVP/WO3/Ag的對(duì)比器件的研究發(fā)現(xiàn)，器件開路電壓的提升主要是由包覆在NaYF4納米顆粒表面的PVP引起。由于PVP能夠與PCBM形成電荷轉(zhuǎn)移復(fù)合物，而且PVP的HOMO能級(jí)（-5.93eV）比P3HT的HOMO能級(jí)（-5.21eV）更深，所以摻入PVP能夠增大有源層的有效帶隙，提高器件的內(nèi)建電勢(shì)，從而提高器件的開路電壓。但是沒有了NaYF4納米顆粒載體，器件的填充因子明顯變差。 通過(guò)對(duì)沒有WO3空穴傳輸層的且結(jié)構(gòu)為ITO/TiO2/P3HT:PCBM:NaYF4/Ag的對(duì)比器件的研究發(fā)現(xiàn)，納米顆粒的引入可以改善有源層的內(nèi)部形貌，有效地提高器件的填充因子。 通過(guò)對(duì)NaYF4顆粒摻雜的且器件結(jié)構(gòu)為ITO/PEDOT:PSS/P3HT:PCBM:NaYF4/LiF/Al的正型結(jié)構(gòu)對(duì)比器件的研究發(fā)現(xiàn)，PVP包覆的NaYF4納米顆粒對(duì)基于P3HT:PCBM共混有源層的聚合物體異質(zhì)結(jié)太陽(yáng)能電池器件性能的提升是具有普遍性的，與器件是否為正型或者反型結(jié)構(gòu)無(wú)關(guān)。 在有機(jī)/無(wú)機(jī)雜化紫外光探測(cè)器方面： 基于GaN、SiC或金剛石等無(wú)機(jī)寬禁帶半導(dǎo)體材料的紫外光探測(cè)器一般需要通過(guò)金屬有機(jī)化學(xué)氣相沉積（MOCVD）或分子束外延（MBE）等復(fù)雜的制備方法來(lái)實(shí)現(xiàn)，導(dǎo)致探測(cè)器的生產(chǎn)成本較高。而且，無(wú)機(jī)半導(dǎo)體材料的禁帶寬度調(diào)節(jié)起來(lái)也十分困難。相比之下，有機(jī)半導(dǎo)體材料及其與無(wú)機(jī)半導(dǎo)體材料形成的雜化材料為低成本、可大面積制備的紫外光探測(cè)器件的實(shí)現(xiàn)提供了相對(duì)簡(jiǎn)單的途徑。另外，通過(guò)調(diào)整有機(jī)材料的化學(xué)結(jié)構(gòu)可以比較容易地調(diào)節(jié)材料的吸收邊位置，所以基于這類材料的紫外光探測(cè)器件在實(shí)現(xiàn)光響應(yīng)的光譜選擇特性時(shí)表現(xiàn)的更為靈活。 基于以上原因，本論文選取帶隙較寬且具有空穴傳導(dǎo)能力的聚乙烯基咔唑（PVK）作為電子給體材料，N型的TiO2二維納米碗陣列（NBs）作為電子受體材料，并利用PVK/TiO2NBs異質(zhì)結(jié)制成具有光譜選擇特性的有機(jī)/無(wú)機(jī)雜化紫外光探測(cè)器。 首先，利用聚苯乙烯（PS）小球膠體模板法和溶膠-凝膠法在ITO襯底表面制備一層高度有序的TiO2二維納米碗陣列。重點(diǎn)研究了TiO2溶膠溶液的濃度對(duì)納米碗陣列形貌的影響，經(jīng)過(guò)優(yōu)化后制備得到的TiO2納米碗結(jié)構(gòu)的直徑約為375nm,碗壁高度約為50nm，寬度約為100nm。由于TiO2的比表面積比較大，可以增加PVK和TiO2異質(zhì)結(jié)的作用面積。 然后，在TiO2二維納米碗陣列結(jié)構(gòu)表面旋涂一層PVK薄膜，制成結(jié)構(gòu)為ITO/TiO2NBs/PVK/WO3/Ag的有機(jī)/無(wú)機(jī)雜化紫外光探測(cè)器器件。ITO在作為電極的同時(shí)，還起到了短波長(zhǎng)濾鏡的作用，使器件表現(xiàn)出了一定程度的光譜選擇特性。器件的具體性能參數(shù)為：器件的光響應(yīng)度峰值位于330nm處，十分靠近UV-B波段（280-320nm），響應(yīng)波長(zhǎng)范圍290-375nm，半峰寬約為38.5nm，且在光照強(qiáng)度為144mWcm-2、波長(zhǎng)為330nm的紫外光照射條件下，偏壓為-5V時(shí)，響應(yīng)度峰值約為8.14A/W。 通過(guò)對(duì)TiO2二維納米碗陣列正面和背面的反射光譜進(jìn)行研究發(fā)現(xiàn)，納米碗陣列結(jié)構(gòu)正面在330nm納米處存在一個(gè)反射峰，而背面在375nm處存在一個(gè)反射峰，這對(duì)整個(gè)器件的波長(zhǎng)選擇特性具有積極的作用。
[Abstract]:Organic electronics has been a research hotspot in the field of physics and chemistry for more than 60 years. Due to its low cost, light weight and large-area fabrication, organic semiconductors have great potential to become substitutes for inorganic semiconductors. In recent years, remarkable progress has been made in the research of organic semiconductors. Organic optoelectronic devices, such as OLED, OPV and OPD, have become possible. Especially OLED, now it has reached the level of commercial application in flat panel display and indoor lighting. There is still a long way to go for the study of OPV and OPD. As a kind of organic optoelectronic devices, conductive polymer-based optoelectronic devices have been widely studied in recent years due to their relatively high performance and relatively simple solution preparation methods. Effects of solar cells and organic / inorganic hybrid UV detectors.
In terms of polymer solar cells:
Although new narrow band gap polymer donors are emerging in endlessly, P3HT is still one of the most difficult polymer donors because of its good absorption and high carrier mobility in 450-600 nm blue-green light band. In addition to the utilization of incident light, the device must break through the inherent limitations of the material itself and further increase the open circuit voltage of the battery device.
Firstly, NaYF4 nanoparticles coated with PVP were synthesized by a simple solvothermal method using NaF, YCl3 xH2O as precursor reactants and PVP as surfactant. XRD data showed that the prepared nanoparticles were cubic phase beta-NaYF4. SEM and TEM characterization results showed that the nanoparticles were between 30 and 45 nm in diameter. It was clearly observed that a thin layer of PVP was coated on the surface of the nanoparticles, enabling NaYF4 nanoparticles to dissolve in the mixed solution of 3 HT: PCBM and o-dichlorobenzene.
Then, the prepared NaYF4 nanoparticles were mixed into the mixed solution of P3HT: PCBM (1:1) and o-dichlorobenzene to prepare the active layer solution. The polymer heterojunction solar cell device with ITO / TiO2 / P3HT: PCBM: NaYF4 / WO3 / Ag structure was designed and fabricated. When the mass fraction of NaYF4 nanoparticles was 0.45wt%, the device properties were studied. The corresponding photovoltaic performance parameters are: open-circuit voltage is 0.62V, short-circuit current density is 9.63mA/cm2, filling factor is 58.3%, energy conversion efficiency is 3.48%. Compared with the device without nano-particle doping, the device performance has been significantly improved.
It is found that the increase of the open circuit voltage is mainly caused by the PVP coated on the surface of NaYF4 nanoparticles. PVP can form charge transfer complex with PCBM, and the HOMO level of PVP (-5.93eV) is higher than that of P3HT. Stage (-5.21 eV) is deeper, so the effective band gap of active layer can be increased by adding PVP, and the built-in potential of the device can be increased, thus the open circuit voltage of the device can be increased.
The comparison device without WO3 hole transport layer and ITO/TiO2/P3HT:PCBM:NaYF4/Ag structure was studied. It was found that the introduction of nanoparticles could improve the internal morphology of the active layer and effectively improve the filling factor of the device.
It is found that PVP-coated NaYF4 nanoparticles can improve the performance of polymer heterojunction solar cell devices based on P3HT:PCBM blend active layer by doping with NaYF4 particles and the device structure is ITO/PEDOT:PSS/P3HT:PCBM:NaYF4/LiF/Al. The inverse structure is independent.
In organic / inorganic hybrid UV detectors,
Ultraviolet photodetectors based on GaN, SiC or diamond have to be fabricated by complex methods such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE), which results in high production cost. Moreover, it is difficult to adjust the band gap of inorganic semiconductor materials. In contrast, organic semiconductors and their hybrid materials with inorganic semiconductors provide a relatively simple way to achieve low-cost, large-area fabrication of ultraviolet detectors. In addition, by adjusting the chemical structure of organic materials, it is relatively easy to adjust the absorption edge position of materials, so based on such materials. The UV detector of the material is more flexible in achieving spectral response characteristics of light response.
Based on the above reasons, PVK with wide band gap and hole conduction ability is selected as electron donor material, N-type titanium dioxide two-dimensional nano-bowl array (NBs) as electron acceptor material, and PVK/TiO2NBs heterojunction is used to fabricate organic/inorganic hybrid UV photodetectors with spectral selectivity.
Firstly, a highly ordered two-dimensional nano-bowl array of titanium dioxide was prepared on ITO substrate by polystyrene (PS) sphere colloid template method and sol-gel method. The width is about 100 nm and the specific surface area of TiO2 is larger than that of PVK.
Then, a layer of PVK film was spin-coated on the surface of the two-dimensional nano-bowl array of titanium dioxide, and a hybrid organic/inorganic ultraviolet detector with ITO/TiO2NBs/PVK/WO3/Ag structure was fabricated. Number: The peak of the photoresponsivity of the device is located at 330 nm, very close to the UV-B band (280-320 nm), the response wavelength range is 290-375 nm, the half-peak width is about 38.5 nm, and the response peak value is about 8.14 A/W when the illumination intensity is 144 mWcm-2, the wavelength is 330 nm, and the bias voltage is - 5 V.
It is found that there is a reflection peak at 330 nm on the front of the nano-bowl array and a reflection peak at 375 nm on the back of the nano-bowl array, which has a positive effect on the wavelength selectivity of the whole device.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TB383.1;TM914.4
本文編號(hào)：2183171
[Abstract]:Organic electronics has been a research hotspot in the field of physics and chemistry for more than 60 years. Due to its low cost, light weight and large-area fabrication, organic semiconductors have great potential to become substitutes for inorganic semiconductors. In recent years, remarkable progress has been made in the research of organic semiconductors. Organic optoelectronic devices, such as OLED, OPV and OPD, have become possible. Especially OLED, now it has reached the level of commercial application in flat panel display and indoor lighting. There is still a long way to go for the study of OPV and OPD. As a kind of organic optoelectronic devices, conductive polymer-based optoelectronic devices have been widely studied in recent years due to their relatively high performance and relatively simple solution preparation methods. Effects of solar cells and organic / inorganic hybrid UV detectors.
In terms of polymer solar cells:
Although new narrow band gap polymer donors are emerging in endlessly, P3HT is still one of the most difficult polymer donors because of its good absorption and high carrier mobility in 450-600 nm blue-green light band. In addition to the utilization of incident light, the device must break through the inherent limitations of the material itself and further increase the open circuit voltage of the battery device.
Firstly, NaYF4 nanoparticles coated with PVP were synthesized by a simple solvothermal method using NaF, YCl3 xH2O as precursor reactants and PVP as surfactant. XRD data showed that the prepared nanoparticles were cubic phase beta-NaYF4. SEM and TEM characterization results showed that the nanoparticles were between 30 and 45 nm in diameter. It was clearly observed that a thin layer of PVP was coated on the surface of the nanoparticles, enabling NaYF4 nanoparticles to dissolve in the mixed solution of 3 HT: PCBM and o-dichlorobenzene.
Then, the prepared NaYF4 nanoparticles were mixed into the mixed solution of P3HT: PCBM (1:1) and o-dichlorobenzene to prepare the active layer solution. The polymer heterojunction solar cell device with ITO / TiO2 / P3HT: PCBM: NaYF4 / WO3 / Ag structure was designed and fabricated. When the mass fraction of NaYF4 nanoparticles was 0.45wt%, the device properties were studied. The corresponding photovoltaic performance parameters are: open-circuit voltage is 0.62V, short-circuit current density is 9.63mA/cm2, filling factor is 58.3%, energy conversion efficiency is 3.48%. Compared with the device without nano-particle doping, the device performance has been significantly improved.
It is found that the increase of the open circuit voltage is mainly caused by the PVP coated on the surface of NaYF4 nanoparticles. PVP can form charge transfer complex with PCBM, and the HOMO level of PVP (-5.93eV) is higher than that of P3HT. Stage (-5.21 eV) is deeper, so the effective band gap of active layer can be increased by adding PVP, and the built-in potential of the device can be increased, thus the open circuit voltage of the device can be increased.
The comparison device without WO3 hole transport layer and ITO/TiO2/P3HT:PCBM:NaYF4/Ag structure was studied. It was found that the introduction of nanoparticles could improve the internal morphology of the active layer and effectively improve the filling factor of the device.
It is found that PVP-coated NaYF4 nanoparticles can improve the performance of polymer heterojunction solar cell devices based on P3HT:PCBM blend active layer by doping with NaYF4 particles and the device structure is ITO/PEDOT:PSS/P3HT:PCBM:NaYF4/LiF/Al. The inverse structure is independent.
In organic / inorganic hybrid UV detectors,
Ultraviolet photodetectors based on GaN, SiC or diamond have to be fabricated by complex methods such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE), which results in high production cost. Moreover, it is difficult to adjust the band gap of inorganic semiconductor materials. In contrast, organic semiconductors and their hybrid materials with inorganic semiconductors provide a relatively simple way to achieve low-cost, large-area fabrication of ultraviolet detectors. In addition, by adjusting the chemical structure of organic materials, it is relatively easy to adjust the absorption edge position of materials, so based on such materials. The UV detector of the material is more flexible in achieving spectral response characteristics of light response.
Based on the above reasons, PVK with wide band gap and hole conduction ability is selected as electron donor material, N-type titanium dioxide two-dimensional nano-bowl array (NBs) as electron acceptor material, and PVK/TiO2NBs heterojunction is used to fabricate organic/inorganic hybrid UV photodetectors with spectral selectivity.
Firstly, a highly ordered two-dimensional nano-bowl array of titanium dioxide was prepared on ITO substrate by polystyrene (PS) sphere colloid template method and sol-gel method. The width is about 100 nm and the specific surface area of TiO2 is larger than that of PVK.
Then, a layer of PVK film was spin-coated on the surface of the two-dimensional nano-bowl array of titanium dioxide, and a hybrid organic/inorganic ultraviolet detector with ITO/TiO2NBs/PVK/WO3/Ag structure was fabricated. Number: The peak of the photoresponsivity of the device is located at 330 nm, very close to the UV-B band (280-320 nm), the response wavelength range is 290-375 nm, the half-peak width is about 38.5 nm, and the response peak value is about 8.14 A/W when the illumination intensity is 144 mWcm-2, the wavelength is 330 nm, and the bias voltage is - 5 V.
It is found that there is a reflection peak at 330 nm on the front of the nano-bowl array and a reflection peak at 375 nm on the back of the nano-bowl array, which has a positive effect on the wavelength selectivity of the whole device.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TB383.1;TM914.4
【參考文獻(xiàn)】
相關(guān)博士學(xué)位論文 前1條
1 陶晨;反型體異質(zhì)結(jié)聚合物太陽(yáng)能電池的研究[D];吉林大學(xué);2010年
本文編號(hào)：2183171
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