三苯甲基改性油溶性碳量子点合成及其在发光器件中的应用

碳量子点团聚将导致严重荧光猝灭,大幅降低其发光效率,阻碍了其作为发光材料在显示和照明器件中的应用。通过主客体掺杂方案可有效解决上述问题,但水溶性的碳量子点不能和有机的主体材料相匹配。针对该问题,本文通过在碳量子点表面接枝亲油性的芳香类官能团,保证碳量子点油溶性的同时使其具备一定的载流子传输性能,采用该方案制备出发光峰在533 nm、荧光量子产率为43%的黄色油溶性碳量子点。将该碳量子点分散到聚甲基丙烯酸甲酯中涂敷在紫外发光二极管(365 nm)灯珠表面,制备的光致发光器件发出明亮黄光(560 nm),最大亮度达到23 000 cd/m~2。进一步将该碳量子点掺杂到聚乙烯基咔唑中作为发光层,制备了主客体掺杂的电致发光器件,器件的发射峰位于552 nm,最大亮度达到35.07 cd/m~2。上述研究表明,合成油溶性的碳量子点发光材料并将其掺杂到母体材料中作为发光层,可有效抑制碳量子点团聚诱导荧光猝灭问题,对发展高性能碳量子点基发光器件具有重要意义。     

基于石墨烯-钙钛矿量子点场效应晶体管的光电探测器

以等离子增强化学气相沉积法制备的石墨烯作为导电沟道材料,将其与无机CsPbI_3钙钛矿量子点结合,设计并制备了石墨烯-钙钛矿量子点场效应晶体管光电探测器.研究和分析了石墨烯作为场效应晶体管的电学特性及其与钙钛矿量子点结合作为光电探测器的光电特性.结果表明,石墨烯在场效应晶体管中表现出良好的电学性质,其与钙钛矿量子点的结合对波长为400 nm的光辐射具有明显的光响应,在光强为12μW时器件光生电流最大为64μA,响应率达6.4 A·W~(-1),对应的光电导增益和探测率分别为3.7×10~4,6×10~7Jones(1 Jones=1 cm·Hz~(1/2)·W~(-1)).     

基于二维材料二硒化锡场效应晶体管的光电探测器

以二硒化锡作为沟道材料,设计并制备基于二硒化锡场效应晶体管的光电探测器.以化学气相输运法制备的二硒化锡纯度高且结晶度良好,对二硒化锡使用机械剥离法制备出层状二硒化锡,薄膜的横向尺寸最大可达25—35μm,最薄厚度仅为1.4 nm,使用图形转移法制备基于二硒化锡的场效应晶体管,表面光滑无褶皱,且表现出良好的电学性质,呈现出n型半导体的特征,作为光电探测器对波长分别为405, 532, 650 nm的三基色光表现出明显的光响应.尤其是对405 nm的蓝紫光响应度最高,在光强为5.40 m W/cm~2时,响应度达到19.83 AW~(–1),外量子效率达到6.07×10~3%,探测率达到4.23×10~(10) Jones,并且具有快速的响应速度,响应反应时间为23.8 ms.结果表明二硒化锡在可见光光探测器和新一代光电子器件中具有潜在的应用前景.     

基于CdSe/ZnS量子点光转化层的高稳定性白光LED器件

采用一步法合成了510,550和630 nm三种峰值的高稳定性、高量子效率核壳结构CdSe/ZnS量子点材料,其量子产率分别达到82%,98%,97%。将该量子点材料取代传统的荧光粉材料,与硅胶均匀混合后作为光转换层涂覆到蓝色InGaN LED芯片上,制备了白光LED器件。通过依次添加不同颜色量子点制备的量子点光转换层,考察了510,550和630 nm三色CdSe/ZnS量子点在硅胶中的不同配比对白光LED器件性能的影响,研究了不同颜色量子点之间的能量转换机制,利用量子点对白光光谱及其色坐标的影响机制,得到优化的白光器件结果及其三色量子点的配比,结果表明,当绿色、黄绿色、红色三种量子点之间的配比为24∶7∶10时,得到高稳定性、高效率的正白光器件特性,在电流20～200 mA范围内,色温变化为4 607～5 920 K,色坐标变化为（0.355 1,0.348 3）～（0.323 4,0.336 1）,显色指数变化为77.6～84.2,器件最高功率效率达到31.69 lm W-1@20 mA。另外,为了进一步考察器件性能稳定的原因,研究了时间、温度以及UV处理对CdSe/ZnS QDs/硅胶混合光转换材料稳定性的影响,结果表明,器件的高稳定性可归因于所采用的一步法合成的核壳结构量子点材料本身的稳定性,研究的优化器件结果是一种低能耗的优质白光光源,可使人们真实地感知物体的原貌,在正白光光源领域具有很好的应用前景。     

ZnO肖特基势垒紫外探测器

以p-Si(111)为衬底,用水热法首次制得六棱微管ZnO。并以此为有源区利用平面磁控溅射技术沉积得到Ag叉指状电报,从而制作了Ag／n-ZnO肖特基势垒结紫外探测器。对该紫外光探测器的暗电流和365nm波长光照下的光电流、光响应和量子效率进行了测试。测试结果表明：Ag和ZnO六棱管间已形成肖特基接触．其有效势垒高度为0．35eV。无光照时,暗电流很小,当用λ=365nm的光照射Ag/n-ZnO肖特基结时．在5．9V偏压时,光生电流分别为25．6,57．9μA。Ag／n-ZnO紫外探测器有明显的光响应特性和较高的量子效率,在366nm波长处,光响应度达到最大值0．161A／W,量子效率为54．7％。     

Mn掺杂Zn-In-S量子点的制备及发光性质研究

制备了Mn掺杂Zn-In-S量子点并研究了Zn/In的量比和反应温度对其发光性质的影响。在Mn掺杂的Zn-In-S量子点的发光谱中观测到一个600 nm发光带。通过改变Zn/In的量比,掺杂量子点的吸收带隙可从3.76 e V(330 nm)调谐到2.82 e V(440 nm),但600 nm发光峰的波长只有略微移动。这些掺杂量子点的最长荧光寿命为2.14 ms。当反应温度从200℃增加到230℃时,掺杂量子点的发光强度增加并达到最大值;而继续升高温度至260℃时,发光强度迅速减弱。此外,测量了Mn掺杂Zn-In-S量子点的变温发光光谱。发现随着温度的升高,发光峰位发生蓝移,发光强度明显下降。分析认为,Mn掺杂Zn-In-S量子点的600 nm发光来自于Mn2+离子的4T1和6A1之间的辐射复合。     

红、绿CdSe@ZnS量子点配比对三波段标准白光LED器件的影响

将一步法合成的具有梯度合金结构的红光、绿光CdSe@ZnS量子点与硅胶均匀混合后,作为光转换层涂覆到蓝色InGaN LED芯片上,制备了不含荧光材料的三波段白光LED器件。研究了峰值为650 nm和550 nm的高效率红、绿量子点在硅胶中的含量及配比对白光LED色坐标以及效率的影响。结果表明,当红、绿量子点配比为2：3时,可得到发射纯正白光的QDs-LED器件,色坐标为（0.322 8,0.335 9）、色温为5 725 K,功率效率为26.61 lm/W,显色指数为72.7。光谱中红、蓝、绿三色发光峰的半高宽分别为30,25,38 nm,表明器件具有很好的单色性和高色纯度。     

大面积单层二硫化钼的制备及其光电性能

过渡金属硫族化合物(TMDCs)材料具有优异的电学和光电性能,在下一代光电子器件中具有广阔的应用前景.然而,大面积均匀生长单层的TMDCs仍然具有相当大的挑战.本工作提出了一种简单而有效的利用化学气相沉积(CVD)制备大面积单层二硫化钼(MoS₂)的方法,并通过调整氧化物前驱体的比例,调整MoS₂单晶/薄膜生长.随后,利用叉指电极掩膜板制备出单层MoS₂薄膜光电探测器.最后,在405 nm激光激发下,不同电压和不同激光功率条件下均表现出高稳定和可重复的光电响应,响应时间可达毫秒(ms)量级.此外,该光电探测器实现了405—830 nm的可见光到近红外的宽光谱检测范围,光响应度(R)高达291.7 mA/W,光探测率(D^*)最高达1.629×10⁹ Jones.基于该CVD制备的单层MoS2薄膜光电探测器具有成本低、能大规模制备,且在可见光到近红外的宽光谱范围内具有良好的稳定性和重复性的优点,为未来电子和光电子器件的应用提供了更多的可能性.     

脉冲功率对含硅量子点SiCx薄膜物相结构及光谱特性的影响

基于硅量子点（Si-QDs）的全硅叠层太阳电池被认为是最有潜质的高效太阳电池之一。目前所报道的硅量子点薄膜存在硅量子点数密度低、缺陷多等问题,限制了硅量子点太阳电池的光电转换效率。微波退火(microwave annealing, MWA)被认为是一种有益于制备纳米结构材料的方法。微波退火的非热效应可以降低形核能,改善薄膜的微结构和光电性能。因此,采用磁控共溅射技术并结合微波退火工艺,在不同的脉冲功率下制备了含硅量子点SiC_x薄膜;采用掠入射X射线衍射(GIXRD)、拉曼(Raman)光谱、紫外-可见-近红外分光光度计和光致发光(PL)光谱表征薄膜的物相结构及光谱特性;研究不同脉冲功率对硅量子点数密度和性能的影响,进而改进磁控共溅射工艺,制备硅量子点数密度较高和性能良好的薄膜。样品的GIXRD谱和Raman谱均显示其中存在硅量子点,其强度先增大后减小;通过谢乐(Scherrer)公式估算出硅量子点尺寸呈现先增大后减小的规律,脉冲功率为80 W时尺寸达到最大(8.0 nm）。在Raman光谱中还观察到中心位于511 cm-1处出现硅量子点Si-Si横向光学振动模式的拉曼峰,其强度也呈现先增大后减小的趋势;对拉曼光谱做最佳高斯(Gauss)分峰拟合,得出薄膜的晶化率均高于62.58%,脉冲功率为80 W时制备的薄膜具有最高的晶化率(79.29%)。上述分析表明薄膜中均有硅量子点的形成,且数量先增加后减小,脉冲功率为80 W时硅量子点数量最多。通过测量样品的透射率T、反射率R等光学参数,利用Tauc公式估算出薄膜的光学带隙,发现带隙值随溅射功率的增加先减小后增大,在脉冲功率为80 W时最小(1.72 eV)。硅量子点尺寸与光学带隙成反比,说明薄膜中的硅量子点具有良好的量子尺寸效应。通过PL光谱分析样品的发光特性,对其做最佳高斯拟合,发现样品中均有6个发光峰。结合Raman光谱的分析结果,可以得出波长位于463~624 nm的发光峰源于硅量子点的作用;而波长位于408和430 nm的发光峰则源于薄膜内部的缺陷态,峰位没有偏移,但强度有变化。根据发光峰对应的波长可计算其能带分布,从而确定缺陷态类型：408 nm的发光峰归因于≡Si°→E_v电子辐射跃迁,430 nm的发光峰则归因于≡Si°→≡Si-Si≡的缺陷态发光。还研究了硅量子点的尺寸对发光峰移动的影响。结果表明,随硅量子点尺寸变小（大）,发光峰蓝移（红移）。综上,溅射功率为80 W时制备的含硅量子点SiC_x薄膜性能最佳。研究结果为硅量子点太阳电池的后续研究奠定了基础。     

石墨烯量子点:制备及检测乙醇-水溶液组分

采用改进的非完全脱水碳化方法制备石墨烯量子点.产物尺寸约6 nm,激发峰355 nm,发射峰458 nm.基于乙醇对石墨烯锯齿边质子化的抑制效应,发现可通过石墨烯量子点荧光光强检测乙醇-水混合溶液组分.在0.01-100%范围内,乙醇体积百分比与发射峰光强增量呈线性关系.本研究为制备石墨烯量子点提供参考,提出了简易的较宽范围的乙醇水溶液含量检测方法 .     

半导体红外量子点发展现状与前景

半导体量子点具有独特的光学与电学性质,特别是红外量子点良好的光稳定性和生物相容性等优点使其在光电器件、生物医学等领域受到广泛关注。综述了吸收或发射光谱位于红外波段的量子点在激光、能源、光电探测以及生物医学等方面的应用现状与前景,归纳了适用于红外量子点材料的制备方法,并对比了不同方法在应用中的优势。半导体红外量子点材料选择丰富、应用形式多样:InAs量子点被动锁模激光器在1.3 μm波长处产生7.3 GHz的近衍射极限脉冲输出;InAs/GaAs量子点双波长激光器可泵浦产生0.6 nW的THz波;PbS量子点掺杂光纤放大器可在1.53 μm中心波长处实现10.5 dB光增益,带宽160 nm;CdSeTe量子点敏化太阳能电池、异质结Si基量子点太阳能电池的总转换效率可达8%和14.8%;胶质HgTe量子点制成的量子点红外探测器(QDIP)可实现3 μm~5 μm中波红外探测,Ge/Si量子点可实现3 μm~7 μm红外探测;CdTe/ZnSe核壳量子点可用于检测DNA序列的损伤与突变。半导体红外量子点上述应用形式的发展,将进一步促进红外光电系统向高效、快速、大规模集成的方向演进,也将极大地促进临床医学中活体成像检测的应用推广。     

Experimental investigation of energy transfer between CdSe/ZnS quantum dots and different-sized gold nanoparticles

Hybrid nanostructures of quantum dots(QDs) and metallic nanostructure are attractive for future use in a variety of optoelectronic devices. For photodetection applications, it is important that the photoluminescence (PL) of QDs is quenched by the metallic nanostructures. Here, the quenching efficiency of CdSe/ZnS core-shell quantum dots (QDs) with different sized gold nanoparticles (NPs) films through energy transfer is investigated by measuring the PL intensity of the hybrid nanostructures. In our research, the gold NPs films are formed by the post-annealing of the deposited Au films on the quartz substrate. We find that the energy transfer from the QDs to the Au NPs strongly depends on the sizes of the Au NPs. For CdSe/ZnS QDs direct contact with the Au NPs films, the largest energy transfer efficiency are detected when the resonance absorption peak of the Au NPs is nearest to the emission peak of the CdSe/ZnS QDs. However, when there is a PMMA spacer between the QDs layer and the Au NPs films, firstly, we find that the energy transfer efficiency is weakened, and the largest energy transfer efficiency is obtained when the resonant absorption peak of the Au NPs is farthest to the emission peak wavelength of CdSe/ZnS QDs. These results will be useful for the potential design of the high efficiency QDs optoelectronic devices.     

以巯基丙酸为稳定剂的水溶性CdTe量子点的水热合成及表征

以巯基丙酸(MPA)为稳定剂,采用水热合成方法在160 ℃下合成水溶性CdTe量子点。研究了不同反应时间及反应前驱体溶液的不同pH值对合成的CdTe量子点光学性质的影响。结果表明:所制得的CdTe量子点的荧光发射波长在510~661 nm范围内连续可调,并且CdTe量子点的光学性质强烈地依赖于反应前驱体溶液的pH值,最佳pH值为9。透射电子显微镜和X射线衍射分析表明所制备的CdTe量子点的形状接近于球形,粒径分布较均匀。与回流方法制备的水溶性量子点相比,高温条件下的水热合成方法简单,反应时间短,CdTe量子点生长速度快,100 min就可生长到3.5 nm,并且所制得的CdTe量子点荧光强度高,稳定性好,荧光量子产率也较高,最高可达44.6%。     

Synthesis of ZnO quantum dots and their agglomeration mechanisms along with emission spectra based on ageing time and temperature

The ZnO quantum dots (QDs) were synthesized with improved chemical solution method. The size of the ZnO QDs is exceedingly uniform with a diameter of approximately 4.8 nm, which are homogeneously dispersed in ethanol. The optical absorption edge shifts from 370 nm of bulk material to 359 nm of QD materials due to the quantum size effect, while the photoluminescence peak shifts from 375 nm to 387 nm with the increase of the density of ZnO QDs. The stability of ZnO QDs was studied with different dispersion degrees at 0 ℃ and at room temperature of 25 ℃. The agglomeration mechanisms and their relationship with the emission spectra were uncovered for the first time. With the ageing of ZnO QDs, the agglomeration is aggravated and the surface defects increase, which leads to the defect emission.     

Broadband light emitting from multilayer-stacked InAs/GaAs quantum dots

We report the effect of the GaAs spacer layer thickness on the photoluminescence(PL) spectral bandwidth of InAs/GaAs self-assembled quantum dots(QDs).A PL spectral bandwidth of 158 nm is achieved with a five-layer stack of InAs QDs which has a 11-nm thick GaAs spacer layer.We investigate the optical and the structural properties of the multilayer-stacked InAs/GaAs QDs with different GaAs spacer layer thicknesses.The results show that the spacer thickness is a key parameter affecting the multi-stacked InAs/GaAs QDs for wide-spectrum emission.     

Synthesis of CdSe/CdS with a simple non-TOP-based route

A convenient and non-TOP-based route for the synthesis of core-shell CdSe/CdS quantum dots (QDs) is developed for the first time. Simple reagents, such as cadmium oxide, selenium powder, sodium sulfide, paraffin and oleic acid with obvious advantages are used to replace organometallics. This simple route allows the preparation of a series of core-shell CdSe/CdS QDs emitting in a wide wavelength range (from 510 to 615 nm). After passivation of CdSe by CdS shell using sodium sulfide as the source of sulfur at 80 °C, the quantum yields (QYs) are improved from 15-30% to 35-50% and remained stable at least for 4 months. A narrow bandwidth (FWHM<50 nm) indicates that the as-prepared QDs have uniform size distribution, desirable dispersibility and good fluorescence properties. The whole procedure can be carried out either open to air or under nitrogen atmosphere, which is simpler, greener and cheaper as compared with TOP-based route.     

超小晶粒锡掺杂CsPbBr3蓝光量子点的合成及其光学性能研究

近年来,铅卤钙钛矿CsPbX₃ (X=Cl,Br或I)因其具有荧光波段可调、荧光量子产率高(Photoluminescence quantum yield,PLQY)以及荧光半峰宽窄等优点而被广泛应用于光电器件领域.然而,与PLQY接近于100%的绿光和红光相比,蓝光卤素钙钛矿的PLQY仍比较低.在此,采用过饱和结晶的方法在室温下合成了粒径低于4 nm的超小晶粒锡(Sn)掺杂CsPbBr₃量子点,并对其结构特性和光学特性进行了研究.结果表明:随着SnBr₂添加量的增大,量子点晶粒的粒径略微减小,荧光发射峰发生蓝移,粒径由3.33 nm (SnBr₂为0.03 mmol)减小到2.23 nm(SnBr₂为0.06 mmol时),对应的荧光发射峰由490 nm蓝移至472 nm.当SnBr₂添加量为0.05 mmol时合成的超小晶粒锡掺杂CsPbBr₃量子点显示出最优的光学性能,其粒径约为2.91 nm,对应的XRD各晶面衍射峰强度最强,...     

Assembly,characterization, and photocatalytic activities of TiO<Subscript>2</Subscript> nanotubes/CdS quantum dots nanocomposites

The semiconductor quantum dots (QDs) can be very efficient to tune the response of photocatalyst of TiO₂ to visible light. In this study, CdS QDs formed in situ with about 8 nm have been successfully deposited onto the surfaces of TiO₂ nanotubes (TNTs) to form TNTs/CdS QDs nanocomposites by use of a simple bifunctional organic linker, thiolactic acid. The diffuse reflectance spectroscopy (DRS) spectra of as prepared samples showed that the absorption edge of the TNTs/CdS composite is extended to visible range, with absorption edge at 530 nm. The photocatalytic activity and stability of TNTs/CdS were also evaluated for the photodegradation of rhodamine B. The results showed that when TNTs/CdS QDs was used, photocatalytic degradation of RhB under visible light irradiation reached 91.6%, higher than 45.4 and 30.5% for P25 and TNTs, respectively. This study indicated that the TNTs/CdS QDs nanocomposites were superior catalysts for photodegradation under visible light irradiation compared with TNTs and P25 samples, which may find wide application as a powerful photocatalyst in environmental field.     

Annealing of In0.45Ga0.55As/GaAs quantum dots overgrown with large monolayer (11 ML) coverage for applications in thermally stable optoelectronic devices

The effects of thermal annealing on the large monolayer (11 ML) coverage of In_0.45Ga_0.55As/GaAs quantum dots (QDs) is being investigated in this study. Low temperature (8 K) photoluminescence (PL) spectra exhibits suppressed blueshift of the strongest PL emission peak even at high temperature annealing (800 °C). TEM and DCXRD characterizations showed the existence of the dots with good crystalline quality at annealing temperatures of 800-850 °C. The physics of annealing induced compositional modification of the InGaAs QDs with various monolayer coverage has been studied by a theoretical model and simulation. All our studies establish the thermal stability of large ML coverage InGaAs QDs, which is desirable for optoelectronic devices required for selective wavelength tuning in specific applications.