多孔硅发光研究获新进展

最近,复旦大学应用表面物理实验室在多孔硅发光研究方面又取得两项新的进展,现介绍如下:1.电致发光的功耗低于文献报道的水平 目前,我们所制成的多孔硅电致发光样品,其发光的阈值电压和电流已减小到 6V,30mA/cm2,比国际上迄今所报道的功耗值都要低.从表1的比较可以看出,我们所获得的电致发光特性达到了文献报道的最好水平.2.光致发光获得迄今所报道的最短波长 由于多孔硅发光的波长与硅柱直径有关,当发光波长进入绿光范围时,硅柱孔径已很细,极易坍塌,使得更细的量子线结构很难实现.迄今国外文献所发表的光致发光谱其中心波长最短约为530nm(…     

MEH-PPV/ZnO纳米晶无机有机复合电致发光器件的研究

以Ⅱ一Ⅵ族无机半导体ZnO纳米颗粒为电子传输层,MEH-PPV为空穴传输层兼发光层,得到的电致发光器件比单层MEH-PPV器件的发光亮度和效率都明显提高。器件结构为ITO／MEH-PPV／ZnO／Al的电致发光光谱同单层PPV器件的光谱出现了不同,在620nm处出现了一个小的发光峰,应该是ZnO的发光。另外,双层结构器件的启亮电压由单层器件的9V降到了4V左右。由I-V曲线及发光光谱可判断出发光区域应在MEH-PPV／ZnO界面处,并且复合区域可能随着电压的变化而变化。     

纳米Si/SiO2多层膜的结构表征及发光特性

采用等离子体化学气相沉积系统生长非晶硅薄膜并用原位等离子体氧化的方法制备出具有不同子层厚度的非晶Si/SiO₂多层膜,然后利用限制性晶化原理使非晶硅层晶化生成纳米硅。利用Raman、TEM等手段对薄膜结构进行了系统表征,在室温下观测到了光致发光信号,其发光峰峰位在750nm附近。进而在样品上下表面蒸镀电极,构建了电致发光原型器件并观测到了室温下的电致发光谱,开启电压约为6V,有两个明显的发光带,分别位于在650nm和520nm处。初步探讨了纳米硅及纳米硅/二氧化硅界面态对发光特性的影响。     

提高多孔硅传感特性的一种新方法(英文)

研究了多孔硅(PS)吸附有机溶剂分子后对多孔硅荧光谱的淬灭效应。结果表明:淬灭多孔硅发光的有机溶剂分子是极性分子,有机溶剂分子的极性不同对多孔硅发光的淬灭程度也不同,且有些有机溶剂分子吸附氧化多孔硅比吸附多孔硅引起的发光淬灭具有更好的可逆性和选择性;用含有胺基的正丁胺(CH3CH2CH2CH2-NH2)作碳源,用射频辉光放电等离子系统在多孔硅表面沉积c n膜对多孔硅进行钝化处理后发现:其电致发光强度明显增强,发光峰位兰移,且在大气中存放60天后,其电致发光谱强度基本不衰减,峰位不再移动。经钝化处理的器件较未经处理的器件具有小的串联电阻Rs和低的驱动电压。这为提高多孔硅的传感特性提供了一种新方法。     

多孔硅发光与量子尺寸效应的实验研究

利用电化学阳极腐蚀的方法制备了多孔硅膜,实验发现多孔硅膜为多层结构,表面层为纳米结构,其余为微米结构,多孔硅的物理及化学结构的研究表明多孔硅是一种表面上含硅、氧、氢、氟元素组成的化合物包覆着的纳米晶硅粒和微米硅丝.多孔硅的发光主要来自表面纳米结构层,亚微米结构层并未见发光,从实验上证实了多孔硅的发光与量子尺寸效应紧密关联.     

多孔硅的电致发光

９０年代安发展起来的发光多孔硅材料在发光的全色性，电致发光的效率以及稳定性等方面取得不少重要进展。介绍了几种多孔硅发光二极管结构及有关的电致发光机理，从共进展的速度以及目前已达量子效率＞１０＾－＾４的水平来看，其进入实际应用的前景是乐观的。     

三波段白光有机电致发光器件及其色稳定性的控制

制备并研究了基于3种小分子荧光材料的白光有机电致发光器件。发光层采用红色发光材料DCJTB掺杂绿光材料Alq3构成混合发光层,与OXD-7构成的蓝色发光层形成异质结的结构,并以NPB为空穴注入层。通过改变结构参数详细研究了发射光谱及其色坐标的电场依赖性。通过分析载流子注入/传输特性,控制激子的复合区域等措施得到了色坐标稳定性好、光谱丰富的高性能白光电致发光器件。经过优化的器件结构可以覆盖更大的可见光区域,当电压从9 V增加到13 V时,色坐标仅从CIE(x,y)=(0.364,0.314)偏移到CIE(x,y)=(0.332,0.291),具有较好的色稳定性。     

硅表面硅镱键合与量子级联结构的发光

用纳秒强激光脉冲制备了纳米硅和硅表面的硅镱键合结构,检测了纳米硅表面硅镱键合的发光特性,并对这种结构相应的光致发光(PL)和电致发光(EL)的动力学机理进行了研究。观察到纳米硅表面硅镱键合在700nm附近尖锐的强发光峰,结合第一性原理计算认为是硅镱键合在弯曲纳米硅表面的局域态发光;利用纳秒脉冲激光沉积技术(PLD)制备多晶硅薄膜,发现由硅镱界面的失配形成表面的突触,其上的硅镱键合产生带隙中的电子局域态,该局域态发光分布在1250~1650nm波长范围,有增强的EL发光;用PLD方法制备硅镱多层膜量子级联结构,测量到光通信窗口的多个发光峰,并观察到随膜层数增加且发光峰增多。     

硅基掺锰富硅氧化硅薄膜的电致发光

硅光子学中的关键问题是研制高效率的硅基光源,文章为此提出了一种实现硅基发光的方法。采用共溅射的方法在n＋型重掺杂硅衬底上制备了富硅氧化硅（SiO2∶Si）薄膜,然后用热扩散法进行了锰（Mn2＋）掺杂和光学活化。高分辨透射电镜观察表明薄膜中形成了3～5 nm的硅纳米晶体。该薄膜在紫外光照射下发射出明亮的绿光,光致发光谱峰位在524 nm（2.36 eV）,一般认为这是来自Mn2＋能级4T1 →6A1基态跃迁的绿光辐射;其荧光寿命为0.8 ms。将该掺锰富硅二氧化硅（SiO2∶Si∶Mn2＋）做成电致发光结构,在低反偏电压下观察到近乎白色的电致发光（EL）,光谱范围覆盖了400～800 nm。研究表明,该电致发光谱来源于薄膜中的Mn2＋以及氧化硅中的缺陷发光中心两者光谱的叠加;Mn2＋的发光是靠薄膜中的热电子来激发的;并由此探讨了薄膜中的硅纳米晶体在电致发光过程中的作用。     

核-壳结构ZnS:Tb/CdS纳米晶的电致发光

利用微乳液方法合成出粒径为4nm的核．壳结构ZnS：Tb／CdS纳米晶。用XRD、TEM及荧光光谱等手段对合成的纳米晶的结构、形态和光学特性分别进行了表征。将ZnS：Tb／CdS纳米晶制作成有机-无机杂化结构电致发光器件,其结构为ITO／poly（3,4-ethylene dioxythiophene）：poly（styrene sulfonate）（PEDOT-PSS）（70nm）／poly（vinyleobarzale）（PVK）（100nm）／ZnS：Tb／CdS纳米晶（120nm）／2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline（BCP）（30nm）／LiF（1．0nm）／Al（100nm）。当驱动电压为13V时,可以测到Tb^3＋离子的两个特征峰。在电致发光光谱中未测到聚合物PVK的发光,说明电子和空穴是在纳米晶层上复合的。当驱动电压为25V时,得到器件的最大亮度为19cd／m^2。     

Characterization of ITO/porous silicon LED structures

The electrical behavior and the electroluminescence (EL) obtained from n- and p-type ITO/porous silicon LEDs have been characterized simultaneously at different temperatures. Stability and aging in air were investigated, and means for avoiding their detrimental effects in the experiments are suggested. The dominating current carrying mechanism responsible for visible light emission in both substrate types has been identified to be Fowler–Nordheim tunneling. This emphasizes the contribution of embedded nanoparticles (quantum dots) rather than the role of nanowires in efficient EL.     

Visible electroluminescence from p-n junction porous Si diode with a polyaniline film contact

We have fabricated a light emitting diode using a p-type conducting polyaniline layer deposited on a n-type porous silicon (PS) layer. The contact formed between a p-type conducting polyaniline layer and a n-type PS wafer has rectified behaviour demonstrated clearly by the I-V curves. The series resistance Rs in the p-type conducting polyaniline/n-PS diode is reduced greatly and has a lower onset voltage compared with ITO/n-PS diode. The PS has an orange photoluminescence (PL) band after coating with polyaniline. Visible electroluminescence (EL) has been obtained from this junction when a forward bias is applied. The emission band is very broad extending from 600-803 nm with a peak at 690 nm.     

Efficient visible electroluminescence from porous silicon diodes with low driven voltage

By using n-butylamine as carbon resource, diamond-like carbon film (DLCF) was deposited on the p-n porous silicon (PS) surface by means of a radio-frequency glow discharge plasma system. Electroluminescent (EL) spectra show that EL intensity of the passivated PS diodes increases by 4.5 times and 30-nm blue-shift of EL peak occurs compared with the diodes without treatment and both of them are stable while the passivated diodes are exposed to the air indoor. The current-voltage (Ⅰ-Ⅴ) characteristics exhibit that the passivated diodes have a smaller series resistance and a lower onset voltage. The EL intensityvoltage (ⅠEL-Ⅴ) relations of the PS devices with different DLCF thicknesses show that only medium DLCF thickness is optimum. These experimental phenomena have been explained based on Raman spectra and IR spectra of the diamond-like carbon films and IR spectra of the passivated PS samples.     

Study of photoconductivity and photoluminescence of organic/porous silicon complexes

In this paper, time-varying photoconductivity (PC) and the photoluminescence (PL) of different complexes were studied. Due to thick polymer layer hindering light penetrating into porous silicon (PS) layer, intrinsic PS luminescence in polymer/PS system disappeared. The physical origin of PL may be related to the recombination mechanisms involving surface defect states such as silicon oxide, siloxene. Due to carrier transfer controlled by different energy barrier, different devices prepared from different doped Si wafer showed opposite current-voltage characteristic.     

Tunable photoluminescence and electroluminescence of size-controlled silicon nanocrystals in nanocrystalline-Si/SiO2 superlattices

We present photoluminescence and electroluminescence of silicon nanocrystals deposited by plasma-enhanced chemical vapor deposition (PECVD) using nanocrystalline silicon/silicon dioxide (nc-Si/SiO₂) superlattice approach. This approach allows us to tune the nanocrystal emission wavelength by varying the thickness of the Si layers. We fabricate light emitting devices (LEDs) with transparent indium tin oxide (ITO) contacts using these superlattice materials. The current-voltage characteristics of the LEDs are measured and compared to Frenkel-Poole and Fowler-Nordheim models for conduction. The EL properties of the superlattice material are studied, and tuning, similar to that of the PL spectra, is shown for the EL spectra. Finally, we observe the output power and calculate the quantum efficiency and power conversion efficiency for each of the devices.     

退火对ZnS/PS复合体系光致发光特性的影响

用脉冲激光沉积(PLD)技术以多孔硅(PS)为衬底生长了ZnS薄膜,分别测量了ZnS、PS以及ZnS/PS复合体系在室温下的光致发光(PL)光谱。结果发现,ZnS/PS复合体系的PL光谱中PS的发光峰位相对于新制备的PS有所蓝移。把该ZnS/PS样品分成三块,在真空400℃分别退火10,20,30 min,研究不同退火时间对ZnS/PS复合体系光致发光特性的影响。发现退火后样品的PL光谱中都出现了一个新的绿色发光带,归结为ZnS的缺陷中心发光。随着退火时间的延长,PS的发光强度逐渐降低且峰位红移。把ZnS的蓝、绿光与PS的红光相叠加,整个ZnS/PS复合体系在可见光区450~700 nm形成一个较宽的光致发光谱带,呈现较强的白光发射。     

Mechanisms of visible electroluminescence in diode structures on the basis of porous silicon: A review

The main mechanisms of the visible electroluminescence (EL) of porous silicon are reviewed. Characteristics of photoluminescence and EL of diode structures based on porous silicon are compared. Metals having a smaller value of the electron work function (3.6 eV, Mg) than do Al and Au are proposed as the material for making contacts in such diode structures to increase the efficiency of their EL in the visible region of the spectrum. The main problems and prospects of light-emitting devices based on porous silicon are formulated.     

ZnO nanorods–polymer hybrid white light emitting diode grown on a disposable paper substrate

We demonstrate intrinsic white light emission from hybrid light emitting diodes fabricated using an inorganic–organic hybrid junction grown at 50 °C on a paper substrate. Cyclotene was first spin coated on the entire substrate to act as a surface barrier layer for water and other nutrient solutions. The active area of the fabricated light emitting diode (LED) consists of zinc oxide nanorods (ZnO NRs) and a poly(9,9‐dioctylfluorene) (PFO) conducting polymer layer. The fabricated LED shows clear rectifying behavior and a broad band electroluminescence (EL) peak covering the whole visible spectrum range from 420 nm to 780 nm. The color rendering index (CRI) was calculated to be 94 and the correlated color temperature (CCT) of the LED was 3660 K. The low process temperature and procedure in this work enables the use of paper substrate for the fabrication of low cost ZnO–polymer white LEDs for applications requiring flexible/disposable electronic devices. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of the polymer emission on the electroluminescence characteristics of n-ZnO nanorods/p-polymer hybrid light emitting diode

Hybrid light emitting diodes (LEDs) based on zinc oxide (ZnO) nanorods and polymers (single and blended) were fabricated and characterized. The ZnO nanorods were grown by the chemical bath deposition method at 50°C. Three different LEDs, with blue emitting, orange-red emitting or their blended polymer together with ZnO nanorods, were fabricated and studied. The current–voltage characteristics show good diode behavior with an ideality factor in the range of 2.1 to 2.27 for all three devices. The electroluminescence spectrum (EL) of the blended device has an emission range from 450 nm to 750 nm, due to the intermixing of the blue emission generated by poly(9,9-dioctylfluorene) denoted as PFO with orange-red emission produced by poly(2-methoxy-5(20-ethyl-hexyloxy)-1,4-phenylenevinylene) 1,4-phenylenevinylene) symbolized as MEH PPV combined with the deep-band emission (DBE) of the ZnO nanorods, i.e. it covers the whole visible region and is manifested as white light. The CIE color coordinates showed bluish, orange-red and white emission from the PFO, MEH PPV and blended LEDs with ZnO nanorods, respectively. These results indicate that the choice of the polymer with proper concentration is critical to the emitted color in ZnO nanorods/p-organic polymer LEDs and careful design should be considered to obtain intrinsic white light sources.     

Effect of surface modification by thermally oxidization and HF etching on UV photoluminescence emission of porous silicon

Photoluminescence of porous silicon (PS) is instable due perhaps to the nanostructure modification in air. The controllable structure modification processes on the as-prepared PS were conducted by thermal oxidization and/or HF etching. The PL spectra taken from thermally oxidized PS showed a stable photoluminescence emission of 355 nm. The photoluminescence emission taken from both of PS and oxidized porous silicon (OPS) samples etched with HF were instable, which can be reversibly recovered by the HF etching procedure. The mechanism of UV photoluminescence is discussed and attributed to the transformation of luminescence centers from oxygen deficient defects to the oxygen excess defects in the thermal oxidized PS sample and surface absorbed silanol groups on PS samples during the chemical etched procedure.