Bandgap Engineering in OH‐Functionalized Silicon Nanocrystals: Interplay between Surface Functionalization and Quantum Confinement

In this work, a systematic first‐principles study of the quasi‐band structure of silicon nanocrystals (Si‐NCs) is provided, focusing on bandgap engineering by combining quantum confinement of the electronic states with OH surface‐functionalization. A mapping between the bandgap, Si‐NC diameter, and the degree of hydroxide coverage is provided, which can be used as a guideline for bandgap engineering. Complementary to first‐principles calculations, the photoluminescence (PL) wavelength of Si‐NCs in the quantum‐confinement regime is measured with well‐defined diameters between 1 and 4 nm. The Si‐NCs are prepared by means of a microplasma technique, which allows a surfactant‐free engineering of the Si‐NCs surface with OH groups. The microplasma treatment technique allows us to gradually change the degree of OH coverage, enabling us, in turn, to gradually shift the emitted light in the PL spectra by up to 100 nm to longer wavelengths. The first‐principles calculations are consistent with the experimentally observed dependence of the wavelengths on the OH coverage and show that the PL redshift is determined by the charge transfer between the Si‐NC and the functional groups, while on the other hand surface strain plays only a minor part.     

Routes to Achieving High Quantum Yield Luminescence from Gas‐Phase‐Produced Silicon Nanocrystals

Plasma‐synthesized silicon nanocrystals with alkene ligands have shown the potential to exhibit high‐efficiency photoluminescence, but results reported in the literature have been inconsistent. Here, for the first time, the role of the immediate post‐synthesis “afterglow plasma” environment is explored. The significant impact of gas injection into the afterglow plasma on the photoluminescence efficiency of silicon nanocrystals is reprorted. Depending on the afterglow conditions, photoluminescence quantum yields of silicon nanocrystals synthesized under otherwise identical conditions can vary by a factor of almost five. It is demonstrated that achieving a fast quenching of the particle temperature and a high flux of atomic hydrogen to the nanocrystal surface are essential for a high photoluminescence quantum yield of the produced silicon nanocrystals.     

Luminescent Colloidal Dispersion of Silicon Quantum Dots from Microwave Plasma Synthesis: Exploring the Photoluminescence Behavior Across the Visible Spectrum

Aiming for a more practical route to highly stable visible photoluminescence (PL) from silicon, a novel approach to produce luminescent silicon nanoparticles (Si‐NPs) is developed. Single crystalline Si‐NPs are synthesized by pyrolysis of silane (SiH₄) in a microwave plasma reactor at very high production rates (0.1–10 g h^?1). The emission wavelength of the Si‐NPs is controlled by etching them in a mixture of hydrofluoric acid and nitric acid. Emission across the entire visible spectrum is obtained by varying the etching time. It is observed that the air oxidation of the etched Si‐NPs profoundly affects their optical properties, and causes their emission to blue‐shift and diminish in intensity with time. Modification of the silicon surface by UV‐induced hydrosilylation also causes a shift in the spectrum. The nature of the shift (red/blue) is dependent on the emission wavelength of the etched Si‐NPs. In addition, the amount of shift depends on the type of organic ligand on the silicon surface and the UV exposure time. The surface modification of Si‐NPs with different alkenes results in highly stable PL and allows their dispersion in a variety of organic solvents. This method of producing macroscopic quantities of Si‐NPs with very high PL stability opens new avenues to applications of silicon quantum dots in optoelectronic and biological fields, and paves the way towards their commercialization.     

热丝法制备硅纳晶颗粒及其发光性质

利用热丝化学气相沉积法,在真空腔中通过选择设定不同加热功率的热丝热解硅烷制备出一系列不同颗粒尺寸的硅纳米颗粒样品。透射电镜分析表明硅纳米颗粒具有结晶良好的纳晶结构。通过自然氧化钝化硅纳米颗粒表面,消除表面悬键的影响,使得硅颗粒具有高效的光致发光特性,发光范围在红光到近红外区,发光特性与量子限域效应相吻合。发光寿命测量表明所制备的硅颗粒的发光寿命在微秒量级,并且通过比较不同硅颗粒分布样品中相同发光波长衰减寿命的差异,揭示了所制备样品中硅纳米颗粒之间存在耦合作用。     

Hydrogen Incorporation in III‐N‐V Semiconductors: From Macroscopic to Nanometer Control of the Materials’ Physical Properties

The effects of hydrogen incorporation in dilute nitride semiconductors, specifically GaAs_1‐xN_x, are discussed. The remarkable consequences of hydrogen irradiation include tuneable and reversible changes in the electronic, optical, structural, and electrical properties of these materials. The highly trapping‐limited diffusion of H atoms in dilute nitrides results in the formation of extremely sharp heterointerfaces between H‐containing and H‐free regions of the crystals. This, in turn, offers an unprecedented possibility to tailor the physical properties of a semiconductor chip in its growth plane with nanometer precision. A number of examples are presented and discussed.     

Surface Chemistry Routes to Modulate the Photoluminescence of Graphene Quantum Dots: From Fluorescence Mechanism to Up‐Conversion Bioimaging Applications

The bandgap in graphene‐based materials can be tuned from 0 eV to that of benzene by changing size and/or surface chemistry, making it a rising carbon‐based fluorescent material. Here, the surface chemistry of small size graphene (graphene quantum dots, GQDs) is tuned programmably through modification or reduction and green luminescent GQDs are changed to blue luminescent GQDs. Several tools are employed to characterize the composition and morphology of resultants. More importantly, using this system, the luminescence mechanism (the competition between both the defect state emission and intrinsic state emission) is explored in detail. Experiments demonstrate that the chemical structure changes during modification or reduction suppresses non‐radiative recombination of localized electron‐hole pairs and/or enhances the integrity of surface π electron network. Therefore the intrinsic state emission plays a leading role, as opposed to defect state emission in GQDs. The results of time‐resolved measurements are consistent with the suggested PL mechanism. Up‐conversion PL of GQDs is successfully applied in near‐IR excitation for bioimaging.     

A Solution‐Processed UV‐Sensitive Photodiode Produced Using a New Silicon Nanocrystal Ink

This article presents a simple and effective method of functionalizing hydrogen‐terminated silicon (Si) nanocrystals (NCs) to form a high‐quality colloidal Si NC ink with short ligands that allow charge transport in nanocrystal solid films. Si NCs fabricated by laser‐pyrolysis and acid etching are passivated with allyl disulfide via ultraviolet (UV)‐initiated hydrosilylation to form a stable colloidal Si NC ink. Then a Si NC‐based photodiode is directly fabricated in air from this ink. Only a solution‐processed poly(3,4‐ethylenedioxy‐thiophene):poly(styrene sulfonate) (PEDOT: PSS) electron blocking layer and top‐ and bottom‐contacts are needed along with the Si NC layer to construct the device. A Schottky‐junction at the interface between the Si NC absorber layer and aluminum (Al) back electrode drives charge separation in the device under illumination. The unpackaged Si NC‐based photodiode exhibites a peak photoresponse of 0.02 A W^?1 to UV light in air, within an order of magnitude of the response of commercially available gallium phosphide (GaP), gallium nitride (GaN), and silicon carbide (SiC) based photodetectors. This provides a new pathway to large‐area, low‐cost solution‐processed UV photodetectors on flexible substrates and demonstrates the potential of this new silicon nanocrystal ink for broader applications in solution‐processed optoelectronics.     

纳米硅颗粒在多孔氧化铝中的光致荧光特性

采用阳极氧化方法制备了多孔硅（Ps），经过超声波充分粉碎PS层得到分散的si纳米颗粒（n-Si），利用高速离心旋转方法将n-si镶嵌到多孔氧化铝（Al2O3）模板中，得到nSi／Al2O3。复合体系。研究了PS、分散的n-Si和n-Si／Al2O3。的荧光（PL）光谱性质，观察到n-Si极强的蓝紫光发射。结果表明，在Al2O3模板中的n-Si，比起PS和丙酮中的发光峰值波长向短波方向“蓝移”，而且半峰全宽（FWHM）也相对变窄。实验现象表明，量子限制效应（QCE）对样品的PL性质有苇要作用，并用QCE对样品的发光“蓝移”现象进行了解释。     

SiO2膜的薄层化对自组织生长Si纳米量子点发光特性的影响

采用低压化学气相沉积方法,依靠纯SiH4气体的热分解反应,在SiO2表面上自组织生长了Si纳米量子点.实验研究了SiO2膜的薄层化对Si纳米量子点光致发光特性的影响.结果表明,当SiO2膜厚度减薄至6nm以下时,Si纳米量子点中的光生载流子会量子隧穿超薄SiO2层,并逃逸到单晶Si衬底中去,从而减少了光生载流子通过SiO2/Si纳米量子点界面区域内发光中心的辐射复合效率,致使光致发光强度明显减弱.测试温度的变化对Si纳米量子点光致发光特性的影响,则源自于光生载流子通过SiO2/Si纳米量子点界面区域附近非发光中心的非辐射复合所产生的贡献.     

Immobilization of Quantum Dots in Nanostructured Porous Silicon Films: Characterizations and Signal Amplification for Dual‐Mode Optical Biosensing

Highly sensitive dual‐mode labeled detection of biotin in well‐characterized porous silicon (PSi) films using colloidal quantum dots (QDs) as signal amplifiers are demonstrated. Optimization of the PSi platform for targeted QD infiltration and immobilization is carried out by characterizing and tuning the porosity, film depth, and pore size. Binding events of target QD‐biotin conjugates with streptavidin probes immobilized on the pore walls are monitored by reflective interferometric spectroscopy and fluorescence measurements. QD labeling of the target biotin molecules enables detection based on a distinct fluorescent signal as well as a greater than 5‐fold enhancement in the measured spectral reflectance fringe shift and a nearly three order of magnitude improvement in the detection limit for only 6% surface area coverage of QDs inside the porous matrix. Utilizing the QD signal amplifiers, an exceptional biotin detection limit of ≈6 fg mm^?2 is demonstrated with sub‐fg mm^?2 detection limits achievable.     

纳米硅量子点的自然形成及其发光特性

用 Si H4 气体的减压 CVD法 ,在氧化硅以及石英基板上自然形成了高密度的 (～ 10 11cm-2 )纳米尺寸的半球状硅晶粒 (硅量子点 ) ,并且对其光学吸收和发光 (Photo- luminescence,PL)特性进行了评价。用表面热氧化了的硅量子点样品 ,在室温条件且在高于 1.2 e V以上的能量范围内观察到了 PL谱。随着量子点尺寸的减少 ,PL谱的光学吸收限移向高能方向。 PL谱的峰值能呈现大幅度的 (约 0 .9e V)斯塔克移动 ,并且 PL谱的强度几乎与温度无关 ,说明发光来自与局域能级相关联的发光和复合过程。     

Evidence for Edge‐State Photoluminescence in Graphene Quantum Dots

For a practical realization of graphene‐based logic devices, the opening of a band gap in graphene is crucial and has proven challenging. To this end, several synthesis techniques, including unzipping of carbon nanotubes, chemical vapor deposition, and other bottom‐up fabrication techniques have been pursued for the bulk production of graphene nanoribbons (GNRs) and graphene quantum dots (GQDs). However, only limited progress has been made towards a fundamental understanding of the origin of strong photoluminescence (PL) in GQDs. Here, it is experimentally shown that the PL is independent of the functionalization scheme of the GQDs. Following a series of annealing experiments designed to passivate the free edges, the PL in GQDs originates from edge‐states, and an edge‐passivation subsequent to synthesis quenches the PL. The results of PL studies of GNRs and carbon nano‐onions are shown to be consistent with PL being generated at the edge sites of GQDs.     

Compact and Stable Quantum Dots with Positive,Negative, or Zwitterionic Surface: Specific Cell Interactions and Non‐Specific Adsorptions by the Surface Charges

A new type of quantum dot (QD) ligand chemistry is introduced that can provide positive, negative, or zwitterionic surface QDs. CdSe/CdZnS core‐shell QDs are decorated with ligands, and the non‐specific and specific interactions of the QDs through their surface charge are investigated with the focus on cellular adsorptions and endocytosis. Zwitterionic QDs are compact with a ligand hydrodynamic thickness of less than 2 nm, they are colloidally very stable over a broad pH range and even in saturated NaCl solution, and they show minimal non‐specific adsorptions. Positive and negative QDs show a very different behavior for cellular adsorption and subsequent incorporation, suggesting mostly energy‐independent pathways for positive QDs and exclusively adenosine triphosphate (ATP)‐dependent pathways for negative QDs. The zwitterionic QD surface ligands can also be used in conjunction with other functional groups, which allows simple conjugations for highly specific targeting whereas retaining the advantages of a zwitterionic QD surface. This QD surface chemistry can provide highly specific and very sensitive imaging with very low background level. Using the mixed QD surface ligand system, we demonstrated streptavidin and antibody QD conjugates that show a signal‐to‐noise ratio that is over 4000 times higher than the unconjugated mixture, which was used as a control case. The QD chemistry reported herein can be easily extended to other functional groups, such as alkynes, azides, or other amines, and can be further used in many future applications, including single‐QD level experiments, sensitive assays, or in vivo applications using anti‐fouling QD probes.     

Surface Modification Strategy Synthesized CsPbX3 Perovskite Quantum Dots with Excellent Stability and Optical Properties in Water

The poor stability of CsPbX₃ (X = Cl, Br, I) perovskite quantum dots (PQDs) in polar solvents such as water, seriously hinders their practical application. Herein, 5-Bromovaleric acid (BVA) is used to replace oleic acid (OA), the most common surface ligand in CsPbX₃ PQDs synthesis. Under the synergic action of oleylamine (OLA), CsPbX₃ PQDs with high water stability can be synthesized directly in water. Because the carboxyl ligands provided by BVA, and the long chain amines provided by OLA formed hydrophobic shells on the surface of CsPbBr₃ PQDs, the obtained CsPbBr₃ PQDs still has high luminescence intensity and photoluminescence quantum yield after being dispersed in water for several days, and the luminescence peak is always maintained at 518 nm. In contrast, the luminescence intensity of CsPbBr₃ PQDs synthesized with OA and OLA is <1% of the initial intensity after only 30 min. CsPbCl₃ and CsPbI₃ PQDs synthesized directly in water by this method also show high water stability. In this study, for the first time the synthesis method of CsPbX₃ PQDs with high water stability using BVA/OLA as surface ligands is proposed, which provides an effective way to explore the synthesis of PQDs that can maintain stability in water.     

Low‐Cost Post‐Growth Treatments of Crystalline Silicon Nanoparticles Improving Surface and Electronic Properties

Freestanding silicon nanocrystals (Si‐ncs) offer unique optical and electronic properties for new photovoltaic, thermoelectric, and other electronic devices. A method to fabricate Si‐ncs which is scalable to industrial usage has been developed in recent years. However, barriers to the widespread utilization of these nanocrystals are the presence of charge‐trapping defects and an oxide shell formed upon ambient atmosphere exposure hindering the charge transport. Here, we exploit low‐cost post‐growth treatment routes based on wet‐etching in hydrofluoric acid plus surface hydrosilylation or annealing enabling a complete native oxide removal and a reduction of the defect density by up to two orders of magnitude. Moreover, when compared with only H‐terminated Si‐ncs we report an enhancement of the conductivity by up to a factor of 400 for films of HF etched and annealed Si‐ncs, which retain a defect density below that of untreated Si‐ncs even after several months of air exposure. Further, we demonstrate that HF etched and hydrosilylated Si‐ncs are extremely stable against oxidation and maintain a very low defect density after a long‐term storage in air, opening the possibility of device processing in ambient atmosphere.     

Electrical‐Polarization‐Induced Ultrahigh Responsivity Photodetectors Based on Graphene and Graphene Quantum Dots

Hybrid quantum dot–graphene photodetectors have recently attracted substantial interest because of their remarkable performance and low power consumption. However, the performance of the device greatly depends on the interfacial states and photogenerated screening field. As a consequence, the sensitivity is limited and the response time is relatively slow. In order to circumvent these challenges, herein, a composite graphene and graphene quantum dot (GQD) photodetector on lead zirconate titanate (Pb(Zr_0.2Ti_0.8)O₃) (PZT) substrates has been designed to form an ultrasensitive photodetector over a wide range of illumination power. Under 325 nm UV light illumination, the device shows sensitivity as high as 4.06 × 10⁹ A W^?1, which is 120 times higher than reported sensitivity of the same class of devices. Plant derived GQD has a broad range of absorptivity and is an excellent candidate for harvesting photons generating electron–hole pairs. Intrinsic electric field from PZT substrate separates photogenerated electron–hole pairs as well as provides the built‐in electric field that causes the holes to transfer to the underlying graphene channel. The composite structure of graphene and GQD on PZT substrate therefore produces a simple, stable, and highly sensitive photodetector over a wide range of power with short response time, which shows a way to obtain high‐performance optoelectronic devices.