Facile and versatile ligand analysis method of colloidal quantum dot.

Colloidal quantum-dots (QDs) are highly attractive materials for various optoelectronic applications owing to their easy maneuverability, high functionality, wide applicability, and low cost of mass-production. QDs usually consist of two components: the inorganic nano-crystalline particle and organic ligands that passivate the surface of the inorganic particle. The organic component is also critical for tuning electronic properties of QDs as well as solubilizing QDs in various solvents. However, despite extensive effort to understand the chemistry of ligands, it has been challenging to develop an efficient and reliable method for identifying and quantifying ligands on the QD surface. Herein, we developed a novel method of analyzing ligands in a mild yet accurate fashion. We found that oxidizing agents, as a heterogeneous catalyst in a different phase from QDs, can efficiently disrupt the interaction between the inorganic particle and organic ligands, and the subsequent simple phase fractionation step can isolate the ligand-containing phase from the oxidizer-containing phase and the insoluble precipitates. Our novel analysis procedure ensures to minimize the exposure of ligand molecules to oxidizing agents as well as to prepare homogeneous samples that can be readily analyzed by diverse analytical techniques, such as nuclear magnetic resonance spectroscopy and gas-chromatography mass-spectrometry.

In-Depth Investigation of the Correlation between Organic Semiconductor Orientation and Energy-Level Alignment Using In Situ Photoelectron Spectroscopy.

Organic semiconductors (OSCs) are of interest for replacing traditional Si-based semiconductors as their flexibility and transparency enable new applications. The properties of OSC materials greatly depend on their orientation and molecular arrangement, which are strongly dependent on the underlying substrate material. Hence, in this study, in situ ultraviolet photoelectron spectroscopy (UPS) is used to elucidate the effect of the substrate on OSC orientation. Two types of OSCs, namely those with shape anisotropy (pentacene, dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene, and dibenzothiopheno[6,5-b:6',5'-f]thieno[3,2-b]thiophene) and those with shape isotropy (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine, tris(4-carbazoyl-9-ylphenyl)amine, and [6,6]-phenyl C71 butyric acid methyl ester), are deposited on different electrode materials. The differences in the UPS spectra of these materials are observed directly. In general, the orientation of anisotropic OSC molecules significantly depends on the substrate properties, while that of the isotropic ones do not. All the anisotropic OSC molecules grown on poly(3,4-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT:PSS) electrodes show a greater degree of molecular ordering than those grown on Au and multiwalled carbon nanotube/PEDOT:PSS electrodes. The molecular arrangements within the OSC/electrode structures are reflected in the energy-level shifts in the corresponding UPS spectra and hence in the electronic configurations. The results of this study should aid the design and synthesis of OSC materials with configurations suitable for organic electronic devices.

Correction: Direct characterization of graphene doping state by in situ photoemission spectroscopy with Ar gas cluster ion beam sputtering.

Correction for 'Direct characterization of graphene doping state by in situ photoemission spectroscopy with Ar gas cluster ion beam sputtering' by Dong-Jin Yun et al., Phys. Chem. Chem. Phys., 2018, 20, 615-622.

Direct characterization of graphene doping state by in situ photoemission spectroscopy with Ar gas cluster ion beam sputtering.

On the basis of an in situ photoemission spectroscopy (PES) system, we propose a novel, direct diagnosis method for the characterization of graphene (Gr) doping states at organic semiconductor (OSC)/electrode interfaces. Our in situ PES system enables ultraviolet/X-ray photoelectron spectroscopy (UPS/XPS) measurements during the OSC growth or removal process. We directly deposit C60 films on three different p-type dopants-gold chloride (AuCl3), (trifluoromethyl-sulfonyl)imide (TFSI), and nitric acid (HNO3). We periodically characterize the chemical/electronic state changes of the C60/Gr structures during their aging processes under ambient conditions. Depositing the OSC on the p-type doped Gr also prevents severe degradation of the electrical properties, with almost negligible transition over one month, while the p-type doped Gr without an OSC changes a lot following one month of aging. Our results indicate that the chemical/electronic structures of the Gr layer are completely reflected in the energy level alignments at the C60/Gr interfaces. Therefore, we strongly believe that the variation of energy level alignments at the OSC/graphene interface is a key standard for determining the doping state of graphene after a certain period of aging.

Effect of Si on the Energy Band Gap Modulation and Performance of Silicon Indium Zinc Oxide Thin-Film Transistors.

The band gap properties of amorphous SiInZnO (a-SIZO) thin-film transistors (TFTs) with different Si concentrations have been studied. The electronic structures of the films, engineered by controlling the Si content, have been investigated through the changes of the band gap and band edge states. Carrier generation at oxygen vacancies can modify the band gap states of oxide thin films. Si suppresses the number of oxygen vacancies-which are carrier generation sites-so shifts the Fermi energy level away from the conduction band. It is difficult to derive the electronic structures of amorphous oxide semiconductors by electrical measurements. Thus, we used a combination of ultraviolet photoelectron spectroscopy, Kelvin probe measurements, and electron energy loss spectroscopy to measure the band gap and electrical performance variations of SIZO TFTs with Si doping. To verify the versatility of Si doping in modulating electronic properties, high-performance depletion-mode inverter circuits consisting of 0.1 to 0.3 wt% Si-doped a-SIZO TFTs were fabricated. These inverter models operate through the threshold voltage difference that arises from the different Si contents. High voltage gains of ~20.62 at a supply voltage of 15 V were obtained with the two TFTs, with a strong dependence on the subthreshold swing.

Impact of Interface Mixing on the Performance of Solution Processed Organic Light Emitting Diodes-Impedance and Ultraviolet Photoelectron Spectroscopy Study.

We investigated interfacial mixing of solution-processed organic light-emitting devices (OLEDs) using impedance spectroscopy (IS) and ultraviolet photoelectron spectroscopy (UPS) and its impact on device performance. We focused on interfacial mixing between a solution-processed cross-linkable hole transport layer (XM) and an emitting layer (EML), formed either by solution processing or vacuum evaporation. The results of IS and UPS clearly indicated that extensive interfacial mixing was unavoidable, even after the XM was cross-linked to make it insoluble and rinsed to remove residual soluble species, if the subsequent EML was solution processed. In addition, we also demonstrated that interfacial mixing indeed increased hole current density in corresponding hole only device (HOD). In fact, the hole injection efficiency could be an order of magnitude better when the EML was solution processed rather than vacuum evaporated. We investigated such behavior to find the desirable process condition of solution-processed OLEDs.

Realization of continuous Zachariasen carbon monolayer.

Rapid progress in two-dimensional (2D) crystalline materials has recently enabled a range of device possibilities. These possibilities may be further expanded through the development of advanced 2D glass materials. Zachariasen carbon monolayer, a novel amorphous 2D carbon allotrope, was successfully synthesized on germanium surface. The one-atom-thick continuous amorphous layer, in which the in-plane carbon network was fully sp2-hybridized, was achieved at high temperatures (>900°C) and a controlled growth rate. We verified that the charge carriers within the Zachariasen carbon monolayer are strongly localized to display Anderson insulating behavior and a large negative magnetoresistance. This new 2D glass also exhibited a unique ability as an atom-thick interface layer, allowing the deposition of an atomically flat dielectric film. It can be adopted in conventional semiconductor and display processing or used in the fabrication of flexible devices consisting of thin inorganic layers.

Defect visualization of Cu(InGa)(SeS)2 thin films using DLTS measurement.

Defect depth profiles of Cu (In1-x,Gax)(Se1-ySy)2 (CIGSS) were measured as functions of pulse width and voltage via deep-level transient spectroscopy (DLTS). Four defects were observed, i.e., electron traps of ~0.2 eV at 140 K (E1 trap) and 0.47 eV at 300 K (E2 trap) and hole traps of ~0.1 eV at 100 K (H1 trap) and ~0.4 eV at 250 K (H2 trap). The open circuit voltage (VOC) deteriorated when the trap densities of E2 were increased. The energy band diagrams of CIGSS were also obtained using Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and DLTS data. These results showed that the valence band was lowered at higher S content. In addition, it was found that the E2 defect influenced the VOC and could be interpreted as an extended defect. Defect depth profile images provided clear insight into the identification of defect state and density as a function of depth around the space charge region.

Large Work Function Modulation of Monolayer MoS2 by Ambient Gases.

Although two-dimensional monolayer transition-metal dichalcogenides reveal numerous unique features that are inaccessible in bulk materials, their intrinsic properties are often obscured by environmental effects. Among them, work function, which is the energy required to extract an electron from a material to vacuum, is one critical parameter in electronic/optoelectronic devices. Here, we report a large work function modulation in MoS2 via ambient gases. The work function was measured by an in situ Kelvin probe technique and further confirmed by ultraviolet photoemission spectroscopy and theoretical calculations. A measured work function of 4.04 eV in vacuum was converted to 4.47 eV with O2 exposure, which is comparable with a large variation in graphene. The homojunction diode by partially passivating a transistor reveals an ideal junction with an ideality factor of almost one and perfect electrical reversibility. The estimated depletion width obtained from photocurrent mapping was ∼200 nm, which is much narrower than bulk semiconductors.

Study on the disparate transition behaviors of the electrical/physical properties in PEDOT:PSS film depending on solvent species under a follow-up solution-treatment process.

In most solution-processed organic devices, a poly(3,4-ethylenedioxythiophene) (PEDOT) polymerized with poly(4-styrenesulfonate) (PSS) film is inevitably affected by various conditions during the subsequent solution-coating processes. To investigate the effects of direct solvent exposure on the properties of PEDOT polymerized with PSS (PEDOT:PSS) films, photoemission spectroscopy-based analytical methods were used before and after solvent-coating processes. Our results clearly indicate that PEDOT: PSS films undergo a different transition mechanism depending on the solubility of the solvent in water. The water-miscible solvents induce the solvation of hydrophilic PSS chains. As a result, this process allows the solvent to diffuse into the PEDOT: PSS film, and a conformational change between PEDOT and PSS occurs. On the other hand, the water-immiscible organic solvents cause the partial adsorption of solvent molecules at the PE surface, which leads to changes in the surface properties, including work function. Based on our finding, we demonstrate that the energy-level alignments at the organic semiconductor/electrode interface for the PEDOT: PSS films can be controlled by simple solvent treatments.

Direct analytical method of contact position effects on the energy-level alignments at organic semiconductor/electrode interfaces using photoemission spectroscopy combined with Ar gas cluster ion beam sputtering.

Poly(3, 4-ethylenedioxythiophene) (PEDOT) polymerized with poly(4-styrenesulfonate) (PSS) is one of the most widely used conducting organic electrodes owing to its outstanding optical/electrical properties and high work function. Because its work function depends significantly on the molecular arrangements between PEDOT and PSS molecules on the surface, the contact position of PEDOT: PSS films on organic semiconductors (OSCs) must also be an essential consideration. However, existing analysis methods based on in situ deposition/analysis are limited in their ability to accurately investigate the electronic structures of the buried interface regions under the solution-processed electrode or OSC layer in organic devices. Therefore, to overcome such limitations, we propose a top-down method based on photoemission spectroscopy analysis combined with Ar gas cluster ion beam (GCIB) sputtering. Through this method, both energy-level alignments and molecular distributions at various OSC/electrode interfaces can be successfully characterized without reference to any deposition process.

Electron energy loss spectroscopy characterization of TANOS (TaN/Al2O3/Si3N4/SiO2/Si) stacks.

The interfacial layer between the Al2O3 layer and the Si3N4 layer formed after postdeposition annealing (PDA) of TaN/Al2O3/Si3N4/SiO2/Si (TANOS) stacks was investigated using transmission electron microscopy (TEM), scanning transmission electron microscopy, and electron energy loss spectroscopy (EELS). From the result of the TEM analysis, it was found that the 2-nm-thick interface layer between Al2O3 and Si3N4 layers was amorphous. The high-loss EELS analysis showed that the phases of the interfacial layer weakly bound together instead of the substoichiometric silicon oxide and amorphous Al2O3 near the bottom interface of the crystalline Al2O3. The low-loss EELS analysis showed that aluminum existed in metallic state at the interface. Therefore, we speculated that SiO(x)N(y) could be formed by oxidation of Si3N4 during PDA and that metallic aluminum could be formed by the decomposition of weakly bound amorphous Al2O3 during electron irradiation. These complicated reactions near the interface could induce oxygen deficiency in the Al2O3 layer and finally degrade the retention properties of TANOS stacks.

Effects of interfacial layer on characteristics of TiN/ZrO2 structures.

To minimize the formation of unwanted interfacial layers, thin interfacial layer (ZrCN layer) was deposited between TiN bottom electrode and ZrO2 dielectric in TiN/ZrO2/TiN capacitor. Carbon and nitrogen were also involved in the layer because ZrCN layer was thermally deposited using TEMAZ without any reactant. Electrical characteristics of TiN/ZrO2/TiN capacitor were improved by insertion of ZrCN layer. The oxidation of TiN bottom electrode was largely inhibited at TiN/ZrCN/ZrO2 structure compared to TiN/ZrO2 structure. While the sheet resistance of TiN/ZrCN/ZrO2 structure was constantly sustained with increasing ZrO2 thickness, the large increase of sheet resistance was observed in TiN/ZrO2 structure after 6 nm ZrO2 deposition. When ZrO2 films were deposited on ZrCN layer, the deposition rate of ZrO2 also increased. It is believed that ZrCN layer acted both as a protection layer of TiN oxidation and a seed layer of ZrO2 growth.

Bandgap measurement of thin dielectric films using monochromated STEM-EELS.

High-resolution electron energy-loss spectroscopy (HR-EELS), achieved by attaching electron monochromators to transmission electron microscopes (TEM), has proved to be a powerful tool for measuring bandgaps. However, the method itself is still uncertain, due to Cerenkov loss and surface effects that can potentially influence the quality of EELS data. In the present study, we achieved an energy resolution of about 0.13 eV at 0.1s, with a spatial resolution of a few nanometers, using a monochromated STEM-EELS technique. We also assessed various methods of bandgap measurement for a-SiNx and SiO2 thin dielectric films. It was found that the linear fit method was more reliable than the onset reading method in avoiding the effects of Cerenkov loss and specimen thickness. The bandgap of the SiO2 was estimated to be 8.95 eV, and those of a-SiNx with N/Si ratios of 1.46, 1.20 and 0.92 were measured as 5.3, 4.1 and 2.9 eV, respectively. These bandgap-measurement results using monochromated STEM-EELS were compared with those using Auger electron spectroscopy (AES)-reflective EELS (REELS).