Work Function Shift Research Articles

Processing follows function: pushing the formation of self-assembled monolayers to high-throughput compatible time scales.

Self-assembled monolayers (SAMs) of organic molecules can be used to tune interface energetics and thereby improve charge carrier injection at metal-semiconductor contacts. We investigate the compatibility of SAM formation with high-throughput processing techniques. Therefore, we examine the quality of SAMs, in terms of work function shift and chemical composition as measured with photoelectron and infrared spectroscopy and in dependency on molecular exposure during SAM formation. The functionality of the SAMs is determined by the performance increase of organic field-effect transistors upon SAM treatment of the source/drain contacts. This combined analytical and device-based approach enables us to minimize the necessary formation times via an optimization of the deposition conditions. Our findings demonstrate that SAMs composed of partially fluorinated alkanethiols can be prepared in ambient atmosphere from ethanol solution using immersion times as short as 5 s and still exhibit almost full charge injection functionality if process parameters are chosen carefully. This renders solution-processed SAMs compatible with high-throughput solution-based deposition techniques.

Probing the switching mechanism in ZnO nanoparticle memristors

We investigate the resistance switching mechanism in memristors based on colloidal ZnO nanoparticles using electroabsorption (EA) spectroscopy. In this EA experiment, we incorporate a small amount of low-bandgap polymer, poly(9,9-dioctylfluorene-co-benzothiadiazole), as a probe molecule in ZnO-nanoparticle memristors. By characterizing this polymer, we can study the change of built-in potential (VBI) in the device during the resistance switching process without disturbing the resistance state by the EA probe light. Our results show that VBI increases when the device is switched to the high resistance state, suggesting a shift of effective workfunction of the electrode. Thus, we attribute the resistance switching to the field-dependent migration of oxygen vacancies associated with the adsorption and desorption of oxygen molecules at the Al/ZnO interface. This process results in the modulation of the interfacial injection barrier, which governs the resistance state of the device.

On the positron in a metal

The self-consistent calculations of the spatial distributions of electrons and potentials in vacancies of metals with a localized positron, the spatial distributions of positrons localized in surface states, and the binding energies of positrons and their lifetimes have been performed in terms of the Kohn-Sham method and the stabilized jellium model. The presence of a localized positron in a vacancy leads to the effect that the vacancy is weakly distinguishable for electron waves: the positron weakens the potential field in the vicinity of the vacancy and leads to a phase shift of the scattering electron wave functions. The calculation of the phase shifts of the wave functions for quasi-free positrons scattered by unperturbed vacancies and the representation of a system of vacancies as a “superlattice” in a metal have made it possible to find the shift of the positron work function and the vacancy contribution to the positron effective mass.

Surface Dipoles and Electron Transfer at the Metal Oxide–Metal Interface: A 2PPE Study of Size-Selected Metal Oxide Clusters Supported on Cu(111)

Two-photon photoemission spectroscopy (2PPE) was employed to investigate the electronic interactions at the interface of size-selected metal oxide clusters (Mo3O9, W3O9, Ti3O6, Mo3O6, W3O6, and Ti5O10) and a Cu(111) surface. The cluster–Cu interactions were probed by work function shifts measured by 2PPE as a function of local cluster coverage. For all the clusters studied, the work functions shifted to higher energies after cluster deposition, indicating negative interfacial dipole moments pointing toward the surface. The magnitudes of the derived interfacial dipoles are found to be in the order Mo3O9 ≈ W3O9 > W3O6 ≈ Mo3O6 > Ti5O10 > Ti3O6. DFT calculations of the electrostatic potentials at the interface and Bader charge analyses were used to assess the relative contributions of electron transfer and the structure-dependent cluster dipole moment to the observed work function shifts (ΔΦ). For the fully oxidized Mo3O9 and W3O9 clusters (+6 cation oxidation states), DFT calculations indicate that electron ...

The effect of post oxide deposition annealing on the effective work function in metal/Al2O3/InGaAs gate stack

The effect of post oxide deposition annealing on the effective work function in metal/Al2O3/ InGaAs gate stacks was investigated. Using a systematic method for effective work function extraction, a shift of 0.3 ± 0.1 eV was found between the effective work function of forming gas annealed samples and vacuum annealed samples. The electrical measurements enabled us to obtain the band alignment of the metal/Al2O3/InGaAs gate stack. This band alignment was confirmed by X-ray photoelectron spectroscopy. The measured shift in the effective work function between different annealing ambient may be attributed to indium out-diffusion during post oxide deposition annealing that is observed in forming gas anneal to a much larger extent than in vacuum.

Analysis of Sensing Mechanisms in a Gold-Decorated SWNT Network DNA Biosensor

We show that carbon nanotube sensors with gold particles on the single-walled carbon nanotube (SWNT) network operate as Schottky barrier transistors, in which transistor action occurs primarily by varying the resistance of Au-SWNT junction rather than the channel conductance modulation. Transistor characteristics are calculated for the statistically simplified geometries, and the sensing mechanisms are analyzed by comparing the simulation results of the MOSFET model and Schottky junction model with the experimental data. We demonstrated that the semiconductor MOSFET effect cannot explain the experimental phenomena such as the very low limit of detection (LOD) and the logarithmic dependence of sensitivity to the DNA concentration. By building an asymmetric oncentricelectrode model which consists of serially-connected segments of CNTFETs and Schottky diodes, we found that for a proper explanation of the experimental data, the work function shifts should be ~ 0.1 eV for 100 pM DNA concentration and ~ 0.4 eV for 100 μM.

Investigation of Solution-Processed Ultrathin Electron Injection Layers for Organic Light-Emitting Diodes

We study two types of water/alcohol-soluble aliphatic amines, polyethylenimine (PEI) and polyethylenimine-ethoxylated (PEIE), for their suitability as electron injection layers in solution-processed blue fluorescent organic light-emitting diodes (OLEDs). X-ray photoelectron spectroscopy is used to determine the nominal thickness of the polymer layers while ultraviolet photoelectron spectroscopy is carried out to determine the induced work-function change of the silver cathode. The determined work-function shifts are as high as 1.5 eV for PEI and 1.3 eV for PEIE. Furthermore, atomic force microscopy images reveal that homogeneous PEI and PEIE layers are present at nominal thicknesses of about 11 nm. Finally, we solution prepare blue emitting polymer-based OLEDs using PEI/PEIE in combination with Ag as cathode layers. Luminous efficiency reaches 3 and 2.2 cd A(-1), whereas maximum luminance values are as high as 8000 and 3000 cd m(-2) for PEI and PEIE injection layers, respectively. The prepared devices show a comparable performance to Ca/Ag OLEDs and an improved shelf lifetime.

Large work function shift of organic semiconductors inducing enhanced interfacial electron transfer in organic optoelectronics enabled by porphyrin aggregated nanostructures

We report on large work function shifts induced by the coverage of several organic semiconducting (OSC) films commonly used in organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs) with a porphyrin aggregated layer. The insertion between the organic film and the aluminum cathode of an aggregated layer based on the meso-tetrakis(1-methylpyridinium-4-yl) porphyrin chloride (porphyrin 1), with its molecules adopting a face-to-face orientation parallel to the organic substrate, results in a significant shift of the OSC work function towards lower values due to the formation of a large interfacial dipole and induces large enhancement of either the OLED or OPV device efficiency. OLEDs based on poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-2,1′,3-thiadiazole)] (F8BT) and incorporating the porphyrin 1 at the cathode interface exhibited current efficiency values up to 13.8 cd/A, an almost three-fold improvement over the efficiency of 4.5 cd/A of the reference device. Accordingly, OPVs based on poly(3-hexylthiophene) (P3HT), [6,6]-phenyl-C61 butyric acid methyl ester (PC61BM) and porphyrin 1 increased their external quantum efficiencies to 4.4% relative to 2.7% for the reference device without the porphyrin layer. The incorporation of a layer based on the zinc meso-tetrakis (1-methylpyridinium-4-yl)porphyrin chloride (porphyrin 2), with its molecules adopting an edge-to-edge orientation, also introduced improvements, albeit more modest in all cases, highlighting the impact of molecular orientation.

The Study of How to Reduce ILD Loss in High-k and Metal Gate Last Process

High-k last and metal gate last process becomes the main stream in 20nm and beyond technology. In high-k last process, the thermal dummy gate oxide (DGO) must be removed before the growth of interfacial layer (IL). In conventional process, to avoid the plasma damage to the device, wet etch is the most popular process to remove DGO. Because the etch rate of ILD(inter layer dielectric) oxide and CESL(CT etch stop layer) layers is much higher than thermal oxide, during the removal of DGO, serious ILD and CESL loss is observed, which will induce many of following process issues, such as high-k/metal residue, gate height variation, work function shift, etc. In this paper, multi-methods are studied to reduce the loss of ILD and CESL layer. The study mainly includes improvements on film quality and optimization of removal process. Finally, the selectivity of ILD oxide and CESL to thermal dummy gate oxide can reach ~1:1.

Flexible PTB7:PC71BM bulk heterojunction solar cells with a LiF buffer layer

Bulk heterojunction solar cells were fabricated using poly[4,8-bis[(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl] (PTB7) and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) after a layer of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) was deposited on a flexible indium tin oxide (ITO)-coated polyethylene terephthalate substrate. The fabricated structures were Al/LiF/PTB7:PC71BM/PEDOT:PSS/ITO with or without a lithium fluoride (LiF) buffer layer, and the effect of the LiF buffer layer on the performance of the solar cells was investigated. The LiF layer significantly increased the open-circuit voltages and fill factors of the solar cells, presumably because of the work function shift of the aluminum cathode. As a result, the conversion efficiency increased from 2.31 to 4.02% owing to the presence of the LiF layer. From the results of a stability test, it was concluded that the inserted LiF layer acted as a shielding and scavenging protector, which prevented the intrusion of some chemical species into the active layer, thereby improving the lifetime of the unpakcaged devices.

Morphology-, synthesis- and doping-independent tuning of ZnO work function using phenylphosphonates

The work function (WF) of ZnO is modified by two types of dipole-bearing phenylphosphonate layers, yielding a maximum WF span of 1.2 eV. H3CO-phenyl phosphonate, with a positive dipole (positive pole pointing outwards from the surface), lowers the WF by ∼350 meV. NC-phenyl phosphonate, with a negative dipole, increases the WF by ∼750 meV. The WF shift is found to be independent of the type of ZnO surface. XPS data show strong molecular dipoles between the phenyl and the functionalizing (CN and OMe) tail groups, while an opposite dipole evolves in each molecular layer between the surface and the phenyl rings. The molecular modification is found to be invariant to supra-bandgap illumination, which indicates that the substrate's space charge-induced built-in potential is unlikely to be the reason for the WF difference. ZnO, grown by several different methods, with different degrees of crystalline perfection and various morphologies and crystallite dimensions, could all be modified to the same extent. Furthermore, a mixture of opposite dipoles allows gradual and continuous tuning of the WF, varying linearly with the partial concentration of the CN-terminated phosphonate in the solution. Exposure to the phosphonic acids during the molecular layer deposition process erodes a few atomic layers of the ZnO. The general validity of the treatment and the fine-tuning of the WF of treated interfaces are of interest for solar cells and LED applications.

Work function shifts of a zinc oxide surface upon deposition of self-assembled monolayers: a theoretical insight

We have investigated at the theoretical Density Functional Theory level the way the work function of zinc oxide layers is affected upon deposition of self-assembled monolayers (SAMs). 4-tert-Butylpyridine (4TBP) and various benzoic acids (BA) were adsorbed on the apolar (101[combining macron]0) ZnO and used as probe systems to assess the influence of several molecular parameters. For the benzoid acids, we have investigated the impact of changing the nature of the terminal group (H, CN, OCH3) and the binding mode of the carboxylic acid (monodentate versus bidentate) on the apolar (101[combining macron]0) surface. For each system, we have quantified the contribution from the molecular core and the anchoring group as well as of the degree of surface reconstruction on the work function shift. For the benzoic acids, the structural reorganization of the surface induces a negative shift of the work function by about 0.3 ± 0.15 eV depending on the nature of the binding mode, irrespective of the nature of the terminal function. The bond-dipole potential strongly contributes to the modification of the work function, with values in the range +1.2 to +2.0 eV. In the case of 4TBP, we further characterized the influence of the degree of coverage and of co-adsorbed species (H, OH, and water molecules) on the ZnO/SAM electronic properties as well as the influence of the ZnO surface polarity by considering several models of the polar (0001) ZnO surface. The introduction of water molecules in the (un)dissociated form at full coverage on the non-polar surface only reduces the work function by 0.3-0.4 eV compared to a reference system without co-adsorbed species. Regarding the polar surface, the work function is also significantly reduced upon deposition of a single 4BTP molecule (from -1.44 eV to -1.73 eV for our model structures), with a shift similar in direction and magnitude compared to the non-polar surfaces.

Organic Solar Cells Based on PTB7:PC71BM with Cs2CO3 as a Cathode Buffer Layer

Bulk heterojunction solar cells were fabricated using poly[[4,8-bis[(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b']dithiophene-2,6-diyl] [3-fluoro-2- [(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl] (PTB7) and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) after a layer of poly(3,4- ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) was deposited on an indium tin oxide (ITO)-coated glass substrate. The fabricated structures were glass/ITO/PEDOT:PSS/PTB7:PC71BM/Cs2CO3/Al with or without the cesium carbonate (Cs2CO3) buffer layer, and the effect of the buffer layer on the performance of the solar cells was investigated. The Cs2CO3 layer with a thickness of 0.8 nm significantly increased the short circuit current density, open-circuit voltages and fill factors of the solar cells, presumably because of the better contact between the active layer and the cathode and the work function shift of the aluminum cathode. As a result, the power conversion efficiency increased from 1.09 to 2.12%. However, when thickness of the Cs2CO3 exceeded 2 nm, significant degradation was observed. From the results of a stability test, it was suggested that the inserted Cs2CO3 layer had a minimal influence on the lifetime of the unpakcaged devices.

First principles investigation of water adsorption and charge transfer on III–V(110) semiconductor surfaces

We report a DFT/GGA study of water adsorption and charge transfer at the relaxed (110) surfaces of several III–V binary semiconductors: GaAs, GaSb, and InAs. Our calculations are the first to show that adsorption of dissociated water changes the (110) surface structure. The characteristic III–V bond rotation through an angle of 30° is reversed. The buckled III–V bond at the semiconductor/water interface rotates into the surface through a new angle, which we calculate to be approximately 11° on all three binaries. Only dissociation of water – as opposed to chemisorption or physisorption – leads to this pseudo-unrelaxed configuration. We calculate geometries and reaction energies for several different adsorption mechanisms and find that molecular adsorption is the most favorable. We are able to reproduce binding configurations and energies for known adsorption sites on GaAs(110), but we also show new calculations for water on GaSb(110) and InAs(110). Lastly, we calculate the shift in electronic work function and induced surface dipole moment due to adsorbed water. We show that shifts in work function maximize at 1 ML of water, consistent with previous experimental works. Analysis of the partial charges and electron density reveals that adsorption of water polarizes the (110) surface, leading to local charge transfer across the semiconductor/water interface.

Work function modification of the (111) gold surface covered by long alkanethiol-based self-assembled monolayers

Many recent experimental studies have demonstrated that the deposition of self-assembled monolayers on a metal electrode can significantly modulate its work function and hence charge injection properties in organic-based devices. In this context, we model here by means of Density Functional Theory (DFT) calculations the deposition of long saturated and partially fluorinated alkanethiol chains on the gold (111) surface and explore the shift in the work function while changing the size and degree of fluorination of the molecular backbone in order to contribute to the definition of design rules. Among all the derivatization schemes, only the introduction of a terminal fluoromethyl unit leads to an appreciable change in the work function shift, further accompanied by a reversal of its sign. The results show pronounced odd-even effects with different origins.

Analysis of slope-intercept plots for arrays of electron field emitters

In electron field emission experiments, a linear relationship in plots of slope vs. intercept obtained from Fowler-Nordheim analysis is commonly observed for single tips or tip arrays. By simulating samples with many tips, it is shown here that the observed linear relationship results from the distribution of input parameters, assuming a log-normal distribution for the radius of each tip. Typically, a shift from the lower-left to the upper-right of a slope-intercept plot has been correlated with a shift in work function. However, as shown in this paper, the same effect can result from a variation in the number of emitters.

Hydrostatic strain enhancement in laterally confined SiGe nanostripes

Strain engineering in SiGe nanostructures is fundamental for the design of optoelectronic devices at the nanoscale. Here we explore a new strategy, where SiGe structures are laterally confined by the Si substrate, to obtain high tensile strain yet avoid the use of external stressors, thus improving the scalability. Spectromicroscopy techniques, finite element method simulations, and ab initio calculations are used to investigate the strain state of laterally confined Ge-rich SiGe nanostripes. Strain information is obtained by tip-enhanced Raman spectroscopy with an unprecedented lateral resolution of \ensuremath{\sim}30 nm. The nanostripes exhibit a large tensile hydrostatic strain component, which is maximal at the center of the top free surface and becomes very small at the edges. The maximum lattice deformation is larger than the typical values of thermally relaxed Ge/Si(001) layers. This strain enhancement originates from a frustrated relaxation in the out-of-plane direction, resulting from the combination of the lateral confinement induced by the substrate side walls and the plastic relaxation of the misfit strain in the (001) plane at the SiGe/Si interface. The effect of this tensile lattice deformation at the stripe surface is probed by work function mapping, which is performed with a spatial resolution better than 100 nm using x-ray photoelectron emission microscopy. The nanostripes exhibit a positive work function shift with respect to a bulk SiGe alloy, quantitatively confirmed by electronic structure calculations of tensile-strained configurations. The present results have a potential impact on the design of optoelectronic devices at a nanometer-length scale.

Flexible PTB7:PC70BM Bulk-Heterojunction Solar Cells with Lif Cathode Buffer Layer

Bulk heterojunction solar cells were fabricated using [poly[[4,8-bis[(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl] (PTB7) and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) after a layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) on a flexible indium tin oxide (ITO)-coated polyethylene terephthalate substrate. The fabricated structures were Al/LiF/PTB7:PC71BM/PEDOT:PSS/ITO with or without a lithium fluoride (LiF) buffer layer, and the influence of the LiF buffer layer on the performance of the solar cells was investigated. The LiF layer significantly enhanced the open-circuit voltages and fill factors of the solar cells presumably because of the work function shift of the aluminum cathode. As a result, the conversion efficiency increased from 2.31% to 4.02% owing to the presence of the LiF layer.

Fine-Tuning the Electrostatic Properties of an Alkali-Linked Organic Adlayer on a Metal Substrate

The performance of modern organic electronic devices is often determined by the electronic level alignment at a metal-organic interface. This property can be controlled by introducing an interfacial electrostatic dipole via the insertion of a stable interlayer between the metallic and the organic phases. Here, we use density functional theory to investigate the electrostatic properties of an assembled structure formed by alkali metals coadsorbed with 7,7,8,8-tetracyanoquinodimethane (TCNQ) molecules on a Ag(100) substrate. We find that the interfacial dipole buildup is regulated by the interplay of adsorption energetics, steric constraints and charge transfer effects, so that choosing chemical substitutions within TCNQ and different alkali metals provides a rich playground to control the systems' electrostatics and in particular fine-tune its work-function shift.

Energy Level Alignment and Morphology of Ag and Au Nanoparticle Recombination Contacts in Tandem Planar Heterojunction Solar Cells

We present the interface characterization of vacuum-deposited metal nanoparticle recombination layers (Ag, Au; 1 nm equivalent thickness) at donor/acceptor heterojunctions comprising copper phthalocyanine (CuPc) and C60 as model interfaces for tandem planar heterojunction organic photovoltaics (TOPVs). We compare the extent to which voltage doubling occurs using these two metal recombination contacts (RC) in TOPVs (ITO/CuPc/C60/(Ag,Au)/CuPc/C60/BCP/Al) and correlate the differences with energetic dissimilarities revealed by UV-photoemission (UPS) and inverse photoemission (IPES) spectroscopies, and morphology as revealed by atomic force microscopy (AFM) and field-emission scanning electron microscopy (FE-SEM). Ag interlayer RCs produce the expected voltage doubling in the open-circuit voltage (VOC) for the TOPV, whereas Au RCs showed poor voltage addition. Significant shifts in ionization potential and electron affinity and shifts in local work function were observed for C60/metal heterojunctions and for heterojunctions based on C60/metal/C60 and for C60/metal/CuPc, with clear evidence for partial charge redistribution between C60 and Ag nanoparticles. AFM and FE-SEM images revealed discrete Ag nanoparticles at the C60 interface, whereas Au/C60 heterojunctions consisted of more uniform Au thin films that wet the C60 surface and penetrated below the surface. These studies point to the need for careful control of both electronic and morphological properties of thin RCs in emerging tandem organic solar cell technologies.