Field-effect transistors (FETs) with channels of two-dimensional transition metal dichalcogenides (2D TMDs) are expected to extend Moore’s law by extreme scaling of contacted gate pitch (CGP) post silicon-sheet-based complementary FET (CFET) devices. The ultrathin body and fully passivated surface of 2D materials result in superior electrostatic control and improved short channel behavior. Challenges such as high contact resistance or lack of doping technology are on the way of 2D-FETs reaching the required performance for high-performance logic applications. Additionally, in order to integrate 2D TMDs in ultra-scaled CMOS devices, developing a patterning scheme via the state-of-the-art extreme ultraviolet (EUV) lithography is essential. In this paper we demonstrate our first results on studying the compatibility and interaction of semiconducting 2D TMDs with EUV environment using a set of characterization techniques that are fit to detect qualitative defects and morphological changes in these atomically thin layers. Our study is focused on semiconducting TMDs that are currently the most promising candidates for transistor channels: MoS2 (NMOS) and WSe2 (PMOS). We report the interaction of EUV photons and photo-electrons with blanket films of MoS2 and WSe2 for different EUV doses in vacuum environment. Based on the current findings we propose design of experiments aiming at developing controllable and tunable modification and patterning of 2D TMDs with the EUV energy and resolution for advanced device nodes.
Graphene-based devices have garnered significant attention for their potential in numerous applications, notably in integrated photonics. For graphene devices to be used in real-world systems, it is necessary to demonstrate competitive device performance, repeatability of results, reliability, and a path to large-scale manufacturing with high yield at low cost. In this study, single-layer graphene electro-absorption modulators serve as a pivotal test vehicle to facilitate wafer-scale integration in a 300mm pilot CMOS foundry, harnessing imec silicon photonics platforms along with the 6- inch graphene transfer capabilities of Graphenea. The patterning of graphene is achieved utilizing a hardmask, with tungsten-based contacts being developed via the damascene method to facilitate CMOS-compatible manufacturing. Through an extensive analysis of inline metrology data during process development along with analysis of hundreds of devices on each wafer, the impact of specific processing steps on the performance could be identified and optimized. Subsequent to optimization, a modulation depth of 50 ± 4 dB/mm is exemplified across 400 devices, measured utilizing 5 V peak-to-peak voltage, achieving electro-optical bandwidths up to 15.1 ± 1.8 GHz for 25μm-long devices. The results achieved are comparable to lab-based record-setting graphene devices of similar design and chemical vapor deposition graphene quality. By demonstrating the reproducibility of the results across hundreds of devices, this work resolves the bottleneck of graphene wafer-scale integration. Furthermore, CMOS-compatible processing enables co-integration of graphene-based devices with other photonics and electronics building blocks on the same chip, and for high-volume low-cost manufacturing.
In this presentation we will report on our recent work on new materials that can be monolithically integrated on high-index contrast silicon or silicon nitride photonic ICs to enhance their functionality. This includes graphene and other 2D-materials for realizing compact electro-absorption modulators and non-linear devices, ferroelectric materials for realizing phase modulators and adiabatic couplers for realizing bistable switches.
Since the discovery of graphene in 2004 by Novoselov and Geim, a lot of research emphasis has been directed towards
its characterization. Most of the important scientific breakthroughs have been obtained on exfoliated graphene (produced via the well known ‘scotch tape’ method), nowadays, different synthetic routes have been developed to obtain largescale graphene. Among several optical techniques, Raman spectroscopy is the one most often employed to characterize the defects, number of graphene layers and other properties of the graphitic films regardless of their fabrication method. In this work, we will report on the microscopic imaging of the two-photon fluorescence (2PF) properties and the second harmonic generation (SHG) in both single layer and few layer graphene.
Alexander Klekachev, Inge Asselberghs, Sergey Kuznetsov, Mirco Cantoro, Jeong Hun Mun, Byung-Jin Cho, Jun-ichi Hotta, Johan Hofkens, Marleen van der Veen, André Stesmans, Marc Heyns, Stefan De Gendt
Graphene possesses unique physical properties, due to its specific energy bands configuration, substantially
different from that of materials traditionally employed in solid-state optoelectronics. Among the variety of remarkable
properties, strong field effect, high transparency in the visible-light range and low resistivity of graphene sheets are the
most attractive ones for optoelectronic applications. Zero-dimensional colloidal semiconductor nanocrystals, known as
quantum dots (QDs), attract immense attention in the field of photonics due to their size-dependent tunable optical
properties.
By combining these two types of nanomaterials together, we demonstrate the role of graphene as an efficient
charge transfer medium from- and to II-VI quantum dots. The optical excitation of II-VI quantum dots dispersed on
single layer graphene results in an electron transfer from the nanocrystals to graphene. This is evidenced from
photoluminescence imaging and confirmed by the electrical measurements on QDs-decorated single layer graphene field
effect transistors (SLG-FET). In the second part of this paper we demonstrate an efficient hole injection from graphene
into QDs-layered nanocrystalline structures and the operation of the corresponding graphene-based quantum dot light
emitting diodes (QD-LED). We also benchmark graphene vs. indium-tin-oxide (ITO) based QD-LEDs in terms of device
electroluminescence intensity performance. Our experimental results show better hole injection efficiency for graphenebased
electrode at current densities as high as 200 mA/cm2 and suggest single layer graphene as a strong candidate to
replace ITO in QD-LED technology.
This manuscript reports that conjugated polymers can show a significant hyperpolarizability, as measured by hyper-
Rayleigh scattering (HRS). First, a disubstituted poly(phenanthrene) is examined. It is shown that the polymer exhibits
an unexpected, but extremely large second-order nonlinear optical (NLO) response, which moreover strongly depends on
the solvent conditions. As the molecular structure of the polymer does not at all fit into the classical paradigms, but yet
an extremely high hyperpolarizability is measured, these observations put these theories into perspective. An explanation
is postulated, which is based on the variation of the conjugation. Second, the hyperpolarizability of regioregular HTcoupled
poly(3-hexylthiophene)s (HT-P3HT)s is measured. It is found that also this conjugated polymer shows a
significant hyperpolarizability, showing that the observed NLO behavior of conjugated polymers is not restricted to one
polymer, but is instead more general. The dependency of the hyperpolarizability on the degree of polymerization is
established.
In the quest for organic second-order nonlinear materials, self-assembled structures based on octupolar molecules have
shown to be promising candidates. The presented work focuses on an octupolar substituted 1,3,5-trisalkynylbenzene that
forms crystals that show significant second-harmonic generation (SHG). Continuous polarization SHG measurements
were performed to elucidate the tensorial nature of this response. Unfortunately the model at hand was unable to fit the
polarization patterns due to depolarization of the second harmonic beam caused by multiple scattering in the sample.
Although the chromophore is clearly achiral, these patterns revealed a different response for left and right circularly
polarized light, also known as SHG circular difference. This implies that these molecules spontaneously assemble in
chiral superstructures. These surprising results were confirmed by circular dichroism spectroscopy, revealing a
monosignate CD band that must be attributed to a supramolecular chiral organization.
Conjugated polymers do not only attract great attention due to their suitability in organic transistors, light emitting
diodes and solar cells, moreover, they posses unexpected record-high second-order nonlinear optical responses.
Nonlinear optical polymers have been reported as attractive materials for space applications such as electro-optic
modulation and optical power limiting. In this work, we report on a new approach for increased second-order nonlinear
properties demonstrated in a series of poly(thiophene) derivatives and poly(phenanthrene)s.
The effect of extending the conjugation length, the deployment of various substituents and configurational locking of the
polyene backbone on the second-order nonlinear optical (NLO) response of a series of indoline based compounds has
been investigated. The compounds were examined using Hyper-Rayleigh scattering (HRS) and relative second-harmonic
generation (SHG) techniques with a femtosecond operating system with a 1300 nm fundamental wavelength. All of the
compounds were found to have high molecular hyperpolarizabilities with β values of up to 1230 × 10-30 esu. At the
macroscopic level-for poled polymer thin films-a strong second-order NLO signal has been detected and d33 values of
up to 217 pm/V are found-a response of some ten times greater than that found for the well known azo dye Disperse
Red 1.
Successfully predicting the frequency dispersion of electronic hyperpolarizabilities is an unresolved challenge in
materials science and electronic structure theory. It has been shown1 that the generalized Thomas-Kuhn sum rules
combined with linear absorption data and measured hyperpolarizabilities at one or two frequencies, may be used to
predict the entire frequency-dependent electronic hyperpolarizability spectrum. This treatment includes two- and threelevel
contributions that arise from the lowest two or three excited state manifolds, enabling us to describe the unusual
observed frequency dispersion of the dynamic hyperpolarizability in high oscillator strength M-PZn chromophores,
where (porphinato)zinc(II) (PZn) and metal(II)polypyridyl (M) units are connected via an ethyne unit that aligns the
high oscillator strength transition dipoles of these components in a head-to-tail arrangement. Importantly, this approach
provides a quantitative scheme to use linear optical absorption spectra and very few individual hyperpolarizability values
to predict the entire frequency-dependent nonlinear optical response. In addition we provide here experimental dynamic
hyperpolarizability values determined by hyper-Rayleigh scattering that underscore the validity of our approach.
Conjugated polymers have been extensively studied and are implemented in devices such as transistors and lightemitting
devices. We will present a solution-based study by linear and nonlinear optical characterization techniques in
which we study the behavior of different substituted poly(thiophene)s. A profound hyper-Rayleigh scattering study has
been performed in their neutral and oxidized oxidation state while continuously monitoring the transition.
The molecular linear and second-order nonlinear optical (NLO) properties of a series of donor (D)-π-acceptor (A)
merocyanine molecules have been studied in three solvents, dimethylformamide (DMF), tetrahydrofuran (THF), and
chloroform (CHCl3). All the compounds have a cyanodicyanomethylidenedihydrofuran electron acceptor system with either a pyridinylidene or quinolinylidene donor group. In high polarity solvents the molecules with a quinolinylidene donor have
larger first hyperpolarizabilities than those with a pyridinylidene donor, while the opposite is true in low polarity solvents.
The molecules under investigation have an aromatizable donor unit, which leads to a high degree of charge separation in the
ground-state; as a result they have a strong tendency to aggregate. To minimize these interactions arene-rich bulky groups
have been introduced in a number of these compounds.
and enhanced GFP (eGFP), enhanced YFP (eYFP) and DsRed have been studied at both the theoretical and experimental
levels. In the case of Dronpa, both approaches are consistent in showing the rather counterintuitive result of a larger
second-order nonlinear polarizability (or first hyperpolarizability) for the protonated state, which has a higher transition
energy, than for the deprotonated, fluorescent state with its absorption at lower energy. Moreover, the hyperpolarizability
value for the protonated form of Dronpa is among the highest reported for proteins. In addition to the pH dependence, we
have found wavelength dependence in the values. These properties are essential for the practical use of Dronpa or other
GFP-like fluorescent proteins as second-order nonlinear fluorophores for symmetry-sensitive nonlinear microscopy
imaging and as nonlinear optical sensors for electrophysiological processes. An accurate value of the first
hyperpolarizability is also essential for any qualitative analysis of the nonlinear images.
New routes have been developed in tuning the nonlinear optical properties of (metallo)organic materials by established
synthetic pathways. Several methods can be used to alter second-order nonlinear optical properties of materials such as
pH-alteration, chemical oxidation or reduction reactions, light triggering,... However, in-situ electrochemical switching
of the nonlinear optical properties of these materials opens a new and challenging research path for exploring the linear
and nonlinear properties of these materials. We are reporting on combined electrochemical and (non)linear optical
experiments. The electrochemical experiments have been conducted in solution and in-situ monitored by hyper-Rayleigh
scattering. Also thin films are shown to be electrochemically altered and in-situ probed by second-harmonic generation.
In recent years there has been significant interest in the ability to switch the second-order nonlinear optical (NLO)
response at the molecular level. A compound can be considered as an NLO switch when the response can be turned to
an 'on 'and 'off' state. Several switching schemes at the molecular level have been envisioned. Earlier schemes used
isomerisation and tautomerisation, causing changes in the nature and/or degree of conjugation between electron donor
and acceptor. An alternative approach is based on lowering the electron donating capacity of the electron donor or the
withdrawing capacity of the acceptor group. Here we will present results based on protonation/deprotonation and
oxidation/reduction of the donor group.
A variety of pyridinium and benzothiazolium-substituted conjugated donor-π-acceptor dipoles are studied by hyper-
Rayleigh scattering (HRS) in solution. We have investigated their potential as strong electron acceptor moiety and a
complete series has been synthesized and characterized. An elongation of the conjugated π-system for each molecule is
made and characterized to see the influence of the elongation of the conjugated π-system. A leveling off of the
hyperpolarizability β is already observed after three subsequent double bonds.
The results of three independently strategies for the optimizations of electro-optic organic chromophores is
presented. The first strategy to enhance the nonlinear optical response, applied at the molecular level, is the
extension of the conjugation path in a ionic chromophore. The second strategy, applied at the supramolecular
level, is the bottom-up nano-engineering of an inclusion complex of the ionic chromophore in an amylose helix.
The third strategy, also applied a the molecular level, is to use a modulated conjugation path between donor and
acceptor in order to localize eigenfunctions on different parts of the molecule. The first hyperpolarizability of
the different series of compounds has been experimentally determined by frequency-resolved femtosecond hyper-Rayleigh scattering. The effects of the three different enhancement strategies are analyzed and interepreted in
terms of the quantum limits.
Modulating the electronic, magnetic and optical properties at the molecular level using an external trigger has been
extended to the field of nonlinear optics. The switching molecule is designed to have a complexation site or a redox
active unit which can guarantee electronic communication over the whole conjugated system. The alteration of the
nonlinear property is then induced by the modulation of the internal charge-transfer due to the response of the molecule
to the external stimulus. This can be achieved by cation binding, protonation/deprotonation or electrochemically.
Sum rules have been shown to impose a fundamental limit on the of nonlinear-optical susceptibility. All of the measured values of the hyperpolarizability and second hyperpolarizability over the last 25+ years, be it on- or off-resonance, fall a factor of 103/2 below these limits. Not only is this result scientifically puzzling on a fundamental level; but, has implications on the kinds of practical devices that can be made. In this work, we discuss molecular engineering techniques that aim to break this bottleneck.
We present the results of the combination of two independently valid optimization strategies for the first hyperpolarizability of ionic organic chromophores. The first strategy to enhance the nonlinear optical response, at the molecular level, is the extension of the conjugation path in the chromophore itself. The second strategy, at the supramolecular level, is the bottom-up nano-engineering of an inclusion complex of the chromophore in an amylose helix by self-assembly. We have studied a series of five (dimethylamino)stilbazolium-type chromophores with increasing conjugation length between the (dimethylamino)phenyl donor ring and the pyridinium acceptor ring in combination with four amylose helices of different molecular weights. The first hyperpolarizability of the self-assembled inclusion complexes has been experimentally determined by frequency-resolved femtosecond hyper-Rayleigh scattering at 800 and 1300 nm. These values are compared with experimental values for the free chromophores in solution and with theoretical values. Where experimental values for the hyperpolarizability in solution were lower than theoretically predicted, an enhancement upon inclusion was observed - with the longest chromophore in the best amylose helix showing an enhancement by one order of magnitude. Molecular modelling of the inclusion of the chromophore suggests that the coplanarity of the two rings is more important than all-trans configuration in the conjugation path. The degree of enhancement, however, is not enough to breach the apparent limit of the first hyperpolarizability which is about an order of magnitude below the fundamental limit calculated by Kuzyk. This analysis confirms the determining role of the arrangement of the excited-state energy levels on the nonlinear response.
Second-order nonlinear optical properties of organic and inorganic materials have been widely investigated. However, it becomes more important to be able to switch the molecules from an 'on' state to an 'off' state, or vise versa. Several switching schemes can be thought of. We will focus our attention to alter the donor properties of metalorganic compounds. Therefore, we will oxidize the metal center of the compound chemically. Since it is more interesting to be able to electrochemically switch the metal center, we developed a combined electrochemistry/hyper-Rayleigh scattering cell to perform in-situ electrochemical switching of the hyper-Rayleigh response.
Electronic structural modifications of previously reported highly conjugated (polypyridyl)metal-(porphinato)zinc(II) NLO chromophores have been carried out. A primary focus of these modifications probed the role played by the porphyrin macrocycle in effecting large molecular hyperpolarizabilities; specifically, its meso-aryl substituents were replaced with electron withdrawing perfluoroalkyl groups. In doing so, we are effectively lowering HOMO and LUMO of the porphyrin fragment by 0.35eV while retaining the extensive mixing of B, Q, and CT states, and enforcing head-to-tail transition dipole alignment of the component metal-polypyridyl and porphyrin based chromophoric building blocks; this enables supermolecular structures with singly degenerate excited states polarized along the long donor-to-acceptor (D-to-A) charge transfer axis. This work will be placed in the context of ongoing electrooptic experiments and efforts aimed at fabricating new materials from these supermolecular chromophoric species.
A series of 2,2':4,4'':4',4'''-quaterpyridinium ligands bearing different N-substituents (methyl, Me; phenyl, Ph; 4-acetylphenyl, AcPh; 2-pyrimidyl, Pym; 3,5-bis-methoxycarbonyl-phenyl, MCP) have been prepared. These compounds feature powerful electron acceptor moieties and hence have been combined with different electron-rich metal centres to give complexes suitable for quadratic nonlinear optical properties. A series of dipolar ruthenium(II) ammine complex salts of the form [RuII(NH3)4LA][PF6]4 and octupolar complex salts of the form [MII(LA)3][PF6]8 (M = Ru(II)/Fe(II), LA = a 2,2':4,4'':4',4'''-quaterpyridinium ligand) have been prepared. These compounds exhibit multiple intense, low energy metal-to-ligand charge-transfer (MLCT) absorptions in the visible region and reversible M(III/II) redox processes. First hyperpolarizabilities have been determined directly by using hyper-Rayleigh scattering and indirectly via calculation from Stark (electroabsorption) spectroscopic data.
A number of novel salts of dipolar cations containing dimethylamino electron donor and pyridinium electron acceptor groups have been prepared and studied by using various physical techniques including hyper-Rayleigh scattering and Stark spectroscopy. In addition to showing very large molecular static first hyperpolarizabilities, several of these salts exhibit pronounced bulk quadratic nonlinear optical effects. Related compounds in which the electron donor is a ruthenium(II) ammine centre have also been investigated, allowing interesting comparisons to be made between transition metal-containing and purely organic nonlinear optical chromophores.
The syntheses and electrooptic properties of a family of nonlinear optical chromophores are described. Typically, these species feature an ethyne-elaborated, highly polarizable porphyrinic component, and metal polypyridyl complexes that serve as integral donor and acceptor elements. The frequency dependence of the dynamic hyperpolarizability of a wide-range of these chromophores, that vary widely with respect to their electronic structure, was determined from hyper-Rayleigh light scattering (HRS) measurements carried out at fundamental incident irradiation wavelengths (λinc) of 830, 1064, and 1300 nm. These data show that: (i) Coupled oscillator photophysics and metal-mediated cross-coupling can be exploited to elaborate high βλ supermolecules that exhibit significant excited-state electronic communication between their respective pigment building blocks; (ii) High-stability metal polypyridyl compounds constitute an attractive alternative to electron releasing dialkyl- and diarylamino groups, the most commonly used donor moieties in a wide-range of established NLO dyes, and long-recognized to be the moiety that often limits the thermal stability of such compounds; (iii) This design strategy clearly enables ready elaboration of extraordinarily large βλ chromophores at telecommunication-relevant wavelengths; and (iv) Multiple charge-transfer (CT) transitions within a single chromophore can be designed to have transition dipole moments of the same or opposite sign; because the sign of the resonance enhancement factor is frequency dependent, appropriate engineering of the relative contributions of these CT states at a given wavelength provides a new means to regulate the magnitude of dynamic hyperpolarizabilities.
Two examples of efficient and reversible switching of the first hyperpolarizability of charge-transfer metalorganic species are presented. The charge transfer is between a metalorganic donor unit and an organic acceptor. In one case, the donor is a ruthenium(I) pentammine complex, the acceptor is an N-methyl-4,4'-bipyridinium ligand. Oxidizing the ruthenium(II) to ruthenium(III) changes the donor to an acceptor and destroys the charge transfer, as evidence by the disappearance of the charge transfer band in linear absorption spectroscopy. In hyper-Rayleigh scattering, a reduction in first hyperpolarizability of at least an order of magnitude is observed. In a second case, the donor is an octamethylferrocene unit, while the donor is a nitro group on a thiophene. Again, oxidizing the octamethylferrocene to octamethylferrocenium reduces the hyperpolarizability with more than an order of magnitude. Both redox processes are fully reversible.
A series of novel metal-organic in-plane complexes trans- (formula available in paper) have been investigated using the hyper-Rayleigh scattering technique. Like other in-plane complexes reported recently they exhibit very large and tunable static first hyperpolarizabilities which are associated with intense visible metal-to-ligand charge-transfer excitations. Moreover, a good correlation was found between the hyperpolarizabilities and the electrochemical properties of the complexes. Furthermore, the effect of the oxidation state of the metal upon the molecular optical nonlinearity has been investigated. Chemical oxidation of the metal is proven to be an excellent tool to reversibly switch the molecular first hyperpolarizabilities of the trans- substituted ruthenium complexes.
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