Reactive Vapor-Phase Inhibitors for Area-Selective Depositions at Tunable Critical Dimensions.

Area-selective depositions (ASD) take advantage of the chemical contrast between material surfaces in device fabrication, where a film can be selectively grown by chemical vapor deposition on metal versus a dielectric, for instance, and can provide a path to nontraditional device architectures as well as the potential to improve existing device fabrication schemes. While ASD can be accessed through a variety of methods, the incorporation of reactive moieties in inhibitors presents several advantages, such as increasing thermal stability and limiting precursor diffusion into the blocking layer. Alkyne-terminated small molecule inhibitors (SMIs)─propargyl, dipropargyl, and tripropargylamine─were evaluated as metal-selective inhibitors. Modeling these SMIs provided insight into the binding mechanism, influence of sterics, and complex polymer network formed from the reaction between inhibitors consisting of alkene, aromatic, and network branchpoints. While a significant contrast in the binding of the SMIs on copper versus a dielectric was observed, residual amounts were detected on the dielectric surfaces, leading to variable ALD growth rates dependent on pattern-critical dimensions. This behavior can be controlled and utilized to direct film growth on patterns only above a critical threshold dimension; below this threshold, both the dielectric and metal features are protected. This method provides another design parameter for ASD processes and may extend its application to broader-ranging device fabrication schemes.

Polarizing white light interferometry for phase measurements using two simultaneous interferograms.

Our research introduces a design for a polarization phase-shifting white light interferometric system (PPS-WLIS) that operates in a transmissive mode for measuring the slope phase of transparent objects. It comprises a cyclic path interferometer (lateral shear interferometer) coupled with a multiplexing Michelson interferometer. The system uses polarization to produce two parallel interferograms with polarization modulated with relative shifts simultaneously. To determine the optical phase, we used a two-step algorithm for phase demodulation that does not necessitate precise phase shifts, making the system more straightforward to operate. As a result, we could observe variations in the object associated with optical phase changes. Furthermore, our method simplifies the phase-shift interferometry process by requiring only one capture, making it an effective way to examine objects at dynamic events. As an illustration, we demonstrated the temperature measurement generated by a section of a candle flame.

Additive Lithography-Organic Monolayer Patterning Coupled with an Area-Selective Deposition.

The combination of area-selective deposition (ASD) with a patternable organic monolayer provides a versatile additive lithography platform, enabling the generation of a variety of nanoscale feature geometries. Stearate hydroxamic acid self-assembled monolayers (SAMs) were patterned with extreme ultraviolet (λ = 13.5 nm) or electron beam irradiation and developed with ASD to achieve line space patterns as small as 50 nm. Density functional theory was employed to aid in the synthesis of hydroxamic acid derivatives with optimized packing density to enhance the imaging contrast and improve dose sensitivity. Near-edge X-ray absorption fine structure spectroscopy and infrared spectroscopy reveal that the imaging mechanism is based on improved deposition inhibition provided by the cross-linking of the SAM to produce a more effective barrier during a subsequent deposition step. With patterned substrates composed of coplanar copper lines and silicon spacers, hydroxamic acids selectively formed monolayers on the metal portions and could undergo a pattern-wise exposure followed by ASD in the first combination of a patternable monolayer with ASD. This material system presents an additional capability compared to traditional ASD approaches that generally reflect a starting patterned surface. Furthermore, this bottoms-up additive approach to lithography may be a viable alternative to subtractive nanoscale feature generation.

Dynamic parallel phase-shifting electronic speckle pattern interferometer.

Methods for measuring variations in diffuse surfaces using electronic speckle pattern interferometry (ESPI) are widely used and well known. In this research, we present an out-of-plane ESPI system coupled to a Michelson configuration to generate simultaneous parallel interferograms with different phase shifts. The system uses circular polarization states to generate parallel phase shifted interferograms. Due to the polarization states, the fringes do not experience a contrast reduction, thus avoiding measurement errors that affect spatial or temporal phase-shifting in interferometry. The basic operating principle of polarization modulation is described, and results that represent the temporal evolution of an aluminum plate are presented. The generation of two simultaneous patterns allows one to track the dynamic performance of the plate.

Phase stepping through polarizing modulation in electronic speckle pattern interferometry.

We have demonstrated a speckle out-of-plane interferometer that employs phase-stepping procedures by means of polarization modulation. The system generates circular polarization states with opposite signs at each arm of the system, which overlap at the output of the interferometer, to generate phase shifts operating a conventional linear polarizer; the emerging polarization states have been analyzed to obtain the shifts needed to process the optical phase. The phase-stepping technique is demonstrated with a two-step algorithm to measure out-of-plane displacement on a flat metal plate.

A three-dimensional micro-electrode array for in-vitro neuronal interfacing.

OBJECTIVE: In this paper, we report on the development of an easy-to-fabricate three-dimensional Micro-Electrode Array (3D-MEA) specifically designed for brain-on-a-dish applications. APPROACH: The proposed device consists of pillar-shaped gold microelectrodes realized by electroplating directly on top of a standard MEA, making this approach highly versatile and convenient for batch fabrication. Moreover, with this simple technique, it is possible to obtain electrodes with a height of more than 100 µm onto different kind of substrates, ranging from glass to flexible plastic ones. MAIN RESULTS: This novel 3D-MEA structure has been validated with acute brain slices, successfully recording both epileptiform-like discharges (upon the administration of 4-AP), and electrically-evoked neuronal activity. The preliminary validation showed a substantial improvement in the signals amplitude with respect to both commercial and custom planar electrodes thanks to a better coupling offered by the peculiar shape of the three-dimensional electrodes. SIGNIFICANCE: Beside the versatility of the fabrication approach, which allows to obtain 3D MEA devices onto both rigid and flexible substrates, the reported validation showed how the pillar approach can outperform standard planar MEA recordings in terms of signal amplitude. Moreover, thanks to the possibility of obtaining multi-level 3D structures within the same device, the proposed fabrication technique offers an interesting and flexible approach for the development of a new family of electrophysiological tools for 3D in vitro electrophysiology, in particular for acute brain slices and 3D neuronal cultures for brain-on-a-dish applications.

Radial polarizing phase-shifting interferometry with applications to single-shot n interferogram measurements and potential usage for white light interferogram analysis.

In this research, we present an interferometric system to analyze transparent samples using interferograms generated by a phase-shifting radial shear grating interferometer for two cases: the first obtaining n simultaneous phase-shifting interferograms using a coherent light source and the second one using sequential phase steps with a white light source. For the first case, the simultaneous interferograms are generated using two optical systems: the first one generates the polarized pattern while the second one consists of a 4f system creating replicas of the output interferograms. By using a 2D sinusoidal phase grating, we have the advantage of obtaining up to nine replicated interferograms, all of them with comparable intensities and having amplitudes modulated by the 2D sinusoidal phase grating diffraction orders as zero-order Bessel's functions. To obtain the optical phase map, several phase shifts are generated by placing a polarizing filter covering each replicated interferogram. We highlight the advantage of using n simultaneous interferograms by comparing resulting optical phases processed by a conventional four-step algorithm against those obtained by an implemented n=N+1 method, reducing errors with noisy interferograms. Results for n=7 and n=9 cases are presented. In addition, we have tested the setup with white light interference techniques by employing the polarizer radial shearing interferometer; for this case, the optical phase is calculated with the four-step and the three-step algorithms. Results of testing the developed system to examine static and dynamic phase objects are also included.

Precise pitch-scaling of carbon nanotube arrays within three-dimensional DNA nanotrenches.

Precise fabrication of semiconducting carbon nanotubes (CNTs) into densely aligned evenly spaced arrays is required for ultrascaled technology nodes. We report the precise scaling of inter-CNT pitch using a supramolecular assembly method called spatially hindered integration of nanotube electronics. Specifically, by using DNA brick crystal-based nanotrenches to align DNA-wrapped CNTs through DNA hybridization, we constructed parallel CNT arrays with a uniform pitch as small as 10.4 nanometers, at an angular deviation <2° and an assembly yield >95%.

Parallel phase shifting radial shear interferometry with complex fringes and unknown phase shift.

We present an interferometric method to analyze transparent samples using complex fringes generated by a parallel phase shifting radial shear interferometer using two coupled interferometers. Parallel interferograms are generated using two interferometers: the first one generates the polarized base pattern, and the second system is used to generate parallel interferograms allowing the adjustment of the x-y positions of the parallel interferograms. To obtain the optical phase map, parallel phase shift is generated by collocating polarizing filters at the output of the system; the polarizers are placed at arbitrary angles since they do not require adjustment because of the phase-recovery algorithm. The optical phase was processed using a two-step algorithm based on a modified Gram-Schmidt orthogonalization method. Such an algorithm has the advantage of not being iterative and is robust to amplitude modulation. The proposed method reduces the number of captures needed in phase-shifting interferometry. We applied the developed system to examine static and dynamics phase objects.

Surface Initiated Polymer Thin Films for the Area Selective Deposition and Etching of Metal Oxides.

The area selective growth of polymers and their use as inhibiting layers for inorganic film depositions may provide a valuable self-aligned process for fabrication. Polynorbornene (PNB) thin films were grown from surface-bound initiators and show inhibitory properties against the atomic layer deposition (ALD) of ZnO and TiO2. Area selective control of the polymerization was achieved through the synthesis of initiators that incorporate surface-binding ligands, enabling their selective attachment to metal oxide features versus silicon dielectrics, which were then used to initiate surface polymerizations. The subsequent use of these films in an ALD process enabled the area selective deposition (ASD) of up to 39 nm of ZnO. In addition, polymer thickness was found to play a key role, where films that underwent longer polymerization times were more effective at inhibiting higher numbers of ALD cycles. Finally, while the ASD of a TiO2 film was not achieved despite blanket studies showing inhibition, the ALD deposition on polymer regions of a patterned film produced a different quality metal oxide and therefore altered its etch resistance. This property was exploited in the area selective etch of a metal feature. This demonstration of an area selective surface-grown polymer to enable ASD and selective etch has implications for the fabrication of both micro- and nanoscale features and surfaces.

Flat Monolayer Graphene Cathodes for Li-Oxygen Microbatteries.

Miniature batteries can accelerate the development of mobile electronics by providing sufficient energy to power small devices. Typical microbatteries commonly use thin-film inorganic electrodes based on Li-ion insertion reaction. However, they rely on the complicated thin-film synthesis method of inorganics containing many elements. Graphene, one atomic layer thick carbon sheet, has diverse physical and chemical properties and is compatible with conventional micron-scale device fabrication. Here, we study the use of chemical vapor deposition (CVD) grown monolayer graphene in a two-dimensional configuration, as a future Li-oxygen microbattery cathode. By maximizing the dissolution of discharge intermediates, we obtain 2610 Ah/ggraphene of capacity corresponding to 20% higher areal cathode energy density and 2.7 times higher cathode specific energy than that can be derived from the same volume or mass of conventional Li-ion battery cathode material. Furthermore, a clear observation on the discharge reaction on composite electrodes and their role in the charging reaction was made, thanks to the two-dimensional monolayer graphene Li-oxygen battery cathode. We demonstrate an easy integration of two-dimensional CVD graphene cathode into microscale devices by simply transferring or coating the target device substrate with flexible graphene layers. The ability to integrate and use monolayer graphene on arbitrary device substrates as well as precise control over a chemical derivation of the carbon interface can have a radical impact on future energy-storage devices.

Fifteen Nanometer Resolved Patterns in Selective Area Atomic Layer Deposition-Defectivity Reduction by Monolayer Design.

Selective area atomic layer deposition (SA-ALD) offers the potential to replace a lithography step and provide a significant advantage to mitigate pattern errors and relax design rules in semiconductor fabrication. One class of materials that shows promise to enable this selective deposition process are self-assembled monolayers (SAMs). In an effort to more completely understand the ability of these materials to function as barriers for ALD processes and their failure mechanism, a series of SAM derivatives were synthesized and their structure-property relationship explored. These materials incorporate different side group functionalities and were evaluated in the deposition of a sacrificial etch mask. Monolayers with weak supramolecular interactions between components (for example, van der Waals) were found to direct a selective deposition, though they exhibit significant defectivity at and below 100 nm feature sizes. The incorporation of stronger noncovalent supramolecular interacting groups in the monolayer design, such as hydrogen bonding units or pi-pi interactions, did not produce an added benefit over the weaker interacting components. Incorporation of reactive moieties in the monolayer component that enabled the polymerization of an SAM surface, however, provided a more effective barrier, greatly reducing the number and types of defects observed in the selectively deposited ALD film. These reactive monolayers enabled the selective deposition of a film with critical dimensions as low as 15 nm. It was also found that the selectively deposited film functioned as an effective barrier for isotropic etch chemistries, allowing the selective removal of a metal without affecting the surrounding surface. This work enables selective area ALD as a technology through (1) the development of a material that dramatically reduces defectivity and (2) the demonstrated use of the selectively deposited film as an etch mask and its subsequent removal under mild conditions.

Multiwavelength wavefront detection based on a lateral shear interferometer and polarization phase-shifting techniques.

We present a multiwavelength analysis of a wavefront detected by a color camera and a lateral shear interferometer. The system employs polarization phase-shifting techniques by rotating a linear polarizer at the output and detecting the phase information through a frequency demodulation algorithm. By considering the phase modulation obtained by rotating the analyzer, a frequency filter centered on the desired peak carries the phase and amplitude information of the detected wavefront. Theoretical approach, the consideration of Jones matrices of each element, and experimental results show the feasibility of the implementation.

Evidence for Ionic Liquid Gate-Induced Metallization of Vanadium Dioxide Bars over Micron Length Scales.

It has recently been shown that the metal-insulator transition in vanadium dioxide epitaxial films can be suppressed and the material made metallic to low temperatures by ionic liquid gating due to migration of oxygen. The gating is only possible on certain crystal facets where volume channels along the VO2's rutile c-axis intersect the surface. Here, we fabricate bars with the c-axis in plane and oriented parallel to or perpendicular to the length of the bars. We show that only bars with the c-axis perpendicular to the bars, for which the volume channels are accessible from the sides of the bar, can be metallized by ionic liquid gating. Moreover, we find that bars up to at least 0.5 µm wide can be fully gated, demonstrating the possibility of the electric field induced migration of oxygen over very long distances, ∼5 times longer than previously observed.

Orientation Control of Block Copolymers Using Surface Active, Phase-Preferential Additives.

Orientation control of thin film nanostructures derived from block copolymers (BCPs) are of great interest for various emerging technologies like separation membranes, nanopatterning, and energy storage. While many BCP compositions have been developed for these applications, perpendicular orientation of these BCP domains is still very challenging to achieve. Herein we report on a new, integration-friendly approach in which small amounts of a phase-preferential, surface active polymer (SAP) was used as an additive to a polycarbonate-containing BCP formulation to obtain perpendicularly oriented domains with 19 nm natural periodicity upon thermal annealing. In this work, the vertically oriented BCP domains were used to demonstrate next generation patterning applications for advanced semiconductor nodes. Furthermore, these domains were used to demonstrate pattern transfer into a hardmask layer via commonly used etch techniques and graphoepitaxy-based directed self-assembly using existing lithographic integration schemes. We believe that this novel formulation-based approach can easily be extended to other applications beyond nanopatterning.

Enabling complex nanoscale pattern customization using directed self-assembly.

Block copolymer directed self-assembly is an attractive method to fabricate highly uniform nanoscale features for various technological applications, but the dense periodicity of block copolymer features limits the complexity of the resulting patterns and their potential utility. Therefore, customizability of nanoscale patterns has been a long-standing goal for using directed self-assembly in device fabrication. Here we show that a hybrid organic/inorganic chemical pattern serves as a guiding pattern for self-assembly as well as a self-aligned mask for pattern customization through cotransfer of aligned block copolymer features and an inorganic prepattern. As informed by a phenomenological model, deliberate process engineering is implemented to maintain global alignment of block copolymer features over arbitrarily shaped, 'masking' features incorporated into the chemical patterns. These hybrid chemical patterns with embedded customization information enable deterministic, complex two-dimensional nanoscale pattern customization through directed self-assembly.

Dynamic phase imaging of microscopic measurements using parallel interferograms generated from a cyclic shear interferometer.

We present a technique which allows us to generate two parallel interferograms with phase shifts of π/2 using a Cyclic Shear Interferometer (CSI) and a polarizing splitter. Because of the use of a CSI, we obtain the derivative phase data map directly, due to its configuration, it is immune to vibrations because the reference wavefront and the object wavefront have a common path; the shearing interferometer is insensitive to temperature and vibration. To obtain the optical phase data map, two interferograms are generated by collocating a polarizing device at the output of the CSI. The optical phase was processed using a Vargas-Quiroga algorithm. Related experimental results obtained for dynamic microscopic transparent samples are presented.

Pattern placement accuracy in block copolymer directed self-assembly based on chemical epitaxy.

The realization of viable designs for circuit patterns using the dense features formed by block copolymer directed self-assembly (DSA) will require a precise and quantitative understanding of self-assembled feature registration to guiding templates or chemical prepatterns. Here we report measurements of DSA placement error for lamellar block copolymer domains indexed to specific lines in the surface chemical prepattern for spatial frequency tripling and quadrupling. These measurements are made possible by the use of an inorganic domain-selective prepattern material that may be imaged upon polymer removal after DSA and a prepattern design incorporating a single feature serving as an in situ registration mark that is identifiable by pattern symmetry in both the prepattern and resulting self-assembled pattern. The results indicate that DSA placement error is correlated with average prepattern line width as well as prepattern pitch uniformity. Finally, the magnitude of DSA placement error anticipated for a uniform, optimized prepattern is estimated.

Thermally Induced Nanoimprinting of Biodegradable Polycarbonates Using Dynamic Covalent Cross-Links.

The introduction of reversible covalent bonds into polymeric systems afford robust, yet dynamic, materials that can respond to external stimuli. A series of aliphatic polycarbonate polymers were synthesized via ring-opening polymerization of furanyl and maleimido-bearing cyclic carbonate monomers. These side chains undergo thermally induced Diels-Alder reactions to afford cross-linked films. Because both the diene and dienophile were incorporated into the same polymer backbone, a protected maleimido group, in the form of the furan adduct, was used. Both the forward and reverse Diels-Alder reaction are triggered thermally, which allows the deprotection of the maleimido group and the subsequent reaction with the furanyl side chains to form cross-links. Random copolymers and poly(ethylene glycol) containing block copolymers were formed using diazabicyclo[5.4.0]undec-7-ene as the catalyst and a thiourea cocatalyst. The polymers form uniform films that can be cross-linked in the bulk state. To further illustrate the dynamic nature of the covalent bonds within the cross-linked films, a patterned silicon mold was used to transfer a series of nanoscale patterns using a thermal nanoimprint process.

Parallel two-step phase shifting interferometry using a double cyclic shear interferometer.

A parallel two-step polarizing phase shifting interferometer based on a Double Cyclic Shear Interferometer (DCSI) is proposed in this paper for quantitative phase imaging. The system has the advantage of retrieving the derivative phase data map directly. Due to its configuration, it presents better stability against external configurations than other types of interferometers. The DCSI generates two π-shifted interferograms, which are recorded by the CCD camera in a single-shot. The separation between parallel interferograms can be varied in the two axes for convenience. To obtain the optical phase data map, a parallel phase shift between interferograms is obtained by rotating a half wave plate retarder. We analyzed the cases of four patterns with shifts of π/2 captured in two shots; the optical phase was processed by a four-step algorithm. Related experimental results obtained for microscopic transparent samples are presented.