This article concentrates on our recent results on several classes of photo- and electro-active organic materials that permit thin film formation and discusses their synthesis, properties, functions and potential applications for electronic and optoelectronic devices. The materials studied include amorphous molecular materials, titanyl phthalocyanine, oligothiophenes with well-defined structures, and non-conjugated polymers containing pendant oligothiophenes or other π-electron systems. The thin films of these materials find potential applications for use in organic electroluminescent, photovoltaic, electrochromic, and other devices.

Organic materials for electronic and optoelectronic devices

Self-assembly is an effective strategy for the creation of periodic structures at the nanoscale. However, because microelectronic devices use free-form design principles, the insertion point of self-assembling materials into existing nanomanufacturing processes is unclear. We directed ternary blends of diblock copolymers and homopolymers that naturally form periodic arrays to assemble into nonregular device-oriented structures on chemically nanopatterned substrates. Redistribution of homopolymer facilitates the defect-free assembly in locations where the domain dimensions deviate substantially from those formed in the bulk. The ability to pattern nonregular structures using self-assembling materials creates new opportunities for nanoscale manufacturing.

https://science.sciencemag.org/content/sci/308/5727/1442.full.pdf

Directed assembly of block copolymer blends into nonregular device-oriented structures.

A new field of organic materials science that deals with amorphous molecular glasses has been opened up. In addition, amorphous molecular materials have constituted a new class of functional organic materials for use in various applications. This article is focused on the recent progress of studies on photo- and electroactive amorphous molecular materials, highlighting photochromic amorphous molecular materials, amorphous molecular resists, and amorphous molecular materials for use in devices such as organic EL devices. The molecular design concepts, syntheses, reactions, molecular and solid-state properties, functions, and device fabrication and performance are described.

Photo- and electroactive amorphous molecular materials—molecular design, syntheses, reactions, properties, and applications

Directed self-assembly of block copolymer blends into nonregular device-oriented structures

In the past decade, the feature size in ultra large-scale integration (ULSI) has been continuously decreasing, leading to nanostructure fabrication. Nowadays, various lithographic techniques ranging from conventional methods (e.g. photolithography, x-rays) to unconventional ones (e.g. nanoimprint lithography, self-assembled monolayers) are used to create small features. Among all these, resist-based electron beam lithography (EBL) seems to be the most suitable technique when nanostructures are desired. The achievement of sub-20-nm structures using EBL is a very sensitive process determined by various factors, starting with the choice of resist material and ending with the development process. After a short introduction to nanolithography, a framework for the nanofabrication process is presented. To obtain finer patterns, improvements of the material properties of the resist are very important. The present review gives an overview of the best resolution obtained with several types of both organic and inorganic resists. For each resist, the advantages and disadvantages are presented. Although very small features (2-5 nm) have been obtained with PMMA and inorganic metal halides, for the former resist the low etch resistance and instability of the pattern, and for the latter the delicate handling of the samples and the difficulties encountered in the spinning session, prevent the wider use of these e-beam resists in nanostructure fabrication. A relatively new e-beam resist, hydrogen silsesquioxane (HSQ), is very suitable when aiming for sub-20-nm resolution. The changes that this resist undergoes before, during and after electron beam exposure are discussed and the influence of various parameters (e.g. pre-baking, exposure dose, writing strategy, development process) on the resolution is presented. In general, high resolution can be obtained using ultrathin resist layers and when the exposure is performed at high acceleration voltages. Usually, one of the properties of the resist material is improved to the detriment of another. It has been demonstrated that aging, baking at low temperature, immediate exposure after spin coating, the use of a weak developer and development at a low temperature increase the sensitivity but decrease the contrast. The surface roughness is more pronounced at low exposure doses (high sensitivity) and high baking temperatures. A delay between exposure and development seems to increase both contrast and the sensitivity of samples which are stored in a vacuum after exposure, compared to those stored in air. Due to its relative novelty, the capabilities of HSQ have not been completely explored, hence there is still room for improvement. Applications of this electron beam resist in lithographic techniques other than EBL are also discussed. Finally, conclusions and an outlook are presented.

/pdf/resists-for-sub-20-nm-electron-beam-lithography-with-a-focus-kriwryl4od.pdf

Resists for sub-20-nm electron beam lithography with a focus on HSQ: state of the art.

A nonpolymer material, calixarene derivative (hexaacetate p‐methnylcalix[6]arene) was tested as a high‐resolution negative resist under an electron beam lithography process It showed under 10‐mm resolution with little side roughness and high durability to halide plasma etching A sub‐10‐nm Ge quantum wire was perfectly etched off without defects Such a performance is suitable for nanoscale device processes

Ultrahigh resolution of calixarene negative resist in electron beam lithography

New nonpolymer materials, calixarene derivatives were tested as high‐resolution negative resists for use in electron beam lithography. Arrays of 12‐nm‐diam dots with a 25 nm pitch were fabricated easily. The sensitivity of calixarene in terms of area dose ranged from 700 to 7000 μC/cm2, and the required dose for dot fabrication was about 105 electrons/dot. The standard area dose for calixarene is almost 20 times higher than that for polymethyl methacrylate (PMMA), but the electron spot dose for dot fabrication by calixarene is almost the same as that for PMMA and other highly sensitive resists such as SAL (chemically amplified negative resist for electron beam made by Shipley). The electron spot dose for such extremely small dots does not seem to depend on standard area dose, but any resist tends to require the same dose under exposure in a 50 keV electron beam writing system. We propose a qualitative exposure model that suggests a tradeoff of dose and dot size. The calixarene seems to be promising materi...

Nanometer‐scale resolution of calixarene negative resist in electron beam lithography

New electron beam (EB) resists made of calixarene resists are introduced. Typical sensitivities of calixarene resists range from 700 µ C/cm2 to 7 mC/cm2. High-density dot arrays with 15 nm diameter constructed using calixarene resist were easily delineated using a point EB lithography system. Our results suggest that the resolution limit of calixarene resists is dominated by a development process such as adhesion to a substrate rather than by the EB profile. Calixarene resists are resistant to etching by halide plasma. We also demonstrated nanoscale devices processed by using calixarene resists. Calixarene resists are promising materials for nanofabrication.

Y. Ohnishi

Papers

Ultrahigh resolution of calixarene negative resist in electron beam lithography

Nanometer‐scale resolution of calixarene negative resist in electron beam lithography

Calixarene Electron Beam Resist for Nano-Lithography

Calixarenes—prospective materials for nanofabrications

Resolution of calixarene resist under low energy electron irradiation