Stochastic simulation studies of molecular resists

The influence of resist molecular weight as well as its architecture becomes important in lithographic scales aiming at sub-45 nm resolution. The effects of processing and resist molecular geometry on line-edge roughness (LER) should be well understood in order to meet the ITRS lithographic specifications. In this work, two-dimensional simulations and comparisons of the LER between films of molecular resists and resist films made of oligomers with the same molecular diameter, showed that in all cases molecular resists have lower LER. Explanations of this behavior are proposed based on molecular architecture and the free volume distribution in the resist film. It was also found that the size of free volume regions is less in molecular resist than in the corresponding oligomers.     

Spatial Mapping of Morphology and Electronic Properties of Air‐Printed Pentacene Thin Films

To accelerate the pace of materials discovery and application, comprehensive links need to be established between a material's structure, properties, and process conditions used to obtain the material and/or final application format. This work examines the dry printing of pentacene thin film transistor (TFT) channels by guard flow‐enhanced organic vapor jet printing (GF‐OVJP), a technique that enables direct, solvent‐free, additive patterning of device‐quality molecular semiconductors in air. Deposition in air entails non‐trivial effects at the boundary between ambient surroundings and the gas jet carrying the semiconductor vapor that influence the morphology and properties of the resulting electronic devices. Synchrotron X‐ray diffraction is employed, complemented by measurement of electronic properties of GF‐OVJP deposited films in a TFT to reveal how the morphology and electronic properties of the films depend on thickness, location within the printed pattern, nozzle translation velocity, and other process parameters. The hole field‐effect mobility of the printed pentacene film is linked quantitatively with its crystallinity, as well as with extent of exposure to ambient air during deposition. The analysis can be extended to accurately predict the performance of devices deposited in air by GF‐OVJP, which are demonstrated here for a planar, large area deposit.     

Performance Optimization of Polymer Solar Cells Using Electrostatically Sprayed Photoactive Layers

Polymer solar cells (PSCs) are fabricated using a novel film deposition method, the electrostatic spray (e‐spray) technique. Stable atomization and uniform deposition of the polymer blend by e‐spray are achieved by manipulating the solution concentration, the solvent composition, and the electric field. The performance of PSCs is primarily influenced by the inherent film morphology of the e‐sprayed polymer‐blend active layers, which is significantly different from that of the conventional films that are formed using the spin‐coating (SC) method. The intrinsically formed interfacial boundaries between the e‐sprayed blend pancakes resist charge transport, which unfavorably influences device efficiency. The internal series resistance (R_S) of the PSCs that are formed using the e‐spray method (e‐spray‐PSC) is significantly reduced by a solvent vapor soaking (SVS) treatment in addition to the conventional thermodynamic nanomorphology controls. The detailed relationship between the morphologies (film morphology and internal nanomorphology) and the R_S is revealed using impedance spectroscopy. The performance of the e‐spray‐PSCs is comparable to those of the PSCs that are fabricated using the SC method under identical conditions. Therefore, the e‐spray method can be used to fabricate ultralow‐cost PSCs, because of the performance results combined with the intrinsic advantages that the e‐spray method is simple and has a low materials loss.     

Solar Cells: Performance Optimization of Polymer Solar Cells Using Electrostatically Sprayed Photoactive Layers (Adv. Funct. Mater. 20/2010)

Polymer solar cells (PSCs) are fabricated using a novel film deposition method, the electrostatic spray (e‐spray) technique. Stable atomization and uniform deposition of the polymer blend by e‐spray are achieved by manipulating the solution concentration, the solvent composition, and the electric field. The performance of PSCs is primarily influenced by the inherent film morphology of the e‐sprayed polymer‐blend active layers, which is significantly different from that of the conventional films that are formed using the spin‐coating (SC) method. The intrinsically formed interfacial boundaries between the e‐sprayed blend pancakes resist charge transport, which unfavorably influences device efficiency. The internal series resistance (R_S) of the PSCs that are formed using the e‐spray method (e‐spray‐PSC) is significantly reduced by a solvent vapor soaking (SVS) treatment in addition to the conventional thermodynamic nanomorphology controls. The detailed relationship between the morphologies (film morphology and internal nanomorphology) and the R_S is revealed using impedance spectroscopy. The performance of the e‐spray‐PSCs is comparable to those of the PSCs that are fabricated using the SC method under identical conditions. Therefore, the e‐spray method can be used to fabricate ultralow‐cost PSCs, because of the performance results combined with the intrinsic advantages that the e‐spray method is simple and has a low materials loss.     

Physical Vapor Deposition of Molecular Glass Photoresists: A New Route to Chemically Amplified Patterning

A negative tone photoresist film, consisting of a molecular glass, a photoacid generator, and an acid labile crosslinker, was prepared by physical vapor deposition, a solvent‐free process. Subsequent to deposition, the coevaporated monomers were exposed using 365 nm radiation, subjected to a post exposure bake step, and developed in aqueous base to produce sub‐micron patterns. Combinatorial techniques were used to aid optimization of the photoresist by systematic variations in composition and exposure dose. Development factors such as concentration and time were also optimized.     

Advanced Ellipsometric Characterization of Conjugated Polymer Films

Conjugated polymers are attracting worldwide attention due to their potential for use as the active layer in advanced electronic, optoelectronic, and energy harvesting applications, and their cost‐effective and low thermal budget processing traits. As the technologies based on these materials develop, new and more sensitive characterization techniques are needed. Recent progress on the use of spectroscopic ellipsometry as a highly sensitive and non‐invasive method to obtain fundamental information about conjugated polymer films is reviewed. After a brief introduction to the practical details of the technique, the use of ellipsometry to determine optical parameters that provide insight into film morphology is described, including physical phase and molecular orientation, and resulting electronic structure. The characterization of layered systems and the use of in‐situ ellipsometry as a means to gain understanding of the kinetics that occur during film deposition and post‐deposition thermal and solvent vapor treatment is also discussed.     

Cover Picture: High Definition Digital Fabrication of Active Organic Devices by Molecular Jet Printing (Adv. Funct. Mater. 15/2007)

A new method for direct patterning of organic optoelectronic/electronic devices using a reconfigurable and scalable printing method is reported by Vladimir Bulovic and co‐workers on p. 2722. The printing technique is applied to the fabrication of high‐resolution printed organic light emitting devices (OLEDs) and organic field effect transistors (OFETs). Remarkably, the final print‐deposited films are evaporated onto the substrate (rather than solvent printed), giving high‐quality, solvent‐free, molecularly flat structures that match the performance of comparable high‐performance unpatterned films. We introduce a high resolution molecular jet (MoJet) printing technique for vacuum deposition of evaporated thin films and apply it to fabrication of 30 μm pixelated (800 ppi) molecular organic light emitting devices (OLEDs) based on aluminum tris(8‐hydroxyquinoline) (Alq₃) and fabrication of narrow channel (15 μm) organic field effect transistors (OFETs) with pentacene channel and silver contacts. Patterned printing of both organic and metal films is demonstrated, with the operating properties of MoJet‐printed OLEDs and OFETs shown to be comparable to the performance of devices fabricated by conventional evaporative deposition through a metal stencil. We show that the MoJet printing technique is reconfigurable for digital fabrication of arbitrary patterns with multiple material sets and high print accuracy (of better than 5 μm), and scalable to fabrication on large area substrates. Analogous to the concept of “drop‐on‐demand” in Inkjet printing technology, MoJet printing is a “flux‐on‐demand” process and we show it capable of fabricating multi‐layer stacked film structures, as needed for engineered organic devices.     

Systematic Control of Nucleation Density in Poly(3‐Hexylthiophene) Thin Films

While molecular ordering via crystallization is responsible for many of the impressive optoelectronic properties of thin‐film semiconducting polymer devices, crystalline morphology and its crucial influence on performance remains poorly controlled and is usually studied as a passive result of the conditions imposed by film deposition parameters. A method for systematic control over crystalline morphology in conjugated polymer thin films by very precise control of nucleation density and crystal growth conditions is presented. A precast poly(3‐hexylthiophene) film is first swollen into a solution‐like state in well‐defined vapor pressures of a good solvent, while the physical state of the polymer chains is monitored using in situ UV–vis spectroscopy and ellipsometry. Nucleation density is selected by a controlled deswelling of the film or by a self‐seeding approach using undissolved crystalline aggregates that remain in the swollen film. Nucleation densities ranging successively over many orders of magnitude are achieved, extending into the regime of spherulitic domains 10 to 100 μm in diameter, a length scale highly relevant for typical probes of macroscopic charge transport such as field‐effect transistors. This method is presented as a tool for future systematic study of the structure‐function relation in semicrystalline semiconducting polymers in a broad range of applications.     

Simultaneous Edge‐on to Face‐on Reorientation and 1D Alignment of Small π‐Conjugated Molecules Using Room‐Temperature Mechanical Rubbing

In this study, room‐temperature mechanical rubbing is used to control the 3D orientation of small π‐conjugated molecular systems in solution‐processed polycrystalline thin films without using any alignment substrate. High absorption dichroic ratio and significant anisotropy in charge carrier mobilities (up to 130) measured in transistor configuration are obtained in rubbed organic films based on the ambipolar quinoidal quaterthiophene (QQT(CN)4). Moreover, a solvent vapor annealing treatment of the rubbed film is found to improve the optical and charge transport anisotropy due to an increased crystallinity. X‐ray diffraction and atomic force microscopy measurements demonstrate that rubbing does not only lead to an excellent 1D orientation of the QQT(CN)4 molecules over large areas but also modifies the orientation of the crystals, moving molecules from an edge‐on to a face‐on configuration. The reasons why a mechanical alignment technique can be used at room temperature for such a polycrystalline film are rationalized, by the plastic characteristics of the QQT(CN)4 layer and the role of the flexible alkyl side chains in the molecular packing. This nearly complete conversion from edge‐on to face‐on orientation by mechanical treatment in polycrystalline small‐molecule‐based thin films opens perspectives in terms of fundamental research and practical applications in organic optoelectronics.     

Rational Design of Small Molecular Donor for Solution‐Processed Organic Photovoltaics with 8.1% Efficiency and High Fill Factor via Multiple Fluorine Substituents and Thiophene Bridge

A series of tetrafluorine‐substituted small molecules with a D₁‐A‐D₂‐A‐D₁ linear framework based on indacenodithiophene and difluorobenzothiadiazole is designed and synthesized for application as donor materials in solution‐processed small‐molecule organic solar cells. The impacts of thiophene π‐bridge and multiple fluorinated modules on the photophysical properties, the energy levels of the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO), charge carrier mobility, the morphologies of blend films, and their photovoltaic properties as electron donor material in the photoactive layer are investigated. By incorporating multiple fluorine substituents of benzothiadiazole and inserting two thiophene spacers, the fill factor (FF), open‐circuit voltage, and short‐circuit current density are dramatically improved in comparison with fluorinated‐free materials. With the solvent vapor annealing treatment, further enhancement in charge carrier mobility and power conversion efficiency (PCE) are achieved. Finally, a high PCE of 8.1% with very‐high FF of 0.76 for BIT‐4F‐ T/PC₇₁BM is achieved without additional additive, which is among one of the highest reported for small‐molecules‐based solar cells with PCE over 8%. The results reported here clearly indicate that high PCE in solar cells based small molecules can be significantly increased through careful engineering of the molecular structure and optimization on the morphology of blend films by solvent vapor annealing.     

Porous Nanostructured Optical Filters Rendered Insensitive to Humidity by Vapor‐Phase Functionalization

Water adsorption in many porous optical coatings can cause a detrimental red‐shift in the optical properties. In this study, a porous nanostructured rugate filter is fabricated using the glancing‐angle deposition (GLAD) technique, and rendered insensitive to large changes in ambient humidity by post‐deposition vapor‐phase functionalization. A central defect mode is added to the stop band of the filter by integrating a phase shift into the sinusoidal refractive‐index profile of the film. By monitoring the wavelength of the defect mode under variable humidity conditions, a six‐times reduction in sensitivity to water vapor is observed upon functionalization with 3,3,3‐trifluoropropyltrichlorosilane. Electrical characterization and advancing aqueous contact‐angle measurements are used to verify the hydrophobic properties of the functionalized thin films.     

Photoinduced Anisotropic Supramolecular Assembly and Enhanced Charge Transport of Poly(3‐hexylthiophene) Thin Films

The self‐organization of organic polymer semiconductors into ordered supramolecular assemblies commensurate with efficient charge transport is achieved by tuning a range of process parameters (e.g., film deposition method (spin vs drop cast), solvent boiling point (low vs high boiling point), polymer‐dielectric interface treatment, and post‐deposition processing (solvent vapor or thermal annealing)). However, these strategies present limitations for large‐scale high‐throughput processing due to associated pre‐ and/or post semiconductor deposition steps. Here, photoinduced anisotropic supramolecular assembly of P3HT chains in solution is demonstrated. UV irradiation provides for enhanced intramolecular ordering of solubilized polymer chains, and thereby effects formation of anisotropic supramolecular polymer assemblies via favorable π–π stacking (intermolecular interaction). Molecular ordering is thus dramatically enhanced with concomitant, enhanced charge transport characteristics of corresponding films. Additional pre‐ and/or post treatments are avoided.     

Microtexture and Grain Boundaries in Freestanding CVD Diamond Films: Growth and Twinning Mechanisms

Three groups of free‐standing chemical vapor deposition (CVD) diamond films formed with variations in substrate temperature, methane concentration, and film thickness are analyzed using high‐resolution electron back‐scattering diffraction. Primarily {001}, {110}, and {111} fiber textures are observed. In addition, corresponding primary and higher order twinning components are found. As interfaces, high angle, low angle, primary twin, and secondary twin boundaries are observed. A growth and a twinning model are proposed based on the sp³ hybridization of the bond in the CH₄ molecule that is used as the deposition medium.     

Titanium-dioxide dielectric films prepared by vapor reaction

The high dielectric constant of TiO2and its low sensitivity to temperature and frequency make TiO2attractive for integrated electronic applications. The most useful technique for preparing titanium-dioxide films on semiconductors and metals is the vapor reaction process. The apparatus developed for film preparation is described, and effects of deposition conditions are discussed. Uniform films are obtained over large areas and film thickness is readily controlled. Films have dielectric constants up to 82 and dissipation factors between 0.008 and 0.03 at 1 kc and a dc leakage resistivity of 5×10¹²ohm/cm. The dielectric constant is relatively frequency insensitive into the gigacycle range.     

Comparative study of the influence of the solvent on the catalytic growth of carbon nanotubes

The catalytic growth by chemical vapor deposition is a well-established route to single-wall carbon nanotubes (SWNTs). In this process, the choice and preparation of the metal catalyst determines the nanotube growth. The system Fe/Mo is known to yield a large percentage of SWNTs. In order to make use of SWNTs in electronic or electromechanical devices, the patterned growth relies on lithography techniques like photolithography or electron beam lithography. Many standard lithographic processes, i.e. the combination of photoresist and lift-off procedure, are not compatible with Fe/Mo catalyst solutions, resulting in low SWNT yield. We present a systematic study of the influence of the catalyst solvent on the patterned SWNT growth. Most remarkably, the use of water as a solvent is the basis for integrating SWNT with the established processing techniques due to its compatibility with any lithographic process and the simultaneous high SWNT yield.     

The Impacts of Cation Stoichiometry and Substrate Surface Quality on Nucleation,Structure, Defect Formation,and Intermixing in Complex Oxide Heteroepitaxy–LaCrO3 on SrTiO3(001)

The ability to design and fabricate electronic devices with reproducible properties using complex oxides is critically dependent on our ability to controllably synthesize these materials in thin‐film form. Structure‐property relationships are intimately tied to film and interface composition. Here the effect of cation stoichiometry on structural quality and defect formation in LaCrO₃ heteroepitaxial films prepared using molecular beam epitaxy is reported. From first principles the regions of stability of various candidate defects, along with the predicted effects of these defects on structural parameters, are calculated as a function of Cr and O chemical potential. Epitaxial LaCrO₃ films readily nucleate and remain coherently strained on SrTiO₃(001) over a wide range of La‐to‐Cr atom ratios, but La‐rich films are of considerably lower structural quality than stoichiometric and Cr‐rich films. Cation imbalances are accompanied by anti‐site defect formation. Cation mixing occurs at the interface for all La‐to‐Cr ratios investigated and is not quenched by deposition on SrTiO₃(001) at ambient temperature. Indiffused La atoms occupy Sr sites. Intermixing is effectively quenched by using molecular beam epitaxy to deposit LaCrO₃ at ambient temperature on defect free Si(001). However, analogous pulsed laser deposition on Si is accompanied by cation mixing.     

SHORT COMMUNICATION: Thin‐film free‐standing monocrystalline si solar cells with heterojunction emitter

We propose a novel approach to thin‐film silicon solar cells, namely the freestanding monocrystalline silicon layer transfer process with heterojunction emitter (FMS‐HJ). High crystallographic quality mono‐Si films were deposited on freestanding porous silicon (PS) films by chemical vapor deposition (CVD). These free‐standing mono‐Si (FMS) films were processed into solar cells by creating a‐a‐Si/c‐Si heterojunction. In our preliminary experiments a thin‐film FMS‐HJ solar cell with 9.6% efficiency was realized in a 20‐μμm‐thin active layer. Copyright © 2005 John Wiley & Sons, Ltd.     

沉积功率和气压对低频氮化硅薄膜应力的影响

利用等离子体增强化学气相沉积(PECVD)工艺,在不同射频功率,不同反应气压条件下制备了氮化硅薄膜。研究了低频工艺中氮化硅薄膜的沉积速率、应力以及厚度均匀性与其二者的关系。结果表明,射频功率的改变直接影响到离子对衬底的轰击效应,而反应气压的改变影响气体分子的平均自由程。离子轰击效应和分子平均自由程对氮化硅薄膜的生长过程产生影响,从而影响沉积速率、应力以及厚度均匀性等基本性质。     

Construction of White‐Light‐Emitting Silk Protein Hybrid Films by Molecular Recognized Assembly among Hierarchical Structures

The fabrication of bio‐hybrid functional films is demonstrated by applying a materials assembly technique. Based on the hierarchical structures of silk fibroin materials, functional molecular/materials, i.e., quantum dots (QDs), can be fixed to amino acid groups in silk fibroin films. It follows that white‐light‐emitting QD silk hybrid films are obtained by hydrogen bond molecular recognition to the –COO^– groups functionalized to blue luminescent ZnSe (5.2 nm) and yellow luminescent CdTe (4.1 nm) QDs in a molar ratio of 30:1 of ZnSe to CdTe QDs. Simultaneously, a systematic blue shift in the emission peak is observed from the QD solution to QDs silk fibroin films. The significant blue shift hints the appearance of the strong interaction between QDs and silk fibroins, which causes strong white‐light‐emitting uniform silk films. The molecular recognized interactions are confirmed by high resolution transmission electron microscopy, field scanning electron microscope, and attenuated total internal reflectance Fourier transform infrared spectroscopy. The QD silk films show unique advantages, including simple preparation, tunable white‐light emission, easy manipulation, and low fabrication costs, which make it a promising candidate for multicomponent optodevices.