A Route Towards Sustainability Through Engineered Polymeric Interfaces

Chemical vapor deposition (CVD) of polymer films represent the marriage of two of the most important technological innovations of the modern age. CVD as a mature technology for growing inorganic thin films is already a workhorse technology of the microfabrication industry and easily scalable from bench to plant. The low cost, mechanical flexibility, and varied functionality offered by polymer thin films make them attractive for both macro and micro scale applications. This review article focuses on two energy and resource efficient CVD polymerization methods, initiated Chemical Vapor Deposition (iCVD) and oxidative Chemical Vapor Deposition (oCVD). These solvent‐free, substrate independent techniques engineer multi‐scale, multi‐functional and conformal polymer thin film surfaces and interfaces for applications that can address the main sustainability challenges faced by the world today.     

A Single‐Chamber System of Initiated Chemical Vapor Deposition and Atomic Layer Deposition for Fabrication of Organic/Inorganic Multilayer Films

A single‐chamber system capable of depositing both organic and inorganic layers by initiated chemical vapor deposition (iCVD) and atomic layer deposition (ALD) is demonstrated to facilitate the fabrication of organic/inorganic hybrid thin film encapsulation (TFE). The chamber geometry and the process conditions of iCVD and ALD are similar to each other, which enabled the design of the single‐chamber system. Both organic and inorganic films deposited via the single‐chamber system produces films with their properties equivalent to those deposited in separate iCVD and ALD reactors. Alternating the deposition mode between iCVD and ALD produces organic/inorganic multilayers with outstanding barrier properties as well as optical transparency mechanical flexibility.     

Chemical Vapor Deposition of Conformal,Functional, and Responsive Polymer Films

Chemical vapor deposition (CVD) polymerization utilizes the delivery of vapor‐phase monomers to form chemically well‐defined polymeric films directly on the surface of a substrate. CVD polymers are desirable as conformal surface modification layers exhibiting strong retention of organic functional groups, and, in some cases, are responsive to external stimuli. Traditional wet‐chemical chain‐ and step‐growth mechanisms guide the development of new heterogeneous CVD polymerization techniques. Commonality with inorganic CVD methods facilitates the fabrication of hybrid devices. CVD polymers bridge microfabrication technology with chemical, biological, and nanoparticle systems and assembly. Robust interfaces can be achieved through covalent grafting enabling high‐resolution (60 nm) patterning, even on flexible substrates. Utilizing only low‐energy input to drive selective chemistry, modest vacuum, and room‐temperature substrates, CVD polymerization is compatible with thermally sensitive substrates, such as paper, textiles, and plastics. CVD methods are particularly valuable for insoluble and infusible films, including fluoropolymers, electrically conductive polymers, and controllably crosslinked networks and for the potential to reduce environmental, health, and safety impacts associated with solvents. Quantitative models aid the development of large‐area and roll‐to‐roll CVD polymer reactors. Relevant background, fundamental principles, and selected applications are reviewed.     

Wafer Scale Solventless Adhesive Bonding with iCVD Polyglycidylmethacrylate: Effects of Bonding Parameters on Adhesion Energies

Initiated chemical vapor deposition (iCVD) polyglycidylmethacrylate (PGMA) thin films are investigated as adhesives for wafer‐scale bonding of 300 mm silicon substrates and demonstrated to form highly uniform, void‐free bond interfaces. The effects of bonding temperature and pressure on critical adhesion energy (G_c) between iCVD PGMA and silicon are studied using the four‐point bend technique. G_c values can be varied over an order of magnitude (0.59–41.6 J m⁻²) by controlling the bonding temperature and the observed dependence is attributed to changes in the physical (diffusion) and chemical (crosslinking) properties of the film. Thermal degradation studies using spectroscopic ellipsometry reveal that the iCVD PGMA films can crosslink when annealed above 120 °C in air. Further, changes in polymer behavior associated with annealing temperature are demonstrated to influence the crack propagation interface between the bonded substrates. These findings demonstrate the feasibility of iCVD polymer films for both temporary “thermoplastic,” and permanent “thermoset” bonding with potential applications in 3D integrated circuit technologies.     

A directly patternable click-active polymer film via initiated chemical vapor deposition (iCVD)

A new “click chemistry” active functional polymer film was directly obtained from a commercially available monomer of propargyl acrylate (PA) via easy, one-step process of initiated chemical vapor deposition (iCVD). Fourier transform infrared (FTIR) spectra confirmed that significant amount of the click-active acetylene functional group was retained after the iCVD process. The degree of crosslinking could be controlled by intentionally adding crosslinker, such as ethylene glycol diacrylate (EGDA) that was polymerized with PA to form click-active, completely insoluble copolymer. The formed iCVD polymers could also be grafted on various inorganic substrates with silane coupling agents. These crosslinking and grafting techniques give iCVD polymers chemical and mechanical stability, which allows iCVD polymers applicable to various click chemistry without any modification of reaction conditions. Pre-patterned iCVD polymer could be obtained via photolithography and an azido-functionalized dye molecule was also successfully attached on iCVD polymer via click chemistry. Moreover, pPA film demonstrated sensitivity to e-beam irradiation, which enabled clickable substrates having nanometer scale patterns without requiring the use of an additional e-beam resist. Direct e-beam exposure of this multifunctional iCVD layer, a 200 nm pattern, and QD particles were selectively conjugated on the substrates via click chemistry. Thus, iCVD pPA has shown dual functionality as of “clickable” e-beam sensitive material.     

Nanocluster deposition for oxide thin film growth at near room temperature

Metal-organic chemical vapor deposition (MOCVD) at near room temperature would not only enable integration of oxide films on polymers but would provide the capability of conformal coating of high-aspect ratio features required for fabrication of many micro-and nanoelectronic devices. The concept of near room temperature MOCVD (nanocluster deposition: NCD) consists of the production of a single phase with nanosized crystalline nuclei by a chemical vapor reaction at the showerhead maintained above the decomposition temperature of the precursors and consequently deposition of the nanosized crystalline films on unheated substrates. Deposition of the nanosized crystalline nuclei on unheated substrates was performed by controlling both the showerhead temperature and the working pressure. The Bi(3)NbO(7) (BNO) films deposited without substrate heating (real temperature of substrate surface: 50?°C) exhibit a crystalline single phase with smooth and dense morphologies, a dielectric constant of 30, a leakage current density of ～10(-6)?A?cm(-2) at 0.3?MV?cm(-1) and a step coverage of approximately 93% for films deposited at 100?°C on high-aspect ratio features. An NCD provides a new platform for near room temperature deposition of oxide thin films, opening the way for film deposition on polymer substrates to enable a flexible electronic device technology.     

A Solvent-Free,Thermally Curable Low-Temperature Organic Planarization Layer for Thin Film Encapsulation

Thin film encapsulation (TFE) is an essential component to ensure reliable operation of environmentally susceptible organic light-emitting diode-based display. In order to integrate defect-free TFE on display with complex surface structures, additional planarization layer is imperative to planarize the surface topography. The thickness of conventional planarization layer is as high as tens of µm, but the thickness must be reduced substantially to minimize the light leakage in smaller devices such as micro light-emitting diodes. In this study, a thin—less than 2 µm—planarization is achieved via solvent-free process, initiated chemical vapor deposition (iCVD). By adapting copolymer from two soft, but curable monomers, glycidyl acrylate (GA) and 2-(dimethylamino)ethyl methacrylate, excellent planarization performance is achieved on various nano-grating patterns. With only 1.5 µm-thick iCVD planarization layer, a 600 nm-deep trench polyurethane acrylate pattern is flattened completely. The TFE fabricated on planarized pattern exhibits excellent barrier property as fabricated on flat glass substrate, which strongly suggests that iCVD planarization layer can serve as a promising planarization layer to fabricate TFE on various types of complicated device surfaces.     

Applying HWCVD to particle coatings and modeling the deposition mechanism

A specific HWCVD variant known as initiated chemical vapor deposition or iCVD has been successfully implemented in the encapsulation of fine particles with polymers. Without using a liquid medium, iCVD enabled the coating of fine particles down to the nanoscale without particle agglomeration. More significantly, iCVD was demonstrated as a versatile surface design methodology in achieving the requisite surface properties by either directly depositing the polymer with the required functionality or through subsequent binding of the functionality on a pre-deposited reactive polymer. The ability to adapt iCVD to an increasingly wider array of substrates and polymer chemistries was aided by understanding iCVD reaction kinetics through mechanistic modeling.     

TiO2功能薄膜的制备及影响其光催化活性的因素

近些年来，TiO2功能薄膜以其卓越的性能，尤其是优异的光催化性能引起研究人员的广泛关注，本文根据国内外近期TiO2功能薄膜的研究现状，对化学气相沉积法，水解一沉淀法，液相沉积法，溶胶－凝胶法，原子层沉积法，溅射法，激光辅助分子束沉积法等化学和物理制备方法进行评述，并比较详细地探讨了表面羟基含量，膜的厚度和孔径，结晶形态，基片种类，掺杂和光强度等因素对TiO2薄膜光催化性能的影响。     

微波等离子体刻蚀处理对金刚石薄膜涂层刀具附着力和切削性能的影响

用HFCVD法在硬质合金（YG6）刀具衬底上沉积金刚石薄膜,用氢微波等离子体刻蚀的方法对衬底进行表面预处理,研究了该预处理技术对WC硬质合金衬底表面成分的影响,进一步探讨了所沉积金刚石薄膜的表面形貌和附着力,并通过难加工材料实际切削试验。研究了所制备的金刚石薄膜涂层刀具的切削性能。试验结果表明,Ar-H2微波等离子体刻蚀脱碳处理是提高金刚石薄膜附着力和改善涂层刀具切削性能的有效预处理方法。     

Inorganic Thin Film Deposition and Application on Organic Polymer Substrates

This review details the emerging area of inorganic thin film coatings on polymer substrates, from examples of applications through to the fabrication processes and the underlying growth mechanism(s). Of particular focus is the use of physical vapor deposition to deposit thin metal and/or metal oxide films onto polymeric materials. This primary focus highlights an area of research, that is, gaining in popularity, as researchers attempt to provide insight into the adaption of a well‐established manufacturing process to be compatible with the ever expanding range of polymer substrates. The motivation for doing so comes from the evolution of existing industry (i.e., the semi‐conductor sector) to fabricate new devices (i.e., flexible electronics). In addition, the research challenges faced in achieving evaporated and sputtered thin film coatings on polymeric substrates, such as mechanical and thermal considerations will be discussed.

     

Strategies for Drug Encapsulation and Controlled Delivery Based on Vapor‐Phase Deposited Thin Films

Vapor‐phase deposition methods allow the synthesis and engineering of organic and inorganic thin films, with high control on the chemical composition, physical properties, and conformality. In this review, the recent applications of vapor‐phase deposition methods such as initiated chemical vapor deposition (iCVD), plasma enhanced chemical vapor deposition (PE‐CVD), and atomic layer deposition (ALD), for the encapsulation of active pharmaceutical drugs are reported. The strategies and emergent routes for the application of vapor‐deposited thin films on the drug controlled release and for the engineering of advanced release nanostructured devices are presented.

     

Epitaxial Lift‐Off of Centimeter‐Scaled Spinel Ferrite Oxide Thin Films for Flexible Electronics

Mechanical flexibility of electronic devices has attracted much attention from research due to the great demand in practical applications and rich commercial value. Integration of functional oxide materials in flexible polymer materials has proven an effective way to achieve flexibility of functional electronic devices. However, the chemical and mechanical incompatibilities at the interfaces of dissimilar materials make it still a big challenge to synthesize high‐quality single‐crystalline oxide thin film directly on flexible polymer substrates. This study reports an improved method that is employed to successfully transfer a centimeter‐scaled single‐crystalline LiFe₅O₈ thin film on polyimide substrate. Structural characterizations show that the transferred films have essentially no difference in comparison with the as‐grown films with respect to the microstructure. In particular, the transferred LiFe₅O₈ films exhibit excellent magnetic properties under various mechanical bending statuses and show excellent fatigue properties during the bending cycle tests. These results demonstrate that the improved transfer method provides an effective way to compose single‐crystalline functional oxide thin films onto flexible substrates for applications in flexible and wearable electronics.     

CVD Polymers for Devices and Device Fabrication

Chemical vapor deposition (CVD) polymerization directly synthesizes organic thin films on a substrate from vapor phase reactants. Dielectric, semiconducting, electrically conducting, and ionically conducting CVD polymers have all been readily integrated into devices. The absence of solvent in the CVD process enables the growth of high‐purity layers and avoids the potential of dewetting phenomena, which lead to pinhole defects. By limiting contaminants and defects, ultrathin (<10 nm) CVD polymeric device layers have been fabricated in multiple laboratories. The CVD method is particularly suitable for synthesizing insoluble conductive polymers, layers with high densities of organic functional groups, and robust crosslinked networks. Additionally, CVD polymers are prized for the ability to conformally cover rough surfaces, like those of paper and textile substrates, as well as the complex geometries of micro‐ and nanostructured devices. By employing low processing temperatures, CVD polymerization avoids damaging substrates and underlying device layers. This report discusses the mechanisms of the major CVD polymerization techniques and the recent progress of their applications in devices and device fabrication, with emphasis on initiated CVD (iCVD) and oxidative CVD (oCVD) polymerization.     

Conformal polymeric thin films by low-temperature rapid initiated chemical vapor deposition (iCVD) using tert-butyl peroxybenzoate as an initiator

Conformal poly(cyclohexyl methacrylate) (pCHMA) thin films were synthesized via initiated chemical vapor deposition (iCVD), with tert-butyl peroxybenzoate (TBPOB) as the initiator, representing the first time that TBPOB has been used as an initiator for iCVD synthesis. Using TBPOB instead of tert-butyl peroxide (TBPO), the rate of iCVD film growth increased by a factor of up to seven at comparable conformality and lower the filament temperature from 257 to 170 °C at a comparable deposition rate of 3 nm/min. The conformal deposition of functional thin films is desired for applications including microfluidics, medical devices and membranes. Lower filament temperatures reduce the heat load to the deposition surface and thus are advantageous for polymeric substrates that are temperature sensitive or monomers that decompose at high temperatures. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results demonstrate the similarity of the TBPOB- to the TBPO-initiated pCHMA main chains. However, the aromatic group in TBPOB provided a unique spectral signature of the polymer chain end group in the FTIR and the peak intensity increased with increase of filament temperature. Scanning electron micrographs (SEMs) revealed that the pCHMA coatings are conformal over non-planar structures; however, at identical process conditions, TBPO-initiated films showed a slightly better conformality due to the lower sticking coefficient of TBPO. At a monomer partial pressure of 0.45, TBPOB has a sticking coefficient value of 0.1188 ± 0.0092, which is ～3 times as high as that of TBPO (0.0413 ± 0.0058). The step coverage is insensitive to filament temperature if the surface concentration of the monomer is fixed.     

Surface-enhanced Raman spectroscopy of the growth of ultra-thin organosilicon plasma polymers on nanoporous Ag/SiO2-bilayer films

A new method for the synthesis of thin bilayer films as surface-enhanced Raman spectroscopy (SERS) active substrates was developed which is based on the combination of plasma polymerization, plasma calcination and Ag-film deposition by means of physical vapor deposition. The surface morphology of prepared substrates was characterized by field emission scanning electron microscopy, atomic force microscopy and electrochemical impedance spectroscopy. These substrates lead to high surface enhancement factors proven by the spectroscopic analysis of adsorbed Trans-1,2 bis-(4-pyridyl) ethylene molecules. By this preparation technique, SERS-active films can be deposited on any substrate. The new SERS substrates were successfully applied to study the growth of ultra-thin hexamethyldisiloxane plasma polymer films. The Raman intensity of the CH-stretching vibration was studied as a function of the film thickness. The surface enhancement decreased sharply at about 20 nm. The resulting increase in the intensity of Raman peaks for thin adsorbed plasma polymer films was observed to be a combination of the electromagnetic enhancement mechanism and the high surface area increase of the rough Ag-surface.     

iCVD growth of poly(N-vinylimidazole) and poly(N-vinylimidazole-co-N-vinylpyrrolidone)

The imidazole group plays an important role in α-chymotrypsin catalysis, metal-ion complexation, counterion or dye binding. Poly(N-vinylimidazole), PVI, is also a good model polymer interacting with neutral salts. The poly(N-vinylimidazole-co-N-vinylpyrrolidone) copolymer P(VI-co-VP), can be used to produce highly functionalized polymers.PVI and P(VI-co-VP) thins films were achieved via initiated chemical vapor deposition (iCVD), a solvent-free process to form films under mild conditions. The polymerization was initiated by hot wire heated tert-butyl peroxide (TBPO). The chemical structure and compositions of the polymers were analyzed using FTIR and XPS. The growth rate of PVI as a function of the pressure inside the iCVD reactor was measured to be 1 nm/h mTorr. The XPS results show that the functional groups were retained in the polymer deposited. For the P(VI-co-VP) deposition, there are more VI groups found in the co-polymer chain even when the reacting monomers were fed in the same ratio.     

Combinatorial initiated chemical vapor deposition (iCVD) for polymer thin film discovery

Initiated chemical vapor deposition (iCVD) is a technique used to synthesize polymer thin films and coatings from the vapor phase in situ on solid substrates via free-radical mechanisms. It is a solventless, low-temperature process capable of forming very thin conformal layers on complex architectures. By implementing a combinatorial approach that examines five initiation temperatures simultaneously, we have realized at least a five-fold increase in efficiency. The combinatorial films were compared to a series of blanket films deposited over the same conditions to ensure the combinatorial system provided the same information. Direct synthesis from the vapor phase allows for in situ control of film morphology, molecular weight and crosslinking, and the combinatorial system decreases the time required to find the relationship between these interrelated properties. Some coatings were tested for antimicrobial performance against E. coli and B. subtilis.     

Characteristics of organic-inorganic hybrid plasma polymer thin films for low-κ ILD applications

This study investigated the effects of plasma power and tetraethylorthosilane (TEOS) to cyclohexene ratios on low-κ organic-inorganic hybrid plasma polymer thin films deposited on silicon (100) substrates. These films were deposited using a plasma enhanced chemical vapor deposition (PECVD) method, in addition to the electrical and mechanical properties of the resulting composites. Cyclohexene and TEOS were used as organic and inorganic precursors, respectively, with hydrogen and argon as precursor bubbler gases. Furthermore, additional argon was used as a carrier gas. The as-grown polymerized thin films were analyzed using ellipsometry, Fourier-transform infrared (FT-IR) spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The ellipsometry results showed the thickness of the hybrid thin film, and the FT-IR spectra showed that the hybrid polymer thin films were completely fragmented and polymerized between cyclohexene and TEOS. AFM results showed that polymer films with a smooth surface could be grown under various deposition conditions, while TEM and XRD showed that the hybrid thin film was an amorphous plasma polymer thin film without porosity. In addition, current-voltage (C-V) curves were prepared to calculate the dielectric constants. Post-annealing was applied to investigate the thermal stability of hybrid plasma polymer thin films in the hardness, Young's modulus, thermal shrinkage, and the dielectric constant at 400 °C.     

Single-chamber filament-assisted chemical vapor deposition of polymer and organosilicate films for air gap interconnect formation

Air gaps introduced at the trench level of advanced interconnects provide a means of lowering effective dielectric constant, k_eff, without the use of mechanically weak ultra low-k films. Filament-assisted chemical vapor deposition (FACVD) is a promising technology for depositing polymers, dielectrics and metals. Initiated chemical vapor deposition (iCVD) is a novel one-step method of depositing polymers in the vapor phase while retaining properties found in solution chemistry. In this paper, we present a 300 mm FACVD tool employing iCVD and FACVD processes to deposit polymer adhesion promoter (AP), decomposable polymer (DP), and permeable SiCOH cap films for air gap integration. By decomposing the iCVD polymer to form voids, we show decreased capacitance for a 160 nm line-space single damascene structure.