Significantly Improve the Thermal Conductivity and Dielectric Performance of Epoxy Composite by Introducing Boron Nitride and POSS.

Dielectric materials with superb thermal and electrical properties are highly desired for high-voltage electrical equipment and advanced electronics. Here, we propose a novel strategy to improve the performance of epoxy composites by employing boron nitride nanosheets (BNNSs) and γ-glycidyl ether oxypropyl sesimoxane (G-POSS) as functional fillers. The resultant ternary epoxy composites exhibit high electrical resistivity (1.63 × 1013 Ω·cm) and low dielectric loss (<0.01) due to the ultra-low dielectric constants of cage-structure of G-POSS. In addition, a high thermal conductivity of 0.3969 W·m-1·K-1 is achieved for the epoxy composites, which is 114.66% higher than that of pure epoxy resin. This can be attributed to the high aspect ratio and excellent thermally conductive characteristics of BNNSs, promoting phonon propagation in the composites. Moreover, the epoxy composite simultaneously possesses remarkable dynamic mechanical properties and thermal stability. It is believed that this work provides a universal strategy for designing and fabricating multifunctional composites using a combination of different functional fillers.

The Recent Advances of Polymer-POSS Nanocomposites With Low Dielectric Constant.

This study provides a comprehensive overview of the preparation methods for polyhedral oligomeric silsesquioxane (POSS) monomers and polymer/POSS nanocomposites. It focuses on the latest advancements in using POSS to design polymer nanocomposites with reduced dielectric constants. The study emphasizes exploring the potential of POSS, either alone or in combination with other materials, to decrease the dielectric constant and dielectric loss of various polymers, including polyimides, bismaleimide resins, poly(aryl ether)s, polybenzoxazines, benzocyclobutene resins, polyolefins, cyanate ester resins, and epoxy resins. In addition, the research investigates the impact of incorporating POSS on improving the thermal properties, mechanical properties, surface properties, and other aspects of these polymers. The entire study is divided into two parts, discussing systematically the role of POSS in reducing dielectric constants during the preparation of POSS composites using both physical blending and chemical synthesis methods. The goal of this research is to provide valuable strategies for designing a new generation of low dielectric constant materials suitable for large-scale integrated circuits in the semiconductor materials domain.

Adjustable Plane Curvature of Covalent Organic Framework Enabling Outstanding Dielectric, Electret, and High-Temperature Processing Properties.

With the rapid development of integrated circuits towards miniaturization and complexity, there is an urgent need for materials with low dielectric constant/loss and high processing temperatures to effectively prevent signal delay and crosstalk. With high porosity, thermal stability, and easy structural modulation, covalent organic frameworks have great potential in the field of low dielectric materials. However, the optimization of dielectric properties by modulating the conjugated/plane curvature structure of covalent organic frameworks (COFs) has rarely been reported. Accordingly, we herein innovatively prepare COF films with adjustable planar curvature, hence possessing ultralow dielectric constant (1.9 at 1 kHz), ultralow dielectric loss at 1 kHz (0.0029 at room temperature, 0.0052 at 200 °C), high thermal decomposition temperature (5 % weight loss temperature, 473 °C) and good hydrophobicity (water contact angle, 105.3°). Also, to the best of our knowledge, we are the first to report that the resulting COF film enables high surface potential (≈320 V) for one week, attributing to its intrinsic high porosity, thus presenting great potential in electret applications. Accordingly, this innovative work provides a readily available and scalable idea to prepare materials with comprehensively excellent dielectric and electret properties as well as high processing temperatures simultaneously for advanced electronic device applications.

Enhancing the Plasma-Resistance Properties of Li2O-Al2O3-SiO2 Glasses for the Semiconductor Etch Process via Alkaline Earth Oxide Incorporation.

To develop plasma-resistant glass materials suitable for semiconductor etching processes, we introduced alkaline earth oxides (ROs) into a Li2O-Al2O3-SiO2 (LAS) glass. Analysis of glass properties with respect to the additives revealed that among the analyzed materials, the LAS material in which Li2O was partially replaced by MgO (MLAS) exhibited the most favorable characteristics, including a low dielectric constant (6.3) and thermal expansion coefficient (2.302 × 10-6/°C). The high performance of MLAS is attributed to the high ionic field strength of Mg2+ ions, which restricts the movement of Li+ ions under the influence of electric fields and thermal vibrations at elevated temperatures. When exposed to CF4/O2/Ar plasma, the etching speed of RO-doped glasses decreased compared with that of quartz and LAS glass, primarily owing to the generation of a high-sublimation-point fluoride layer on the surface. Herein, MLAS demonstrated the slowest etching speed, indicating exceptional plasma resistance. X-ray photoelectron spectroscopy analysis conducted immediately after plasma etching revealed that the oxidation-to-fluorination ratio of Li was the lowest for MLAS. This observation suggests that the presence of Mg2+ ions in the plasma discharge inhibits the migration of Li+ ions toward the surface, thereby contributing to the excellent plasma resistance of MLAS.

Comparison of the Properties of Epoxy Resins Containing Various Trifluoromethyl Groups with Low Dielectric Constant.

A series of epoxy resins containing various trifluoromethyl groups were synthesized and thermally cured with diaminodiphenylmethane (DDM) and aminophenyl sulfone (DDS). All epoxy resins exhibited excellent thermal stability with the glass transition temperatures of above 128 °C and 5% weight loss temperatures of above 300 °C. DDS-cured epoxy resins possessed higher thermal stability than that of DDM-cured epoxy resins, while DDM-cured epoxy resins showed better mechanical, dielectric, and hydrophobic properties. Additionally, DDM-cured epoxy resins with different locations and numbers of trifluoromethyl groups showed flexural strength in the range of 95.55~152.36 MPa, flexural modulus in the range of 1.71~2.65 GPa, dielectric constant in the range of 2.55~3.05, and water absorption in the range of 0.49~0.95%. These results indicate that the incorporation of trifluoromethyl pendant groups into epoxy resins can be a valid strategy to improve the dielectric and hydrophobic performance.

Sustainable Dielectric Films with Ultralow Permittivity from Soluble Fluorinated Polyimide.

In the rapidly growing area of high-frequency communications, polyimide films with ultralow dielectric constant and dielectric loss, adequate insulating strength, and recyclability are in high demand. Using a synthesized soluble fluorinated polyimide, a series of recyclable porous dielectric films with varying porosities were fabricated in this study through nonsolvent-induced phase separation. By manipulating the mass ratio of the binary solvent used to dissolve the polyimide, the shape, size, and size distribution of the pores generated throughout the polyimide matrix can be accurately regulated. The porosity and average pore size of the as-prepared porous films were adjustable between 71% and 33% and between 9.31 and 1.00 µm, respectively, which resulted in a variable dielectric constant of 1.51-2.42 (100 kHz) and electrical breakdown strength of 30.3-119.7 kV/mm. The porous sPI film with a porosity rate of 48% displayed a low dielectric constant of 2.48 at 10 GHz. Coupled with their superior thermal stability, mechanical characteristics, and recyclability, these porous polyimide films are highly promising for constructing high-frequency microelectronic devices.

Reliability Characteristics of Metal-Insulator-Semiconductor Capacitors with Low-Dielectric-Constant Materials.

In this study, the reliability characteristics of metal-insulator-semiconductor (MIS) capacitor structures with low-dielectric-constant (low-k) materials have been investigated in terms of metal gate area and geometry and thickness of dielectric film effects. Two low-k materials, dense and porous low-k films, were used. Experimental results indicated that the porous low-k films had shorter breakdown times, lower Weibull slope parameters and electric field acceleration factors, and weaker thickness-dependence breakdowns compared to the dense low-k films. Additionally, a larger derivation in dielectric breakdown projection model and a single Weilbull plot of the breakdown time distributions from various areas merging was observed. This study also pointed out that the porous low-k film in the irregular-shaped metal gate MIS capacitor had a larger dielectric breakdown time than that in the square- and circle-shaped samples, which violates the trend of the sustained electric field. As a result, another breakdown mechanism exists in the irregular-shaped sample, which is required to explore in the future work.

Overall Improvement in Dielectric, Water Resistance and Mechanical Properties of Polyimide Film via Synergy between GO and Sandwich-type Porous Structure.

Simultaneous improvement in dielectric, water resistance and mechanical properties of polyimide (PI) films is critical for their practical use, but difficult to achieve. Herein, a sandwich-type porous GO/PI film with excellent comprehensive properties was obtained through integrating a GO-containing complex, fluorine-containing porous structure and sandwich-type distribution of porous structure by a simple, low-cost and green breath figure method. With the addition of only a small amount of GO-containing complex, a low dielectric constant of 2.21, water absorption of 0.51%, increment in dielectric constant after moisture treatment of 1.60% and high tensile strength of 113.1 MPa, tensile modulus of 1.70 GPa, with 35.39%, 79.42%, 81.81% of reduction and 17.22%, 21.43% of increase compared to PI film were shown, respectively. Moreover, these properties could be adjusted through regulating the component and porous structure by changing the parameters of breath figure method. These outstanding properties make the film a promising candidate for high-performance low-dielectric materials.

Rational Design of Fluorinated Phthalonitrile/Hollow Glass Microsphere Composite with Low Dielectric Constant and Excellent Heat Resistance for Microelectronic Packaging.

High-performance composites with a resin matrix are urgently required for electronic packaging due to their low dielectric constant, outstanding high temperature resistance, excellent corrosion resistance, light weight and easy molding. In this work, hollow-glass-microsphere (HGM)-filled fluorinated-phthalonitrile (PBDP) composites, with filler contents ranging from 0 to 35.0 vol.%, were prepared in order to modify the dielectric properties of the phthalonitrile. Scanning electron microscopy (SEM) observations indicate that the modified HGM particles were uniformly dispersed in the matrix. The PBDP/27.5HGM-NH2 composite demonstrates a low dielectric constant of 1.85 at 12 GHz. The 5% thermogravimetric temperature (T5) of composites with silanized HGM filler (481-486 °C) is higher than the minimum packaging-material requirements (450 °C). In addition, the heat-resistance index (THRI) of PBDP/HGM-NH2 composites reached as high as 268 °C. the storage modulus of PBDP/HGM-NH2 composites were significantly increased to 1283 MPa at 400 °C, an increase by 50%, in comparison to that of PBDP phthalonitrile resin (857 MPa). The excellent dielectric and thermal properties of the present composites may pave a way for comprehensive applications in electronic packaging and thermal management for energy systems.

A Novel Diamine Containing Ester and Diphenylethane Groups for Colorless Polyimide with a Low Dielectric Constant and Low Water Absorption.

In this study, a novel diamine monomer containing ester and phenyl moieties, 1,2-diphenylethane-1,2-diyl bis(4-aminobenzoate) (1,2-DPEDBA), was synthesized through a three-step reaction. Using this diamine, a novel polyimide (PI) film was prepared with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) as a counter dianhydride through a typical two-step chemical imidization. For comparison, poly(pyromellitic dianhydride-co-4,4'-oxydianiline) (PMDA-ODA PI) was also synthesized via thermal imidization. The resulting 6-FDA-DPEDBA PI film was not only soluble in common polar solvents with high boiling points, such as N,N-dimethylacetamide (DMAc) and N,N-dimethylformamide (DMF), but also soluble in common low-boiling-point polar solvents, such as chloroform (CHCl3) and dichloromethane (CH2Cl2), at room temperature. The resulting novel PI showed a 5% weight loss temperature (T5d) at 360 °C under a nitrogen atmosphere. The resulting PI film was colorless and transparent with a transmittance of 87.1% in the visible light region ranging from 400 to 760 nm. The water absorption of the novel PI film was of 1.78%. The PI film also possessed a good moisture barrier and hydrophobicity. Furthermore, the resulting PI film displayed a low dielectric constant of 2.17 at 106 Hz at room temperature. In conclusion, the novel PI film exhibited much better optical transparency, lower moisture absorption, and a lower dielectric constant as well as better solubility than the PMDA-ODA PI film, which is insoluble in any solvent, although its thermal stability is not better than that of PMDA-ODA PI.

Impedance and Dielectric Properties of PVC:NH4I Solid Polymer Electrolytes (SPEs): Steps toward the Fabrication of SPEs with High Resistivity.

In the present article, a simple technique is provided for the fabrication of a polymer electrolyte system composed of polyvinyl chloride (PVC) and doped with varying content of ammonium iodide (NH4I) salt using solution-casting methodology. The influences of NH4I on the structural, electrochemical, and electrical properties of PVC have been investigated using X-ray diffraction, electrochemical impedance spectroscopy (EIS), and dielectric properties. The X-ray study reveals the amorphous nature of the polymer-salt complex. The EIS measurement revealed an ionic conductivity of 5.57 × 10-10 S/cm for the electrolyte containing 10 wt.% of salt. Our hypothesis is provided, which demonstrated the likelihood of designing highly resistive solid electrolytes using the concept of a polymer electrolyte. Here, the results showed that the resistivity of the studied samples is not dramatically decreased with increasing NH4I. Bode plots distinguish the decrease in resistance or impedance with increasing salt contents. Dielectric measurements revealed a decrease in the dielectric constant with the increase of NH4I content in the PVC polymer. The relaxation time and dielectric properties of the electrolytes confirmed their non-Debye type behavior. This pattern has been validated by the existence of an incomplete semicircle in the Argand plot. Insulation materials with low εr have found widespread applications in electronic devices due to the reduction in delay, power dissipation, and crosstalk. In addition, an investigation of real and imaginary parts of electric modulus leads to the minimized electrode polarization being reached.

Benzocyclobutene-functionalized hyperbranched polysiloxane for low-k materials with good thermostability.

Although hyperbranched polysiloxanes have been extensively studied, they have limited practical applications because of their low glass transition temperatures. In this study, we synthesized benzocyclobutene-functionalized hyperbranched polysiloxane (HB-BCB) via the Piers-Rubinsztajn reaction. The synthesized material was cured and crosslinking occurred at temperatures greater than 200 °C, forming a low-k thermoset resin with high thermostability. The structure of the resin was characterized using nuclear magnetic resonance (NMR) spectroscopy, viz. 1H NMR and 13C NMR spectroscopy. 29Si NMR spectroscopy was used to calculate the degree of branching. Differential scanning calorimetry, dynamic mechanical analysis, and thermogravimetric analysis revealed that the cured resin possesses good high-temperature mechanical properties and exhibits a high thermal decomposition temperature (Td5 = 512 °C). In addition, the cured resin has a low dielectric constant (k = 2.70 at 1 MHz) and low dissipation factor (2.13 × 10-3 at 1 MHz). Thus, the prepared resin can function as a low-k material with excellent high-temperature performance. These findings indicate that the performance of crosslinked siloxane is significantly attributed to the introduction of BCB groups and the formation of the highly crosslinked structure.

The Evolution of Organosilicon Precursors for Low-k Interlayer Dielectric Fabrication Driven by Integration Challenges.

Since the application of silicon materials in electronic devices in the 1950s, microprocessors are continuously getting smaller, faster, smarter, and larger in data storage capacity. One important factor that makes progress possible is decreasing the dielectric constant of the insulating layer within the integrated circuit (IC). Nevertheless, the evolution of interlayer dielectrics (ILDs) is not driven by a single factor. At first, the objective was to reduce the dielectric constant (k). Reduction of the dielectric constant of a material can be accomplished by selecting chemical bonds with low polarizability and introducing porosity. Moving from silicon dioxide, silsesquioxane-based materials, and silica-based materials to porous silica materials, the industry has been able to reduce the ILDs' dielectric constant from 4.5 to as low as 1.5. However, porous ILDs are mechanically weak, thermally unstable, and poorly compatible with other materials, which gives them the tendency to absorb chemicals, moisture, etc. All these features create many challenges for the integration of IC during the dual-damascene process, with plasma-induced damage (PID) being the most devastating one. Since the discovery of porous materials, the industry has shifted its focus from decreasing ILDs' dielectric constant to overcoming these integration challenges. More supplementary precursors (such as Si-C-Si structured compounds), deposition processes (such as NH3 plasma treatment), and post porosity plasma protection treatment (P4) were invented to solve integration-related challenges. Herein, we present the evolution of interlayer dielectric materials driven by the following three aspects, classification of dielectric materials, deposition methods, and key issues encountered and solved during the integration phase. We aim to provide a brief overview of the development of low-k dielectric materials over the past few decades.

High-Performance Cyanate Ester Resins with Interpenetration Networks for 3D Printing.

As the 3D printing technology is getting more and more popular and useful, demands for materials for 3D printing have increased significantly. Cyanate ester (CE) resin possesses the characteristics of high heat distortion temperature and high glass transition temperature, outstanding mechanical properties, low dielectric constant, and excellent water uptake. However, CE resin has not been widely used in 3D printing of UV curing because it is difficult for photopolymerizable groups to graft onto the chains of CE resin. On the other hand, the glass transition temperature (Tg) of the homopolymer of the tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA) outclasses that of other acrylates. Although THEICTA is particularly advantageous to prepare a UV-curing prepolymer with high glass transition temperature, it also cannot be directly used for fabricating heat-resistant 3D-printed parts because it is solid and adding diluents will reduce the thermal stability of printed objects. This study is unique in producing 3D-printed materials, in which the THEICTA tactfully dissolves in low viscosity (about 100 mPa·s under 25 °C) bisphenol E cyanate (BECy) without sacrificing two kinds of bulk material properties. In the process of 3D printing, the carbon-carbon double bonds from THEICTA are cured by radical polymerization. Postprinting thermal treatment transforms three cyanate groups to a triazine ring structure. Additionally, the two kinds of structures are interpenetrating. The high-performance 3D-printing material has potential in fields ranging from space flight and aviation to the automotive and electronic industry.

Low Dielectric Constant Polyimide Obtained by Four Kinds of Irradiation Sources.

Irradiation is a good modification technique, which can be used to modify the electrical properties, mechanical properties, and thermal properties of polymer materials. The effects of irradiation on the electrical properties, mechanical properties, and structure of polyimide (PI) films were studied. PI films were irradiated by a 1 MeV electron, 3 MeV proton, 10 MeV proton, and 25 MeV carbon ion. Dielectric constant, dielectric loss, and resistance measurements were carried out to evaluate the changes in the electrical properties; moreover, the mechanical properties of the pristine and irradiated PI were analyzed by the tensile testing system. The irradiation induced chemical bonds and free radicals changes of the PI films were confirmed by the Fourier transform infrared (FTIR) spectra, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR). The dielectric constant of the PI films decreases with the increase of fluences by the four kinds of irradiation sources.

Electrical Characteristics and Reliability of Nitrogen-Stuffed Porous Low-k SiOCH/Mn2O3-xN/Cu Integration.

In our previous study, a novel barrier processing on a porous low-dielectric constant (low-k) film was developed: an ultrathin Mn oxide on a nitrogen-stuffed porous carbon-doped organosilica film (p-SiOCH(N)) as a barrier of the Cu film was fabricated. To form a better barrier Mn2O3-xN film, additional annealing at 450 °C was implemented. In this study, the electrical characteristics and reliability of this integrated Cu/Mn2O3-xN/p-SiOCH(N)/Si structure were investigated. The proposed Cu/Mn2O3-xN/p-SiOCH(N)/Si capacitors exhibited poor dielectric breakdown characteristics in the as-fabricated stage, although, less degradation was found after thermal stress. Moreover, its time-dependence-dielectric-breakdown electric-field acceleration factor slightly increased after thermal stress, leading to a larger dielectric lifetime in a low electric-field as compared to other metal-insulator-silicon (MIS) capacitors. Furthermore, its Cu barrier ability under electrical or thermal stress was improved. As a consequence, the proposed Cu/Mn2O3-xN/p-SiCOH(N) scheme is promising integrity for back-end-of-line interconnects.

Self-Toughening and Self-Enhancement Poly(arylene ether nitrile) with Low Dielectric Constant by Solid Crosslinking Reaction.

A novel poly(arylene ether nitrile) terminated with hydroxyl groups (PEN-OH) was synthesized successfully. The effects of heat-treatment temperature on the thermal properties, mechanical properties, and dielectric properties of the PEN-OH films were studied in detail. Due to the cross-linking reaction occurring, at high temperature, among the nitrile groups on the side of the PEN-OH main chain to form a structurally stable triazine ring, the structure of materials changes from a linear structure to a bulk structure. Thus, the thermal properties and mechanical properties were improved. In addition, the occurrence of cross-linking reactions can reduce the polar groups in the material, leading to the decrease of dielectric constant. As the heat-treatment temperature increased, the glass-transition temperature increased from 180.6 °C to 203.6 °C, and the dielectric constant decreased from 3.4 to 2.8 at 1 MHz. Proper temperature heat-treatment could improve the tensile strength, as well as the elongation, at the break of the PEN-OH films. Moreover, because of the excellent adhesive property of PEN-OH to copper foil, a double-layer flexible copper clad laminate (FCCL) without any adhesives based on PEN-OH was prepared by a simple hot-press method, which possessed high peel strength with 1.01 N/mm. Therefore, the PEN-OH has potential applications in the electronic field.

Purification of Perovskite Quantum Dots Using Low-Dielectric-Constant Washing Solvent "Diglyme" for Highly Efficient Light-Emitting Devices.

Cesium lead halide (CsPbX3, X = Cl, Br, or I) perovskite quantum dots (QDs) are known as ionic nanocrystals, and their optical properties are greatly affected by the washing solvent used during the purification process. Here, we demonstrate the purification process of CsPbBr3 perovskite QDs using low-dielectric-constant solvents to completely remove impurities, such as the reaction solvent and desorbed ligands. The use of the ether solvent diethylene glycol dimethyl ether (diglyme), having a low dielectric constant of ε = 7.23, as a poor solvent for reprecipitation allowed for multiple wash cycles, which led to high purity and high photoluminescence quantum yield for CsPbBr3 QDs. The light-emitting device constructed with the CsPbBr3 QDs and washed twice with diglyme (two-wash) showed a low turn-on voltage of 2.7 V and a peak external quantum efficiency of over 8%. Thus, the purification of perovskite QDs with multiple wash cycles using a low-dielectric-constant solvent is an effective approach for enhancing not only the optical properties but also the efficiency of perovskite quantum dot light-emitting devices.

Acetalised Galactarate Polyesters: Interplay between Chemical Structure and Polymerisation Kinetics.

In spite of the progress that has made so far in the recent years regarding the synthesis of bio-based polymers and in particular polyesters, only few references address the optimisation of these new reactions with respect to conversion and reaction time. Related to this aspect, we here describe the transesterification reaction of two different acetalised galactarate esters with a model aliphatic diol, 1,6-hexanediol. The kinetics of these two apparently similar reactions is compared, with a focus on the conversion while varying the concentration of a di-butyltin oxide catalyst (DBTO), respectively, the used N2 flow-rate. During the first stage of polymerisation, the molecular weight of the end-products is more than doubled when using a 250 mL/min flow as opposed to an almost static N2 pressure. Additionally, the resulted pre-polymers are subjected to further polycondensation and the comparison between the obtained polyesters is extended to their thermal, mechanical and dielectrical characterisation. The influence of the acetal groups on the stability of the polyesters in acidic conditions concludes the study.

Particles adsorbed at various non-aqueous liquid-liquid interfaces.

Particles adsorbed at liquid interfaces are commonly used to stabilise water-oil Pickering emulsions and water-air foams. The fundamental understanding of the physics of particles adsorbed at water-air and water-oil interfaces is improving significantly due to novel techniques that enable the measurement of the contact angle of individual particles at a given interface. The case of non-aqueous interfaces and emulsions is less studied in the literature. Non-aqueous liquid-liquid interfaces in which water is replaced by other polar solvents have properties similar to those of water-oil interfaces. Nanocomposites of non-aqueous immiscible polymer blends containing inorganic particles at the interface are of great interest industrially and consequently more work has been devoted to them. By contrast, the behaviour of particles adsorbed at oil-oil interfaces in which both oils are immiscible and of low dielectric constant (ε<3) is scarcely studied. Hydrophobic particles are required to stabilise these oil-oil emulsions due to their irreversible adsorption, high interfacial activity and elastic shell behaviour.