JP-7856862-B2 - Polymer capacitor comprising a solution-treated n-type conductive polymer

JP7856862B2JP 7856862 B2JP7856862 B2JP 7856862B2JP-7856862-B2

Inventors

リー、チーファン
ホアン、チュン－ター
ヤン、チー－ユアン
シモーネ、ファビアーノ
マルク－アントワーヌ、シュテッケル

Assignees

ウエストラ、マテリアルズ、アクチボラグ

Dates

Publication Date: 20260511
Application Date: 20240209
Priority Date: 20230210

Claims (13)

A polymer capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-treated n-type conductive polymer having a conductivity of at least 100 S/cm, and the n-type conductive polymer is poly(benzodifraglan) (PBFDO), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid)-co-3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione] (PDADF), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid) (PDADF-P), or a mixture thereof .
The polymer capacitor according to claim 1, wherein the solution-treated N-type conductive polymer has heat resistance up to 225°C.
The polymer capacitor according to claim 1, wherein the work function of the solution-treated n-type conductive polymer is at least 4.7 eV.
The polymer capacitor according to claim 1, wherein the solution-treated n-type conductive polymer does not contain side chains.
The polymer capacitor according to claim 1, wherein the anode is tantalum (Ta) and the dielectric layer is tantalum oxide ( Ta2O5 ).
The polymer capacitor according to claim 1, wherein the anode is niobium(II) oxide (NbO) and the dielectric layer is niobium(V) oxide ( Nb₂O₅ ) .
The polymer capacitor according to claim 1, wherein the anode is aluminum (Al) and the dielectric layer is aluminum oxide ( Al₂O₃ ) .
The polymer capacitor according to claim 1, wherein the polymer capacitor is in the form of a rectangular SMD chip.
The polymer capacitor according to claim 1, wherein the polymer capacitor is cylindrical in shape.
The polymer capacitor according to any one of claims 1 to 9 , wherein the polymer capacitor is sealed.
A method for manufacturing a polymer capacitor comprising an anode, a dielectric layer, and a cathode, wherein the cathode comprises a solution-treated n-type conductive polymer having a conductivity of at least 100 S/cm, and the n-type conductive polymer is poly(benzodifraglan) (PBFDO), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid)-co-3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione] (PDADF), poly[(2,2'-(2,5-dihydroxy-1,4-phenylene)diacetic acid) (PDADF-P), or a mixture thereof, and the method is a) A step of preparing the anode and dielectric layer, b) A step of preparing a polymer capacitor by applying a cathode material onto the dielectric layer, c) A method comprising the step of drying the polymer capacitor.
The method described above is a) The method according to claim 11 , further comprising the step of sealing the polymer capacitor.
The method described above is a') The process further includes a step of preparing an anode and a dielectric layer by anodizing the anode material, The method according to claim 11 , wherein step a') is performed before step a).

Description

This invention relates to polymer capacitors comprising a solution-treated n-type conductive polymer, and to a method for producing aqueous n-type conductive polymers for use in such devices. Water-based conductive polymer inks have a wide range of industrial applications, including antistatic coatings, polymer capacitors, organic solar cells, displays (LCD/OLED), and printed electronics. PEDOT:PSS is a commercially available p-type (hole transport) water-based conductive polymer ink with a pure electrical conductivity exceeding 1 S cm⁻¹ , and can reach values exceeding 4000 S cm⁻¹ with secondary doping or post-treatment. However, when considering complementary components for semiconductor devices and circuits, water-based n-type (electron transport) conductive polymers become important. The BBL:PEI ethanol-based inks reported in International Publication Nos. 2022/106017 and 2022/106018 represent a first step toward environmentally friendly solvent-type n inks. However, several issues partially limit their application. First, ethanol has stringent requirements regarding fire prevention during manufacture, transport, storage, and use. Furthermore, the inks disclosed in the above applications are limited to deposition methods such as spray casting, spin casting, and similar methods due to their large particle size. As can be seen from the above references, the maximum electrical conductivity of BBL:PEI inks is less than 10 S cm⁻¹ , making them unsuitable for devices sensitive to sheet resistance. Recently, Fei Huang et al. reported a solution-treated n-type conductive polymer poly(benzodifraglan) (PBFDO) with an electrical conductivity exceeding 2000 S/cm (Nature, 2022, s41586-022-05295-8). Developing water-based n-type CP inks with high conductivity, processability, and stability comparable to PEDOT:PSS remains a challenging scientific and industrial endeavor with far-reaching implications for cost-effective printed organic electronics. Polymer capacitors are electrolytic capacitors (e-caps) equipped with a solid conductive polymer electrolyte. There are four types: polymer tantalum electrolytic capacitors (polymer Ta-e-caps), polymer aluminum electrolytic capacitors (polymer Al-e-caps), hybrid polymer capacitors (hybrid polymer Al-e-caps), and polymer niobium oxide electrolytic capacitors. Polymer Ta-e-caps are available in rectangular surface-mount device (SMD) chip styles. Polymer Al-e-caps and hybrid polymer Al-e-caps are available in rectangular surface-mount device (SMD) chip styles, cylindrical SMD (V-chip) styles, or radial lead versions (single-ended). Polymer capacitors are characterized by particularly low internal equivalent series resistance (ESR) and high ripple current ratings. While these electrical parameters are similar to solid tantalum capacitors in terms of temperature dependence, reliability, and service life, they exhibit significantly better temperature dependence and a considerably longer service life than aluminum electrolytic capacitors with non-solid electrolytes. Polymer e-caps typically have higher leakage current ratings than other solid or non-solid electrolytic capacitors. Polymer capacitors are also available in hybrid structures. Hybrid polymer-aluminum electrolytic capacitors combine solid polymer electrolytes and liquid electrolytes. These types are characterized by low ESR values, low leakage current, and resistance to transients. However, like non-solid e-caps, they have a temperature-dependent service life. Polymer capacitors are primarily used in power supplies for integrated electronic circuits, acting as buffers, bypasses, and decoupling capacitors in flat or compact designs. Therefore, they compete with multilayer ceramic capacitors (MLCCs), but offer higher capacitance values and do not exhibit microphonic effects (such as Class 2 and Class 3 ceramic capacitors). The most important electrical characteristic of the electrolyte in an electrolytic capacitor is its electrical conductivity. The electrolyte forms the counter electrode, i.e., the cathode, of the electrolytic capacitor (e-cap). The advantages of solid polymer electrolytes are their significantly lower ESR and low temperature dependence of electrical parameters. Currently available polymer electrolytes are made from precursors consisting of extremely small base materials that can penetrate even the smallest pores. The size of this precursor limits the pore size of the etched aluminum anode foil or the tantalum powder. Capacitor manufacturing requires controlling the polymerization rate. Too fast polymerization results in incomplete anode coverage, while too slow polymerization increases production costs. Neither the precursor, the polymer, nor its residues can chemically or mechanically attack the anode oxide. Polymer electrolytes must possess high stability over long periods and across a wide temperature range. Currently available polymer e-capacitors employ either polypyrrole (PPy) or polythiophene (PED