TWI298339B - High dielectric constant nanocomposite and embedded capacitor comprising the same - Google Patents

Description

1298339

FIELD OF THE INVENTION The present invention relates to a nanocapacitor, and more particularly to a built-in capacitor having a high = two material and a built-in material comprising the material. Door; 1 electric "Nano-composite composite material and the prior art. With the construction of wireless communication products, the trend toward miniaturization and short-term development of ancient jr, the electronic production accounted for how to improve the functionality of the functional substrate. The development of the direction, the primary issue. In the degree, it becomes the development of electronic assembly technology. The first figure shows the separation of Baizhi ((the resistor r, the capacitor c, the surface of the substrate 1 is separated from the substrate 1 to provide the active element energy. screte) substrate, where the original A passive component such as a sense L is mounted on an auxiliary work such as the integrated circuit 2

However, since the above-mentioned passive components such as the resistor R, the Thunder, the τ _ _ _ _ _ tail valley, and the inductor L occupy most of the surface of the substrate 1, and as the circuit is complicated, the number of passive components increases accordingly. This type of separate substrate is hindered in the development of miniaturization. To further increase the density of passive components to improve functionality

The thickness of the substrate is described as having an integrated substrate. Figure lb shows an integrated substrate. As shown in the figure, the integrated substrate differs from the separate substrate in that the passive element resistance r, the capacitance C, the inductance l, and the like are laminated on the substrate by means of a substrate overlap to conform to the high density of the element.

〇424-9617TWF(nl);02910038;Renee.ptd Page 5 1298339 V. Description of invention (2) The requirements for tempering are currently used to make capacitors in integrated substrates. The main brakes are used. I is called a mixture of internal tantalum dielectric ceramic particles (such as barium titanate). The effect of the dipole arrangement of the spherical ceramics in the base of the grease and the oxygen resin matrix is ^=, and the effect of the ring dipole polarization will be offset, so that the electricity is increased by the number of ceramics... The dielectric of the material causes the mechanical properties of the substrate to be reduced, and it is not only 7 i: large: falling, so this is also currently no high-intermediate; heart: 基板 (substrate with internal-extinguishing capacitor) Adventive = positive 5 type substrate how to prepare high dielectric nano-scale mixed materials, the reason. Therefore, such as the bottleneck and focus of development. In view of the above, the object of the present invention is to provide a high dielectric constant nano composite material prepared by a capacitor, and a built-in capacitor for a built-in electric constant nano composite material. . Ij uses the above high dielectric (1) ί: to find out that 'utilized in epoxy resin base', such as carbon nanotubes, carbon black and graphite, etc., σ River: adding conductive particles, = quality (when the carbon nanotube content The 2.5 phmn tree is designed to reduce the dielectric ceramic particles, and the dielectric constant value increases the brittleness of the substrate itself, and can be charged, so that the epoxy is not maintained. The mechanical properties of the resin. SUMMARY OF THE INVENTION Accordingly, the present invention proposes a high dielectric constant that is too devoid of IP, no water, a post-water composite, page 6 0424-9617TlF(nl); 02910038; Renee.ptd 1298339

V. Description of the invention (3) comprising a polymer substrate, a substrate, and a dielectric ceramic =: J: electrical particles are distributed in the polymer. The dielectric constant of the composite material is ί: In the molecular substrate 'and the plate is formed with - ί t:: Tibetan, f 'including - substrate, the base of the composite layer, wherein:: half = - metal layer formed above - Nai, 苴 to The dielectric constant of the small spoon into the female material layer is 1 0 0

a carbon=i two polymer substrate, a dielectric ceramic particle, and an anaesthetic particle are distributed in the polymer substrate, and the third metal is formed above the composite layer; U

DETAILED DESCRIPTION OF THE INVENTION The above-mentioned polymer substrate is preferably made of a thermosetting tree, such as epoxy wax, polyamidoamine, BT resin (bismaleinude/triazine), cyanate resin (cyanate ester), polydimethyl phenoxy resin [P〇ly (2,6-diffiethylphenyl ether)] or a combination thereof. According to the present invention, the carbon-based nano conductive particles may be carbon nanotubes, carbon nanotubes, carbon sixty, carbon black, graphite or a combination thereof. Its content is better known as 0·5~1Ophrs ° '

According to the present invention, the above dielectric ceramic particles may be lead magnesium bismuth, barium titanate, cerium oxide, aluminum oxide, titanium oxide or a combination thereof. The content thereof is preferably from 0 to 60 vol%, and the particle diameter thereof is preferably from 1 〇〇 ηη to 15 〇〇 nm. The high dielectric constant nano composite material provided by the invention can meet the requirements of the integrated substrate for the built-in capacitor material, and break through the existing capacitance,

------- V. Invention description (4) ------ ί: Library: bottleneck of functional materials, and through application process, design, degree integration; = Li* complete advanced function built-in type The establishment of a high-function, high-density bauxite I-board industry. The above-mentioned objects, features, and advantages will be more apparent from the following detailed description of the preferred embodiments. An embodiment illustrates the invention. In the first embodiment, a carbon-based nano-conducting particle is added to the door-knife material to prepare a high-density 賫 賫 太 2 2 composite material; in the second embodiment, the polymer base is used in the polymer matrix:;;;; Dielectric tweezers are used to produce a high dielectric constant, and the carbon-based nano-conducting particles used in the examples are nano-negative, electro-chemical particles, etc., and the preparation methods thereof will be individually described below. Further, in the example, the epoxy resin is used as the polymer substrate, but it is suitable for use in the present invention, and the present invention is not limited thereto, and polyplylimide or bismaleimide may be used. Triazine), cyanate _ ester, polydimethyl phenoxy resin [p〇ly (2,6 — dimethyiphenyi ether)] or a combination thereof with an epoxy resin. Synthesis of carbon nanotubes (CNT) 1. Take a quantitative amount of Μ(Ν〇3)χ (where μ is mainly Fe and Ni) in deionized water, and add citric acid to stir to completely dissolve.

0424-9617TWF(η1);02910038;Renee.p td Page 8 1298339 V. INSTRUCTIONS (5) Ban Li 2·concentrate remove solvent and place it at 1〇〇. The oven is dried in an oven and then calcined in a high temperature furnace at 70 ° C for 2 hrs. The product is a metal catalyst. After cooling to room temperature, it is ground with a spider. 3 · Take a quantitative amount of the metal catalyst dispersed in the ethanol solution, oscillate 5~1 Omins by ultrasonic wave, drop it onto the quartz substrate, and heat it to 丨〇〇~丨2〇 i to evaporate the alcohol. 4. Place the quartz substrate containing the catalyst in a quartz reaction tube, and pass gas (helium, argon and acetylene) to set the reaction temperature (65〇~8〇〇°c) and the gas flow rate (2 0~4). The carbon nanotube synthesis started after 0 m 1 / mi η). 5 · After reacting 3 0~1 2 0 m i ns, cool to room temperature and the product is a carbon nanotube (Multi-wal1 CNT). First Embodiment Synthesis of High Dielectric Epoxy/Carbon Nano Conductive Particle Composites 1. Take epoxy resin (Union Carbide Co., ERL 4221, 3, 4-epoxycyclohexylmethyl-3, 4-epoxy-cyclohexane-ca Rboxylate) 5.0g, hardener (MeHHPA,

Hexahydro-4-methylphthalic anhydride ) 5 · Og, catalyst (BDMA, N, N_dimethyl benzylamine) (K25g and solvent (according to the viscosity adjustment), stir at room temperature, then add carbon nanotubes 0.5~ lOphrs and dispersant (Brij56), ball milled for 12hrs 〇2. Pour the finished varnish into the mold frame and pump for 3hrs under high vacuum at 80 °C until no bubbles are formed.

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—1298339 V. INSTRUCTIONS (6) 3. Break the vacuum, remove the mold frame into a high temperature oven, pre-harden at 20 Torr for 20 mins, and then warm to 丨(9) to harden lhrs. 〆4·When the temperature is raised to room temperature, the hardened sheet is taken out, which is a high dielectric % oxy-resin/nanocarbon tube composite. The SEM image is shown in Fig. 2. 〆5 · According to the above method, conductive particles such as nanocarbon black and graphite (having an average particle diameter of carbon black of lOnm to 70 nm, and an average particle diameter of graphite of 8 〇〇 to 1 〇〇〇· instead of carbon nanotubes) are high. Preparation of Dielectric Epoxy Resin Composite Samples 0 6. The dielectric properties of the above samples were tested with the HP42 9 1A RF Impedance Meter under the condition of $ J. The results are shown in Table 1. The results are shown in the figure. Oxygen tree month's dielectric constant is higher than the addition force before = eve (generally, the dielectric constant of oxygen resin is between 3 and 4), Lu Xun carbon tube and carbon black, improve the dielectric effect Especially good. U 〃, is nano _

0424-9617TWF(nl);02910038;Renee.ptd Page 10 1298339 V. INSTRUCTIONS (7) Table 1 Dielectric constant of high dielectric ring bismuth resin/conductive particle composite

Epoxy carbon-based nano-conducting particles (phrs) Dk (1MHz) Dk (30MHz) Dk (100MHz) E 4221 — 3.2 3.0 3.0 E 4221 Carbon nanotubes (0.5) 188 31 13 E 4221 Carbon nanotubes (2.5) 353 230 123 E 4221 Carbon nanotubes (5. 〇) 484 361 263 E 4221 Carbon black (Carbot 2000) (1.0) 188 50 15 E 4221 Carbon black (Carbot 2000) (5.0) 737 386 173 E 4221 Carbon black (Degussa XE2B) (5.0) 236 215 145 E 4221 Graphite (Aldrich) (5.0) 11 5.9 5.0 Second Embodiment High Dielectric Epoxy/Carbon Nano Conductive Particles/Ceramic Particle Composite

0424-9617IW(nl) ;02910038;Renee.ptd Page 11 1298339 V. Description of Invention (8) 1. Take epoxy resin (Union Carbide Co, ERL 4221, 3, 4-epoxycyclohexylmethyl-3, 4-epoxy -cyclohexane~ca rboxylate) 5.0g, hardener (MeHHPA,

Hexahydro-4-methy 1phtha1ic anhydride) 5. Og, catalyst (BDMA, N, N-dimethyl benzylamine) 0.25g and solvent (according to the viscosity adjustment) at room temperature, evenly add nano carbon Tube 0·5~5phrs with dielectric ceramic particles 1 〇~6〇ν〇ι% (pottery type and amount of pottery as shown in Table 2) ball milled to mix 1 2 hrs. 2. Pour the finished raw glue water (v a r n i s h) into the mold frame and draw 3 h r s ' under a vacuum of 8 〇 C until no bubbles are formed. 3 · Break the vacuum and remove the mold frame into the high temperature oven at 丨2 〇. The underarm is precured for 20 mins and then warmed to 16 Torr. It hardens for 1 hrs. 4 · Waiting for warming to room temperature 'The plate is taken out as a high dielectric epoxy/carbon nanotube/ceramic particle composite. The SEM image is shown in Figure 3. 5. The dielectric ceramic particles shown in Table 2 have an average particle diameter of between 100 nm and 1500 nm. 6. The dielectric properties of the above samples were tested under normal temperature and pressure using an HP42 9 1 A RF impedance meter. The results are shown in Table 2. As a result, it was revealed that the epoxy resin of the carbon-based nano-conductive particles had a much larger dielectric constant than that before the addition.

1298339_ V. INSTRUCTIONS (9) Table 2 High dielectric ring tantalum resin/carbon-based nano-conducting particles/dielectric ceramic particle composite dielectric constant carbon-based nano Dk Epoxy conductive grain ceramic particle Dk (30MHz) Dk (vol%) (1MHz) (100MHz) (phrs) E 4221 - — 3.2 3.0 3.0 PMN 8.6 E 4221 - (20) S.8 8.5 BaTi03 11.7 E 4221 - (20) 12.2 11.6 E 4221 CNT(5) PMN 127 69.0 42.6 (20) E 4221 CNT (5) PMN 315 46.4 29.2 (30) E 4221 CNT (5) BaTi03 402 88.0 44.9 (20) Although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the present invention. The invention is to be understood as being limited by the scope of the appended claims.

1298339 BRIEF DESCRIPTION OF THE DRAWINGS The first drawing shows a conventional discrete substrate. Figure 1 b shows an integrated substrate. Fig. 2 is an SEM image of the high dielectric epoxy/nanocarbon nanotube composite obtained in the first embodiment. Figure 3 is an SEM image of the high dielectric epoxy/nanocarbon tube/ceramic particle composite obtained in the second embodiment. DESCRIPTION OF SYMBOLS 1~substrate; R~resistive element L~inductive element C~capacitive element 1C~Integrated circuit

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Claims (1)

,::3⁄4 Thai 1298339 'lu? VI. Patent application scope ' . . --------_ ' 1 · A high dielectric constant nanocapacitor (embedded Capacitor) material, suitable for a built-in electro-polymer substrate; a coating comprising: a carbon-based nano-conductive particle distributed, a dielectric ceramic particle distributed in the substrate, and a dielectric of the composite In the constant two sub-substrate, such as by biting straight and smashing; the frequency of 1MHz is more than 1〇〇. 2 · As in the material of the first paragraph of the patent application, JL is an ancient eight-worker m, described as a high dielectric constant nanocomposite, in which the molecular substrate of the same molecule is thermoset 3 · as claimed in the first item '曰—Materials, in which the polymer substrate is produced. L's two '丨 electric hanging number nano composite grease, cyanic acid vinegar resin, polydimethyl hydrazine resin, poly-branched amine, ^ tree / , ^ ^ # A coil of gas resin or a combination thereof. 4 · If the patent application scope is 1 Jg Θ Ψ β π $ a 1 member of the high dielectric constant nanocomposite # > +, # si ^ V electric tweezers are carbon nanotubes, nano carbon spheres, Stone anti-60, anti-black, graphite or a combination thereof. 5 · For example, the first item of the patent scope of the application is from the dielectric constant nanocomposite of the 咼 所述 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ For 0.5] 〇Phrs. 6 · For the δ month patent range 1 ^ +4-, i Φ ^ ^ ^ ^ ^ The high dielectric constant nanocomposite ^ η ^ , , , , . . . is lead magnesium bismuth, barium titanate , cerium oxide, emulsified, emulsified titanium or a combination thereof. 7 · As claimed in the patent application, the high dielectric constant nanocomposite crucible described in 苴Φ兮八Φf, wherein the dielectric ceramic particle contains 8. As claimed in the first paragraph ιρ3: + is 0~6〇V〇1%. # ^i φ β Α φ > The high dielectric constant nanocomposite described by the younger brother p, + + has a particle size between 1 00 nm and 1 500 nm. 0424-9617TWF(nl);02910038;Renee.ptd Page 15 1298339 The built-in embedded capacitor includes: a substrate; a genus layer formed on the substrate; On the first metal layer, wherein the nano-refill material layer has a dielectric constant of 1 〇〇 or more, and at least one high-material bismuth and stone ruthenium-containing conductive particles are distributed in the polymer substrate; And a second metal layer is formed over the nano composite layer. 10. The built-in capacitor of claim 9, wherein the substrate is a germanium substrate or a copper foil substrate. [11] The built-in capacitor of claim 9, wherein the polymer substrate is a thermosetting resin. 1 2 · The built-in capacitor according to claim 9 wherein the polymer substrate is epoxy resin, polyamine, BT resin, cyanate resin, polydimethyl phenoxy resin Or a combination thereof. 1 3 The built-in capacitor of claim 9, wherein the stone counter-anoe conductive particles are carbon nanotubes, carbon spheres, carbon sixty, carbon black, graphite or a combination thereof. 1 4 - The built-in electric valley as described in claim 9 wherein the conductive material content of the stone is ～10 phrs. 1 5 The built-in capacitor as described in claim 9 further includes a dielectric ceramic particle distributed in the polymer substrate. 1 6. The built-in capacitor as described in claim 5, wherein the dielectric ceramic particles are lead magnesium bismuth, barium titanate, cerium oxide, aluminum oxide, oxygen 1298339__ VI. Application for patent scope Titanium or a combination thereof. 1 7. The built-in capacitor of claim 15, wherein the dielectric ceramic particle content is 0 to 60 vol%. 1 8. The built-in capacitor of claim 15 wherein the dielectric ceramic particles have a particle size between 100 nm and 1500 nm. 0424-9617TWF(nl);02910038;Renee.ptd Page 17