CN105198491A - Method for preparing ceramic substrate containing conductive copper cylinder - Google Patents

Method for preparing ceramic substrate containing conductive copper cylinder Download PDF

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Publication number
CN105198491A
CN105198491A CN201510583151.9A CN201510583151A CN105198491A CN 105198491 A CN105198491 A CN 105198491A CN 201510583151 A CN201510583151 A CN 201510583151A CN 105198491 A CN105198491 A CN 105198491A
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ceramic substrate
nano
hole
conducting film
technology
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CN201510583151.9A
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CN105198491B (en
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陈明祥
刘松坡
程浩
陈珍
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Polytron Technologies Inc of Wuhan
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Wuhan Lizhida Science & Technology Co Ltd
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Abstract

The invention provides a method for preparing a ceramic substrate containing a conductive copper cylinder. The method includes the steps that first, through holes are prepared in the ceramic substrate through a laser boring technology; then a metal seed layer is deposited on the surface of the substrate through a sputtering technology, and the thickness of the seed layer is increased through electroplating; afterwards, the substrate is soaked in a wall bracing solution made of a carbon nanomaterial, and a conducting film is formed on each hole wall under the action of ultrasound or jet; at last, the ceramic substrate with the surface being provided with a metal circuit and internally provided with the conductive copper cylinder is prepared through the pattern electroplating and corrosion technology. Due to the facts that the carbon nanomaterial is good in electricity-conducting and heat-conducting property and the binding force of the carbon nanomaterial and ceramic is high, the performance and reliability of the ceramic substrate are improved. Meanwhile, the nanocarbon wall bracing technology is adopted for preparing the conductive copper cylinder. Compared with an existing chemical plating and conducting polymer hole-filling technology, the method has the advantages of being simple in technology, environmentally friendly in material, low in cost, suitable for mass production and the like.

Description

A kind of ceramic substrate preparation method containing conduction copper column
Technical field
The invention belongs to electronic manufacturing field, particularly a kind of ceramic substrate preparation method containing conduction copper column.
Background technology
Along with three-dimensional packaging technology development and level of integrated system improve, be in the power device manufacturing processed of representative with large-power light-emitting diodes (LED), igbt (IGBT), laser diode (LD) etc., the preparation of heat-radiating substrate and select and become crucial sport technique segment, and directly have influence on use properties and the reliability of device.For high power LED device, the 70%-80% due to input electric power changes heat (only having about 20%-30% to be converted into luminous energy) into, and LED chip area is little, and device power density (is greater than 100W/cm very greatly 2), therefore heat radiation becomes the gordian technique that high-power LED encapsulation must solve.If can not in time chip heating be derived and be dissipated, amount of heat will be gathered in LED inside, junction temperature of chip will progressively raise, LED performance is made to reduce (as luminous efficiency reduction, red shift of wavelength etc.) on the one hand, thermal stresses will be produced in LED body on the other hand, cause a series of integrity problem (as service life reduction, colour temperature change etc.).
For power electronic device encapsulation, substrate, except possessing basic support, wiring (electrical interconnection) function, also requires to have higher heat conduction, insulation, high temperature resistant, proof voltage ability and thermal matching energy.Heat-radiating substrate conventional is at present TFC (thick film ceramic substrate), DBC (Direct Bonding ceramic substrate) and DPC (Direct Electroplating ceramic substrate).Wherein, TFC adopts silk screen printing and high-sintering process to prepare, and cost is lower, but circuit low precision (being greater than 0.2mm), and be difficult to prepare conduction copper column structure; And DBC by Copper Foil and ceramic plate at high temperature eutectic sinter and form, finally according to cabling requirement, form interconnection line with etching mode.Have interface bond strength high, electric current leads to the advantages such as loading capability is large, is applicable to very much IGBT device encapsulation requirement.But due to preparation process make use of high temperature under the eutectic reaction of (being greater than 1000 DEG C), higher to equipment and process control overflow, production cost is higher, also cannot prepare conduction copper column structure.
DPC substrate preparation technology flow process as shown in Figure 1, is characterized in the Seed Layer adopting sputter coating to electroplate as ceramic surface, adopts electroless copper as the Seed Layer of electroplating in ceramic hole.First this technique utilize laser drilling to form through hole on a ceramic substrate, then adopt sputter coating mode in ceramic substrate surface metal refining Seed Layer, then the via hole is realized with electroless plating, graphic making is completed by photoetching, developing process, increase copper layer thickness and filling perforation with plating mode, make finally by removing photoresist and corroding Seed Layer completing substrate.Because DPC preparation have employed semiconductor fabrication, there is the advantages such as technological temperature is low, circuit is meticulous, and conductive and heat-conductive copper post can be prepared on ceramic substrate, be very applicable to the high-power LED encapsulation demand that alignment precision is high, integration density is high.
As shown in Figure 2, it adopts conductive paste directly to fill ceramic endoporus to existing DPC (conductive paste filling perforation) preparation technology's flow process, is prepared by graphic plating completing substrate.
Key prepared by DPC substrate is conduction copper column preparation.General employing laser drilling forms through hole on a ceramic substrate, then adopts electro-coppering to fill, and realizes the interconnection and interflow (conduction and heat conduction) of ceramic substrate upper and lower surface.But because pottery is isolator, could realize electroplating filling perforation after hole wall must be made to conduct electricity.Technical scheme conventional at present comprises: 1) adopt magnetron sputtering technique at hole wall Direct precipitation metal.But the straight hole that, aspect ratio less for aperture is larger, cannot realize all standing of hole wall metal level, make electro-coppering structure in hole discontinuous, be difficult to realize interconnection; 2) electroless plating technology is adopted to realize the via hole, as shown in Figure 1.Shortcoming is that chemical plating technology is complicated, three-waste pollution serious (reductive agent formaldehyde is harmful to), and use is very limited; 3) conductive polymers (as conductive paste or conductive resin) directly filling vias is adopted, as Fig. 2.Shortcoming is filling small hole difficulty, need be heating and curing (sintering), and the electrical and thermal conductivity performance of weighting material is poor after filling perforation.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, propose a kind of ceramic substrate preparation method containing conduction copper column, this ceramic substrate has the advantages that yield rate is high and reliability is strong.
A kind of ceramic substrate preparation method containing conduction copper column provided by the invention, first be by laser boring and the solid wall liquid that preparation has the ceramic substrate of Seed Layer to be placed in nano-carbon material prepares, take out flood for some time under ultrasonication after and dry, ceramic hole wall forms conducting film; Finally by graphic plating and etching process, prepare surperficial containing metal circuit, the inner ceramic substrate containing conduction copper column.
The present invention adopts nano-carbon material wall bracing technology to substitute traditional chemical-copper-plating process, and the conducting film utilizing physical action to be formed directly is electroplated, and prepares the ceramic substrate containing conduction copper column.Due to the conducting film excellent property that nano-carbon material wall bracing technology is formed, make a concerted effort strong, improve ceramic substrate yield rate and reliability with ceramic junction, and technique is simple, material environment friendly, cost is low.
Accompanying drawing explanation
Fig. 1 is existing DPC substrate preparation technology schema (electroless plating filling perforation).
Fig. 2 is existing DPC substrate preparation technology schema (conductive paste filling perforation).
Fig. 3 is DPC ceramic substrate preparation technology schema (nano-sized carbon Gu Bi process) of the present invention.
Fig. 4 is the solid wall process flow sheet of nano-carbon material of the present invention.
Fig. 5 is nano-carbon material wall bracing technology schematic diagram of the present invention.Wherein 51 is ceramic substrate, and 52 is ceramic through hole, and 53 is metal seed layer, and 54 is nano-carbon layer (conducting film), and 55 is metallic circuit layer, and 56 is electro-coppering post.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.It should be noted that at this, the explanation for these embodiments understands the present invention for helping, but does not form limitation of the invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
As shown in Figure 3, DPC ceramic substrate preparation method flow process provided by the invention is as follows: first adopt laser drilling prepare through hole on a ceramic substrate and carry out ultrasonic cleaning, again by sputtering technology in substrate surface and aperture metal refining Seed Layer, and by plating increase seed layer thickness to 2-5 micron; Then utilize nano-carbon material to carry out Gu Bi process and form conducting film (as Figure 4 and 5) at hole wall; Obtain the ceramic substrate of band conducting film through hole; The ceramic substrate of containing metal circuit and conduction copper column is prepared finally by graphic plating (pasting dry film, photoetching, development and plating) and etching process (etching Seed Layer).
The process forming conducting film at hole wall by nano-carbon material wall bracing technology is described as follows:
Ceramic substrate after laser boring is placed in the solid wall liquid of nano-carbon material preparation, takes out flood for some time under ultrasonication after and dry, ceramic hole wall forms conducting film.
Described nano-carbon material is Graphene, nano graphite flakes, nano-carbon powder or its mixture etc.; The characteristic dimension (sheet thickness or particle diameter) of nano-carbon material is less than or equal to 300nm, and preferable range is 1.0-100.0nm; Described solid wall liquid is made up of nano-carbon material, deionized water and tensio-active agent, and wherein the quality of nano-carbon material is 1.0-5.0% than content; Described solid wall liquid pH value is 9.5-10.5, is regulated by sodium hydroxide or ammoniacal liquor; Described tensio-active agent can select Sodium dodecylbenzene sulfonate, alkyl phosphorus carboxylate salt or Sodium hexametaphosphate 99 etc., and its volume ratio content is 0.1-1.0%; The described ultrasonic immersing time is 3-5 minute, and bake out temperature is 50-70 DEG C.
Described Ceramic Substrate Material is aluminum oxide, aluminium nitride, beryllium oxide, silicon carbide etc.; Described through-hole diameter is 50-200um.
Example:
Embodiment 1
The present embodiment treatment step is:
1) punch: adopt laser apparatus to prepare the array through-hole that diameter is 100um on alumina ceramic substrate (thickness is 0.5mm);
2) pre-treatment: by ceramic substrate ultrasonic cleaning 5 minutes in deionized water, acetone, ethanolic soln successively, dry up post-drying (100 DEG C, 30 minutes);
3) sputter coating: ceramic substrate is placed in coating equipment, deposits 200nm titanium (Ti) and 200nm copper (Cu) as Seed Layer by sputtering technology successively at substrate surface;
4) plating thickens: adopt electric plating of whole board copper technology, make seed layer thickness increase to 3 μm;
5) the solid wall liquid of configuration: 1 gram of Graphene, 100 grams of deionized waters, 1ml Sodium hexametaphosphate 99s being uniformly mixed, is 10.0 by potassium hydroxide regulator solution pH value;
6) Gu Bi: ceramic substrate is put into solid wall liquid, take out under ultrasonication after room temperature immersion 3min, dries at 50 ~ 60 DEG C;
7) microcorrosion: ceramic substrate is placed in the Sodium Persulfate solution of 5%, removes by the injection of solution and corrosive nature the Graphene that ceramic surface copper film adsorbs;
8) graphic plating and filling perforation: by thickness be the dry film laminating of 50um on a ceramic substrate, realize graphical, then make copper layer thickness be increased to 35um by plating by exposure, developing process, and realize filling perforation;
9) remove photoresist and corrosion: adopt 10% potassium hydroxide solution to remove remaining dry film glue, and adopt sulphuric acid soln to corrode residual Seed Layer;
10) surface treatment: adopt Electroless Silver Plating at layers of copper surface deposition 3um silver layer, is finally placed in 1% oxidation resistance liquid and soaks 3 minutes, dry rear for subsequent use by substrate.
Embodiment 2:
The present embodiment treatment step is:
1) punch: adopt laser apparatus to prepare the array through-hole that diameter is 200um on aluminium nitride ceramic substrate (thickness is 1.0mm);
2) pre-treatment: by ceramic substrate ultrasonic cleaning 5 minutes in deionized water, acetone, ethanolic soln successively, dry up post-drying (100 DEG C, 30 minutes);
3) sputter coating: ceramic substrate is placed in coating equipment, deposits 100nm titanium (Ti) and 200nm copper (Cu) as Seed Layer by sputtering technology successively at substrate surface;
4) plating thickens: adopt electric plating of whole board copper technology, make seed layer thickness be increased to 5 μm;
5) the solid wall liquid of configuration: 3 grams of nano graphite flakes, 100 grams of deionized waters, 2ml alkyl phosphorus carboxylic acid sodium being uniformly mixed, is 10.5 by ammoniacal liquor regulator solution pH value;
6) Gu Bi: ceramic substrate is put into solid wall liquid, take out under ultrasonication after room temperature immersion 5min, dries at 50 ~ 60 DEG C;
7) microcorrosion: ceramic substrate is placed in the Sodium Persulfate solution of 10.0%, removes by the injection of solution and corrosive nature the graphite flake that ceramic surface copper film adsorbs;
8) graphic plating and filling perforation: by thickness be the dry film laminating of 100um on a ceramic substrate, realize graphical, then make copper layer thickness be increased to 80um by plating by exposure, developing process, and realize filling perforation;
9) remove photoresist and corrosion: adopt 10% potassium hydroxide solution to remove remaining dry film glue, and adopt sulphuric acid soln to corrode residual Seed Layer;
10) surface treatment: adopt chemical nickel and gold (NiAu) technique successively in layers of copper surface deposition 3um nickel dam and 0.1um layer gold, rinsing is for subsequent use after drying.
Embodiment 3:
The present embodiment treatment step is:
1) punch: adopt laser apparatus to prepare the array through-hole that diameter is 50um on beryllium oxide ceramics substrate (thickness is 0.38mm);
2) pre-treatment: by ceramic substrate ultrasonic cleaning 5 minutes in deionized water, acetone, ethanolic soln successively, dry up post-drying (100 DEG C, 30 minutes);
3) sputter coating: ceramic substrate is placed in coating equipment, deposits 100nm titanium (Ti) and 200nm copper (Cu) as Seed Layer by sputtering technology successively at substrate surface;
4) plating thickens: adopt electric plating of whole board copper technology, make seed layer thickness be increased to 2 μm;
5) the solid wall liquid of configuration: 5 grams of nano-carbon powders, 100 grams of deionized waters, 3ml Sodium dodecylbenzene sulfonatees being uniformly mixed, is 9.5 by potassium hydroxide regulator solution pH value;
6) Gu Bi: ceramic substrate is put into solid wall liquid, take out under ultrasonication after room temperature immersion 3min, dries at 50 ~ 60 DEG C;
7) microcorrosion: ceramic substrate is placed in the Sodium Persulfate solution of 10.0%, removes by the injection of solution and corrosive nature the nano-carbon powder that ceramic surface copper film adsorbs;
8) graphic plating and filling perforation: by thickness be the dry film laminating of 60um on a ceramic substrate, realize graphical, then make copper layer thickness be increased to 30um by plating by exposure, developing process, and realize filling perforation;
9) remove photoresist and corrosion: adopt 10% potassium hydroxide solution to remove remaining dry film glue, and adopt sulphuric acid soln to corrode residual Seed Layer;
10) surface treatment: adopt Electroless Silver Plating at layers of copper surface deposition 2um silver layer, is finally placed in 1% oxidation resistance liquid and soaks 3 minutes, dry rear for subsequent use by substrate.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the content disclosed in this embodiment and accompanying drawing.The equivalence completed under not departing from spirit disclosed in this invention so every or amendment, all fall into the scope of protection of the invention.

Claims (10)

1. prepare the method for band conducting film through hole on a ceramic substrate for one kind, the method is by laser boring and preparation has the ceramic substrate of Seed Layer to be placed in the solid wall liquid of nano-carbon material preparation, take out flood for some time under ultrasonication after and dry, ceramic hole wall forms conducting film.
2. a kind of method preparing band conducting film through hole on a ceramic substrate as claimed in claim 1, it is characterized in that, described nano-carbon material is Graphene, nano graphite flakes, nano-carbon powder or its mixture, and its characteristic dimension is less than or equal to 300nm, and optimal size is 1.0nm-100.0nm.
3. a kind of method preparing band conducting film through hole on a ceramic substrate as claimed in claim 1, it is characterized in that, described solid wall liquid is made up of nano-carbon material, deionized water and tensio-active agent, wherein the mass content of nano-carbon material is 1.0-5.0%, and the volume ratio content of tensio-active agent is 0.1-1.0%.
4. a kind of method preparing band conducting film through hole on a ceramic substrate as claimed in claim 1, it is characterized in that, described solid wall liquid pH value is 9.5-10.5, is regulated by sodium hydroxide or ammoniacal liquor.
5. a kind of method preparing band conducting film through hole on a ceramic substrate as claimed in claim 1, it is characterized in that, the described ultrasonic immersing time is 3-5 minute, and bake out temperature is 50-70 DEG C, and described seed layer thickness is 2.0-5.0um.
6. a kind of method preparing band conducting film through hole on a ceramic substrate as claimed in claim 3, it is characterized in that, described tensio-active agent is Sodium dodecylbenzene sulfonate, alkyl phosphorus carboxylate salt or Sodium hexametaphosphate 99.
7. the ceramic substrate preparation method containing conduction copper column, first laser boring is also prepared the solid wall liquid having the ceramic substrate of Seed Layer to be placed in nano-carbon material preparation, take out flood for some time under ultrasonication after and dry, ceramic hole wall forms conducting film; Finally by graphic plating and etching process, prepare surperficial containing metal circuit, the inner ceramic substrate containing conduction copper column.
8. a kind of ceramic substrate preparation method containing conduction copper column as claimed in claim 7, it is characterized in that, described Ceramic Substrate Material is aluminum oxide, aluminium nitride, beryllium oxide or silicon carbide, and described conduction copper column and through-hole diameter are 50-200um.
9. a kind of ceramic substrate preparation method containing conduction copper column as claimed in claim 7, it is characterized in that, described solid wall liquid is made up of nano-carbon material, deionized water and tensio-active agent, wherein the mass content of nano-carbon material is 1.0-5.0%, the volume ratio content of tensio-active agent is 0.1-1.0%, described solid wall liquid pH value is 9.5-10.5, is regulated by sodium hydroxide or ammoniacal liquor.
10. a kind of ceramic substrate preparation method containing conduction copper column as claimed in claim 9, it is characterized in that, described tensio-active agent is Sodium dodecylbenzene sulfonate, alkyl phosphorus carboxylate salt or Sodium hexametaphosphate 99, the described ultrasonic immersing time is 3-5 minute, bake out temperature is 50-70 DEG C, and described seed layer thickness is 2.0-5.0um.
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Cited By (8)

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CN106017515A (en) * 2016-05-28 2016-10-12 惠州市力道电子材料有限公司 Double-face interdigital electrode, and processing method and application thereof
CN106129240A (en) * 2016-08-05 2016-11-16 江苏新宝玛光电制造有限公司 High-power LED chip based on Graphene material and COB method for packing thereof
TWI618821B (en) * 2017-04-21 2018-03-21 萬億股份有限公司 Method for manufacturing traces of pcb
CN108323003A (en) * 2018-01-24 2018-07-24 深圳市牧泰莱电路技术有限公司 A kind of ceramic circuit-board and its manufacturing method with plated-through hole
CN108774052A (en) * 2018-06-11 2018-11-09 三峡大学 A kind of graphite containing graphene/ceramics conducing composite material and preparation method thereof
CN108950496A (en) * 2018-08-22 2018-12-07 广州鸿葳科技股份有限公司 A kind of surface treatment method and its application based on the 5G communication technology with ceramic resonance body
CN113161738A (en) * 2021-05-25 2021-07-23 中国电子科技集团公司第二十九研究所 Preparation method of low-frequency broadband curved surface circuit
CN114434894A (en) * 2022-02-21 2022-05-06 江西柔顺科技有限公司 Copper foil graphite film and preparation method thereof

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CN103413791A (en) * 2013-08-22 2013-11-27 广州天极电子科技有限公司 Ceramic copper-coated film heat sink module with good heat dissipation efficiency and manufacturing method thereof
CN104661449A (en) * 2015-02-16 2015-05-27 珠海元盛电子科技股份有限公司 Hole metallization method based on laser activation technology
CN104735914A (en) * 2015-04-15 2015-06-24 遂宁市英创力电子科技有限公司 Method for using AlN ceramic substrate to produce circuit board

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CN102695370A (en) * 2012-06-18 2012-09-26 惠州市富济电子材料有限公司 Preparation method of ceramic circuit board
CN103413791A (en) * 2013-08-22 2013-11-27 广州天极电子科技有限公司 Ceramic copper-coated film heat sink module with good heat dissipation efficiency and manufacturing method thereof
CN104661449A (en) * 2015-02-16 2015-05-27 珠海元盛电子科技股份有限公司 Hole metallization method based on laser activation technology
CN104735914A (en) * 2015-04-15 2015-06-24 遂宁市英创力电子科技有限公司 Method for using AlN ceramic substrate to produce circuit board

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106017515A (en) * 2016-05-28 2016-10-12 惠州市力道电子材料有限公司 Double-face interdigital electrode, and processing method and application thereof
CN106129240A (en) * 2016-08-05 2016-11-16 江苏新宝玛光电制造有限公司 High-power LED chip based on Graphene material and COB method for packing thereof
CN106129240B (en) * 2016-08-05 2019-04-16 江苏新宝玛光电制造有限公司 High-power LED chip and its COB packaging method based on graphene material
TWI618821B (en) * 2017-04-21 2018-03-21 萬億股份有限公司 Method for manufacturing traces of pcb
US10306768B2 (en) 2017-04-21 2019-05-28 Triallian Corporation Method for manufacturing traces of PCB
CN108323003A (en) * 2018-01-24 2018-07-24 深圳市牧泰莱电路技术有限公司 A kind of ceramic circuit-board and its manufacturing method with plated-through hole
CN108774052A (en) * 2018-06-11 2018-11-09 三峡大学 A kind of graphite containing graphene/ceramics conducing composite material and preparation method thereof
CN108774052B (en) * 2018-06-11 2020-11-20 三峡大学 Graphene-containing graphite/ceramic conductive composite material and preparation method thereof
CN108950496A (en) * 2018-08-22 2018-12-07 广州鸿葳科技股份有限公司 A kind of surface treatment method and its application based on the 5G communication technology with ceramic resonance body
CN113161738A (en) * 2021-05-25 2021-07-23 中国电子科技集团公司第二十九研究所 Preparation method of low-frequency broadband curved surface circuit
CN113161738B (en) * 2021-05-25 2021-08-31 中国电子科技集团公司第二十九研究所 Preparation method of low-frequency broadband curved surface circuit
CN114434894A (en) * 2022-02-21 2022-05-06 江西柔顺科技有限公司 Copper foil graphite film and preparation method thereof

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Address after: 430000 Hubei Wuhan Wuhan East Lake hi tech Zone Four Road 40 Gezhouba Dam Sun City 23 103

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Denomination of invention: A preparation method of ceramic substrate containing conductive copper column

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