CN112687787B - Manufacturing method of polycrystal series LED copper alloy bonding wire - Google Patents
Manufacturing method of polycrystal series LED copper alloy bonding wire Download PDFInfo
- Publication number
- CN112687787B CN112687787B CN202011589273.6A CN202011589273A CN112687787B CN 112687787 B CN112687787 B CN 112687787B CN 202011589273 A CN202011589273 A CN 202011589273A CN 112687787 B CN112687787 B CN 112687787B
- Authority
- CN
- China
- Prior art keywords
- copper
- tungsten
- powder
- ball milling
- diameter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
A manufacturing method of a polycrystal series LED copper alloy bonding wire is characterized in that a base material is prepared by a powder ball milling method, and after heat treatment, the base material is drawn by a wire drawing machine.
Description
Technical Field
The invention belongs to the technical field of semiconductor materials, and particularly relates to a manufacturing method of a polycrystal series LED copper alloy bonding wire.
Background
The bonding lead has the function of connecting the silicon chip electrode with the external leading-out terminal of the lead frame, transmits the electric signal of the chip and radiates the heat generated in the chip, and is a key material for packaging the integrated circuit. Wire bonding is a focused manifestation of the extremely small feature sizes and the extremely large yields of semiconductor production, with the former being manifested in ever decreasing wire spacing and the latter being manifested in progressively increasing production efficiency. The fine pitch bonding requires a connecting wire with higher strength and rigidity, the length of a Free Air Ball (Free Air Ball) and a heat affected zone (heat affected zone) is controlled to meet the requirement of the fine pitch bonding, higher and higher requirements are provided for the technical indexes of the bonding wire in the large-scale integrated circuit and LED packaging, the demand of high-performance and ultra-fine bonding wires is rapidly increased, the density of a chip is continuously improved, higher requirements are provided for the reliability of bonding materials, the bonding wire (a bonding alloy wire, a bonding copper wire, a bonding alloy wire and the like) plays a role in connecting a silicon chip electrode and an external leading-out terminal of a lead frame, transmits an electric signal of the chip and emits heat generated in the chip, and the fine pitch bonding wire is a key material for packaging the integrated circuit. The bonding silver wire and the bonding silver alloy wire are used in microelectronic packaging, especially in LED packaging, due to their excellent electrical properties (such as reduction of high-frequency noise of devices, reduction of heat generation of high-power LEDs, etc.), good stability and appropriate cost factors. The pure copper or copper alloy wires used at present are all made by a chemical method, so that the efficiency is low and the conductivity is poor.
Disclosure of Invention
The invention mainly discloses a method for manufacturing a polycrystal series connection LED copper alloy bonding wire, which mainly comprises a substrate manufacturing stage and a wire drawing stage.
A substrate manufacturing stage:
a manufacturing method of a polycrystal series LED copper alloy bonding wire mainly comprises the following steps:
s1, preparing nanocrystalline copper powder and nanocrystalline tungsten powder, wherein the diameter of the nanocrystalline copper powder is not more than 2.0 microns, and the diameter of the nanocrystalline tungsten powder is not more than 1.0 micron;
s2, mixing the nano-crystalline copper powder and the nano-crystalline tungsten powder in a proportion of 7: 3, putting the mixture into a ball mill for ball milling, wherein the main rotating speed of the ball mill is controlled at 350r/min, and the ball-to-material ratio in the ball mill is 7: 1;
s3, adding absolute ethyl alcohol as a ball milling medium in the ball milling process, wherein the volume ratio of the total amount of the nano-crystal copper powder and the nano-crystal tungsten powder to the total amount of the absolute ethyl alcohol is 50:1, and the total ball milling time is 24H;
s4: after the ball milling is finished, putting the powder into a drying box for drying, wherein the drying temperature is 150-;
s5, after drying, placing the powder into a cylindrical die, placing the die on a press machine for compaction, wherein the diameter of the bottom of the cylindrical die is 3cm, the height of the die is 10cm, and the pressure of the press machine on the top of the cylinder is more than 1.5T;
and S6, taking the compacted matrix out of the die, and sintering in a vacuum heating box at 1750 ℃ for 38.5 hours.
S7, cooling the copper-tungsten alloy rod with the diameter of 3cm and the height of 10cm, which is obtained by sintering, to room temperature, placing the copper-tungsten alloy rod in a heating furnace for heating for 1h at the heating temperature of 300 ℃ and 500 ℃, and cooling to room temperature again after heating;
a wire drawing stage:
s1: placing the copper-tungsten alloy rod in a roller press for rolling to form a copper-tungsten alloy rod with the diameter of 0.5 cm;
s2, drawing the 0.5cm alloy rod by using a wire drawing machine, wherein the die of the wire drawing machine is a die with the diameter of 0.1cm, unidirectional drawing is adopted in the wire drawing process, and the angle of the die is 13 degrees;
s3: placing the 0.1cm copper-tungsten alloy in a precision wire drawing machine for drawing for multiple times to obtain a copper-tungsten alloy bonding wire with the diameter of 0.011-0.015mm, wherein the deformation rate of the wire is 3-5% in the wire drawing process;
preferably, in the ball milling stage, the ball milling tank used in the ball mill is made of polyurethane material, and the material of the grinding balls in the ball milling tank is high-hardness ceramic.
Preferably, the drying box is filled with a protective gas.
Preferably, the copper-tungsten alloy rod is cooled by an oil bath during cooling to room temperature after sintering.
Preferably, the copper-tungsten alloy rod is cooled in a furnace cooling mode in the process of cooling to room temperature after heat treatment.
Compared with the prior art, the invention has the following characteristics: because the melting points and the physical properties of the copper material and the tungsten material are different, the base material is manufactured by adopting a ball milling method. The greater the interparticle attractive forces in the alloy, the greater the component forces acting on the particles, which makes the rearrangement of the particles proceed more rapidly. In addition, because the powder is fine and has a large specific surface area, the surface activity and the lattice activity are simultaneously increased, which is more beneficial to the sintering. The alloy has good electric and thermal conductivity.
Drawings
FIG. 1 is an image of tungsten copper powder upon ball milling for 10H.
FIG. 2 is an image of tungsten copper powder upon ball milling for 24H.
Fig. 3 is an image of tungsten copper powder upon ball milling for 36H.
FIG. 4 is a graph of densification as a function of soak time after sintering at 1750 degrees.
Fig. 5 shows the morphology of the voids formed inside the tungsten particles after sintering.
Fig. 6 shows the structure inside the material after the copper has been heavily evaporated.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
EXAMPLE 1
A manufacturing method of a polycrystal series LED copper alloy bonding wire mainly comprises the following steps:
s1, preparing nano-crystal copper powder and nano-crystal tungsten powder, wherein the diameter of the nano-crystal copper powder is 1.8 microns, and the diameter of the nano-crystal tungsten powder is 0.8 microns.
S2, mixing the nanocrystalline copper powder and the nanocrystalline tungsten powder in a ratio of 7: 3, putting the mixture into a ball mill for ball milling, wherein the main rotating speed of the ball mill is controlled at 350r/min, and the ball-to-material ratio in the ball mill is 7: 1; in the ball milling stage, a ball milling tank used in the ball mill is made of polyurethane materials, and the grinding balls in the ball milling tank are made of high-hardness ceramics.
It should be noted that mechanical ball milling can effectively increase the solid powder content of the powder feed, improve the homogeneity of the powder charge, and promote densification of the solid phase sintering.
And S3, adding absolute ethyl alcohol as a ball milling medium in the ball milling process, wherein the volume ratio of the total amount of the nano-crystal copper powder and the nano-crystal tungsten powder to the total amount of the absolute ethyl alcohol is 50:1, and the total ball milling time is 24H. The anhydrous ethanol does not have chemical reactions affecting production needs, has a low boiling point, can volatilize in the drying process, is convenient to recover, and reduces cost input. The surface tension of the absolute ethyl alcohol liquid is also smaller, so that the powder is not agglomerated. Low cost, no toxicity and environment friendship.
S4: after the ball milling is finished, the powder is placed in a drying box for drying, and the drying box is filled with protective gas, so that unnecessary oxides generated with air in the drying process are avoided. The drying temperature is 150 ℃, and the drying time is 8 h.
It should be noted that, in the process of preparing the tungsten-copper alloy by using the ball milling process in the prior art, the acting force on the copper crystal cell surface and the tungsten crystal cell surface of the tungsten-copper alloy generated by using the ball milling method is small, so that the mechanical property of the generated alloy is poor.
The tungsten-copper powder ball-milled for 24h is smoother, finer in particle size and high in dispersity compared with tungsten-copper powder ball-milled for 10h, the mutual attraction among particles in the alloy is larger, the component force acting on the two particles is larger, and the particles are rearranged more quickly. In addition, the powder is fine, the specific surface area is large, the surface activity and the lattice activity are simultaneously increased, and the sintering process is facilitated.
And S5, after drying, placing the powder into a cylindrical die, placing the cylindrical die on a press machine for compaction, wherein the diameter of the bottom of the cylindrical die is 3cm, the height of the cylindrical die is 10cm, and the pressure of the press machine on the top of the cylinder is 3T. The pressure die can be removed after compacting the powder, which can be realized according to the prior art.
In addition, the detection shows that the copper content of the tungsten copper material obtained by sintering has concentration gradient in the material, and the copper content is lost under no pressure. The loss of copper increases the content of tungsten in the material which is actually sintered, and the higher the sintering temperature is, the longer the high-temperature heat preservation time is, the lower the content of copper is, thus leading to the reduction of the conductivity of the alloy.
The density of the sintered body is increased to some extent with the increase of the molding pressure. This is due to the fact that the increase in pressure increases the densification of the material during the third stage of pressing, i.e. if the pressure is increased beyond a certain value, and the pressing and friction forces on the powder are greater than the elastic stress, the particles will plastically deform to fill the powder gaps, and the density will increase further. On the other hand, because the nanocrystalline copper particles themselves have very large surface energy free energy, if the pressing pressure is further increased to enable the copper particles to be plastically deformed, the surface free energy of the nanocrystalline copper particles is further increased, the melting point of the nanocrystalline copper particles is further reduced, and the nanocrystalline copper particles can be infiltrated with the tungsten particles at a lower temperature to start the densification process of the material.
And S6, taking the compacted matrix out of the die, and sintering in a vacuum heating box at 1750 ℃ for 38.5 hours, wherein the temperature is kept at 1750 ℃ for 150 min. If the temperature and holding time exceed a certain level and the copper is greatly lost, the relative compactness of the material even exceeds 100 percent. For example, if the surface of the material is not sealed after vacuum sintering at 1400 ℃ and heat preservation for 5 hours, the sintering density can even reach 101.72%. The reason is that the high temperature is too high, and the high temperature heat preservation time is too long. The higher the density of the alloy, the higher the relative content of tungsten crystals and the poorer the conductivity of the metal. Therefore, as shown in fig. 4, it is found through experimental data that in the process of sintering at 1750 ℃, when the temperature is maintained for 150min after the alloy is heated to the highest temperature, the compactness of the alloy is in a stage where the alloy is not lost, and the distance between the copper alloy unit cell and the tungsten alloy unit cell is the closest, so that the cooled alloy has better conductivity.
After the prepared powder is pressed, molded and sintered, observation is carried out under a scanning electron microscope, and the observation shows that the sintering temperature of the material is higher than the melting point temperature of copper, the copper is melted and changed into a liquid phase during sintering, and the liquid copper can fully and uniformly infiltrate the tungsten framework due to the viscous flow of the liquid copper and the capillary force action among tungsten particles in the material, and meanwhile, the tungsten particles are rearranged and contacted with each other, and the copper in the sample is relatively and uniformly surrounded around the tungsten particles. It was also observed that the porosity in the sintered samples decreased with the time of ball milling. This results in an alloy with a greater number of tungsten and copper crystals. Prior art studies of the sintering principle of tungsten copper materials indicate that interparticle spacing and liquid phase volume are functions of the forces acting on the alloy particles. Let F be the connecting force between two particles by liquid phase bridging and obtain the following relationship:
F＝2πvrcosΥ-πr2△P
wherein v is the surface free energy of the liquid phase evaporation interface; Δ P is the liquid phase capillary pressure; γ, r are variables related to particle spacing and liquid phase volume. The above formula may be rewritten as F ═ F (D), where D is the interparticle distance of tungsten and is affected by the liquid phase volume V and the tungsten particle volume V0. When the liquid phase volume and the antenna are kept constant, F is reduced along with the increase of D. The smaller the tungsten particles are, the more uniform the distribution of the tungsten particles is, the smaller the D value is, the larger the F value is, and the more the tungsten particles are close to each other. Therefore, under the condition that the mixed powder is subjected to heat preservation for 150min after being compacted and the temperature is kept higher than the melting point (1083.4 ℃) of copper and lower than the melting point (3390 ℃) of tungsten, the densification process of the alloy is quicker to carry out, so that the alloy has better mechanical and electrical properties, better ductility and wire drawing capability.
And S7, cooling the sintered copper-tungsten alloy rod with the diameter of 3cm and the height of 10cm to room temperature in an oil bath cooling mode, then placing the copper-tungsten alloy rod in a heating furnace for heating for 1h at the heating temperature of 300 ℃, and cooling to room temperature again after heating is finished.
A wire drawing stage:
s1: placing the copper-tungsten alloy rod in a roller press for rolling to form a copper-tungsten alloy rod with the diameter of 0.5 cm;
s2, drawing the 0.5cm alloy rod by using a wire drawing machine, wherein the die of the wire drawing machine is a die with the diameter of 0.1cm, unidirectional drawing is adopted in the wire drawing process, and the angle of the die is 13 degrees;
s3: and (3) placing the 0.1cm copper-tungsten alloy in a precision wire drawing machine for drawing for multiple times, and obtaining a copper-tungsten alloy bonding wire with the diameter of 0.011-0.015, wherein the deformation rate of the wire is 3.36% in the wire drawing process.
EXAMPLE 2
1. A manufacturing method of a polycrystal series LED copper alloy bonding wire mainly comprises the following steps:
s1, preparing nano-crystal copper powder and nano-crystal tungsten powder, wherein the diameter of the nano-crystal copper powder is 0.8 micron, and the diameter of the nano-crystal tungsten powder is 0.5 micron.
S2, mixing the nanocrystalline copper powder and the nanocrystalline tungsten powder in a ratio of 7: 3, putting the mixture into a ball mill for ball milling, wherein the main rotating speed of the ball mill is controlled at 350r/min, and the ball-to-material ratio in the ball mill is 7: 1; in the ball milling stage, a ball milling tank used in the ball milling machine is made of polyurethane materials, and the grinding balls in the ball milling tank are made of high-hardness ceramics.
And S3, adding absolute ethyl alcohol as a ball milling medium in the ball milling process, wherein the volume ratio of the total amount of ball milling powder to the total amount of the absolute ethyl alcohol is 50:1, and the total ball milling time is 24H.
S4: and after the ball milling is finished, putting the powder into a drying oven for drying, wherein the drying oven is filled with protective gas, the drying temperature is 200 ℃, and the drying time is 8 hours.
And S5, after drying, placing the powder into a cylindrical die, placing the die on a press machine for compaction, wherein the diameter of the bottom of the cylindrical die is 3cm, the height of the die is 10cm, and the pressure of the press machine on the top of the cylinder is 5T.
And S6, taking the compacted matrix out of the die, and sintering in a vacuum heating box at 1750 ℃ for 38.5 hours. Wherein the temperature is kept for 150min at 1750 ℃.
And S5, cooling the sintered copper-tungsten alloy rod with the diameter of 3cm and the height of 10cm to room temperature by adopting an oil bath method, and then heating the copper-tungsten alloy rod in a heating furnace for 1h at the heating temperature of 400 ℃. And the heat treatment time is 4min, protective gas is introduced into the heating furnace for protection during the heat treatment, and the temperature is cooled to room temperature again after the heating is finished. And the copper-tungsten alloy rod is cooled in a furnace cooling mode in the process of cooling to room temperature after heat treatment.
A wire drawing stage:
s1: placing the copper-tungsten alloy rod in a roller press for rolling to form a copper-tungsten alloy rod with the diameter of 0.5 cm;
s2, drawing the 0.5cm alloy rod by using a wire drawing machine, wherein the die of the wire drawing machine is a die with the diameter of 0.1cm, unidirectional drawing is adopted in the wire drawing process, and the angle of the die is 13 degrees;
s3: and (3) placing the 0.1cm copper-tungsten alloy in a precision wire drawing machine for drawing for multiple times, and obtaining a copper-tungsten alloy bonding wire with the diameter of 0.011-0.015mm, wherein the deformation rate of the wire is 3.86% in the wire drawing process.
The invention is well implemented in accordance with the above-described embodiments. It should be noted that, based on the above structural design, in order to solve the same technical problems, even if some insubstantial modifications or colorings are made on the present invention, the adopted technical solution is still the same as the present invention, and therefore, the technical solution should be within the protection scope of the present invention.
Claims (5)
1. A manufacturing method of a polycrystal series LED copper alloy bonding wire is characterized in that: the method mainly comprises the following steps:
s1, preparing nanocrystalline copper powder and nanocrystalline tungsten powder, wherein the diameter of the nanocrystalline copper powder is not more than 2.0 microns, and the diameter of the nanocrystalline tungsten powder is not more than 1.0 micron;
s2, mixing the nanocrystalline copper powder and the nanocrystalline tungsten powder in a ratio of 7: 3, putting the mixture into a ball mill for ball milling and mixing, wherein the main rotating speed of the ball mill is controlled at 350r/min, and the ball-material ratio in the ball mill is 7: 1;
s3, adding absolute ethyl alcohol as a ball milling medium in the ball milling process, wherein the volume ratio of the total amount of the nano-crystal copper powder and the nano-crystal tungsten powder to the total amount of the absolute ethyl alcohol is 50:1, and the total ball milling time is 24H;
s4: after the ball milling is finished, putting the mixed powder into a drying box for drying, wherein the drying temperature is 150-;
s5, after drying, placing the mixed powder into a cylindrical die, placing the cylindrical die on a press machine for compaction, wherein the diameter of the bottom of the cylindrical die is 3cm, the height of the cylindrical die is 10cm, and the pressure of the press machine on the top of the cylinder is more than 1.5T;
s6, taking the compacted matrix out of the die, and then placing the compacted matrix in a vacuum heating box for sintering, wherein the sintering temperature is 1750 ℃, the sintering time is 38.5 hours, and the temperature is kept at 1750 ℃ for 150 min;
s7, cooling the copper-tungsten alloy rod with the diameter of 3cm and the height of 10cm, which is obtained by sintering, to room temperature, placing the copper-tungsten alloy rod in a heating furnace for heating for 1h at the heating temperature of 300 ℃ and 500 ℃, and cooling to room temperature again after heating;
a wire drawing stage:
s1: placing the copper-tungsten alloy rod in a roller press for rolling to form a copper-tungsten alloy rod with the diameter of 0.5 cm;
s2, drawing the 0.5cm alloy rod by using a wire drawing machine, wherein the die of the wire drawing machine is a die with the diameter of 0.1cm, unidirectional drawing is adopted in the wire drawing process, and the angle of the die is 13 degrees;
s3: and (3) placing the 0.1cm copper-tungsten alloy in a precision wire drawing machine for drawing for multiple times to obtain a copper-tungsten alloy bonding wire with the diameter of 0.011-0.015mm, wherein the deformation rate of the wire is 3-5% in the wire drawing process.
2. The method for manufacturing the copper alloy bonding wire of the polycrystalline series LED according to claim 1, wherein the method comprises the following steps: in the ball milling stage, a ball milling tank used in the ball mill is made of polyurethane materials, and the grinding balls in the ball milling tank are made of high-hardness ceramics.
3. The method for manufacturing the copper alloy bonding wire of the polycrystalline series LED according to claim 1, wherein the method comprises the following steps: the drying box is filled with protective gas.
4. The method for manufacturing the copper alloy bonding wire of the polycrystalline series LED according to claim 1, wherein the method comprises the following steps: and the copper-tungsten alloy rod is cooled by adopting an oil bath in the process of cooling to room temperature after sintering.
5. The method for manufacturing the copper alloy bonding wire of the polycrystalline series LED according to claim 1, wherein the method comprises the following steps: and cooling the copper-tungsten alloy rod in a furnace cooling mode in the process of cooling to room temperature after heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011589273.6A CN112687787B (en) | 2020-12-29 | 2020-12-29 | Manufacturing method of polycrystal series LED copper alloy bonding wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011589273.6A CN112687787B (en) | 2020-12-29 | 2020-12-29 | Manufacturing method of polycrystal series LED copper alloy bonding wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112687787A CN112687787A (en) | 2021-04-20 |
| CN112687787B true CN112687787B (en) | 2022-08-16 |
Family
ID=75454877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011589273.6A Active CN112687787B (en) | 2020-12-29 | 2020-12-29 | Manufacturing method of polycrystal series LED copper alloy bonding wire |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112687787B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329956A (en) * | 1995-11-17 | 2002-01-09 | 奥斯兰姆施尔凡尼亚公司 | Tungsten-copper composite powder |
| CN1544673A (en) * | 2003-11-13 | 2004-11-10 | 北京科技大学 | Process for preparing W-Cu alloy by mechanical activation and chemical activation method |
| CN102500615A (en) * | 2011-10-21 | 2012-06-20 | 厦门虹鹭钨钼工业有限公司 | Method for manufacturing tungsten-copper alloy rods and wires |
| CN104588655A (en) * | 2015-01-13 | 2015-05-06 | 马鞍山市兴隆铸造有限公司 | Preparation technology for high-strength high-conductivity copper alloy guide lines |
| CN108251685A (en) * | 2018-01-22 | 2018-07-06 | 北京科技大学 | A kind of tungsten dispersed and strengthened copper-based composite material and preparation method thereof |
| WO2018192217A1 (en) * | 2017-04-19 | 2018-10-25 | 京东方科技集团股份有限公司 | Thin-film transistor and preparation method therefor, array substrate and preparation method therefor, and display panel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107799496B (en) * | 2017-09-01 | 2020-05-22 | 华南理工大学 | High-reliability copper alloy bonding wire for electronic packaging and preparation method thereof |
-
2020
- 2020-12-29 CN CN202011589273.6A patent/CN112687787B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329956A (en) * | 1995-11-17 | 2002-01-09 | 奥斯兰姆施尔凡尼亚公司 | Tungsten-copper composite powder |
| CN1544673A (en) * | 2003-11-13 | 2004-11-10 | 北京科技大学 | Process for preparing W-Cu alloy by mechanical activation and chemical activation method |
| CN102500615A (en) * | 2011-10-21 | 2012-06-20 | 厦门虹鹭钨钼工业有限公司 | Method for manufacturing tungsten-copper alloy rods and wires |
| CN104588655A (en) * | 2015-01-13 | 2015-05-06 | 马鞍山市兴隆铸造有限公司 | Preparation technology for high-strength high-conductivity copper alloy guide lines |
| WO2018192217A1 (en) * | 2017-04-19 | 2018-10-25 | 京东方科技集团股份有限公司 | Thin-film transistor and preparation method therefor, array substrate and preparation method therefor, and display panel |
| CN108251685A (en) * | 2018-01-22 | 2018-07-06 | 北京科技大学 | A kind of tungsten dispersed and strengthened copper-based composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112687787A (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI355424B (en) | Process for producing niobium suboxide | |
| CN108495831A (en) | The manufacturing method of silicon nitride sintered base plate, silicon nitride sintered base plate piece, loop substrate and silicon nitride sintered base plate | |
| CN111848165B (en) | P-type bismuth telluride thermoelectric material and preparation method thereof | |
| CN1937856B (en) | Rare earth basic-metal resistance size for metal base board based rare earth thick film circuit and its preparing process | |
| CN103194629B (en) | Method for preparing tungsten molybdenum copper composite material | |
| CN100549195C (en) | A kind of filled skutterudite-base thermoelectrical composite material and preparation method thereof | |
| CN106756376A (en) | tungsten-copper alloy and its processing method and application | |
| CN107994115A (en) | A kind of Pb/Ba codopes BiCuSeO thermoelectric materials and preparation method thereof | |
| CN106906388B (en) | A kind of preparation method of silumin | |
| CN106518052A (en) | Method for preparing fine-grained barium titanate temperature-sensitive ceramic and product thereof | |
| CN111041318A (en) | Tungsten-copper alloy and preparation method thereof | |
| CN112687787B (en) | Manufacturing method of polycrystal series LED copper alloy bonding wire | |
| CN112723875B (en) | Gallium oxide doped tin oxide ceramic target material and preparation method thereof | |
| CN110106419A (en) | A kind of device and method preparing composite material of molybdenum and copper | |
| Ding et al. | Microstructure and properties of WCu composites with low copper content at different sintering temperatures | |
| CN107507909A (en) | A kind of porous p-type Bi2Te3Base thermoelectricity material and preparation method thereof | |
| EP1905742A1 (en) | MICROPOWDER OF Nb COMPOUND AND PROCESS FOR PRODUCTION THEREOF | |
| CN102433481B (en) | Preparation method of AlN-particle-reinforced copper composite heat sink material and thereof | |
| KR100428948B1 (en) | A production method of tungsten nano powder without impurities and its sintered part | |
| CN113584337B (en) | Preparation method of tungsten-copper composite material with low copper content and product | |
| KR970001558B1 (en) | Method for composite powder | |
| Tao et al. | Properties, phases and microstructure of microwave sintered W-20Cu composites from spray pyrolysiscontinuous reduction processed powders | |
| CN108103336B (en) | Bi1-xSbxThermoelectric material and preparation method thereof | |
| KR20150087601A (en) | Thermoelectric material for thermoelectric device | |
| CN110707205B (en) | Method for improving Te-based thermoelectric joint performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |