CN1116130C - Process for preparing copper film - Google Patents
Process for preparing copper film Download PDFInfo
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- CN1116130C CN1116130C CN 00110288 CN00110288A CN1116130C CN 1116130 C CN1116130 C CN 1116130C CN 00110288 CN00110288 CN 00110288 CN 00110288 A CN00110288 A CN 00110288A CN 1116130 C CN1116130 C CN 1116130C
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- 239000010949 copper Substances 0.000 title claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 238000005097 cold rolling Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 208000037656 Respiratory Sounds Diseases 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005482 strain hardening Methods 0.000 description 5
- 239000007769 metal material Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- Metal Rolling (AREA)
- Conductive Materials (AREA)
Abstract
The present invention relates to a preparing method for copper films. The present invention is characterized in that nanometer metal Cu of which the crystal grain size is smaller than 100 nms is used as raw materials; the purity is higher than 99.995 wt%, and the density is within the interval of 8.91(+/-)0.03 g/cm<3>; the raw materials are rolled in the cold mode at the room temperature, and the deformation speed rate ranges from 1*10<-5> to 1*10<1> /s. Copper films prepared by the present invention have the advantages of favorable surface quality, small thickness and simple technology. The present invention can be realized by common rolling equipment.
Description
Technical field
The present invention relates to the technology of preparing of metallic material film, a kind of preparation method of copper film is provided especially.
Background technology
So-called " film " be meant to three-dimensional space wherein one dimension be very little, this one dimension refers to the thickness of film, it has been generally acknowledged that the film of the following thickness of 1 μ m is a film, the above person of 1 μ m is a thick film, but does not have obvious limit here.The method for preparing metallic membrane has many kinds, industry in 18th century, and people just can prepare solid film by electroless plating and glow discharge deposition.In recent years, developed vacuum evaporation deposition, thermospray, sputtering sedimentation or the like technology of preparing again in succession, in the mechanical workout, rolling method also commonly used reduces the size of product thickness direction, and this method is widely used in the plastic working field.Rolling technology is relevant to Deformation velocity, deformation extent, temperature parameter or the like with many factors, rollingly when rolling, whether produce softening (replying and recrystallize) immediately by metal and be divided into hot rolling and cold rolling, generally metal at recrystallization temperature (0.4Tm, Tm is a fusing point) above rollingly be called hot rolling, and the cold rolling material that is meant directly at room temperature carries out without heating.General with the blank of specializing in cold rolling usefulness that passes through hot-roll forming or hot-finished material as raw material, on cold-rolling mill, be rolled behind the descaling.When cold rolling in the metal because of the motion and the long-pending work-hardening effect that produces in various degree of plug of dislocation, thereby limited the distortion of materials ability.This work-hardening effect just can be carried out further machining deformation after must eliminating by appropriate heat treatment.Therefore, hot and cold processing treatment has repeatedly become the traditional technology of most metal material processing distortion.Though it is good that cold rolling material has surface quality, characteristics such as physical strength height, when cold rolling between passage deflection little, annealing process is loaded down with trivial details, and economic cost is big etc., and shortcoming also often makes it to be restricted.In addition, being pricked the material final thickness, also thicker (the rolled minimum thickness of normal four-roller cold-rolling mill is 0.25mm.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of copper film, its copper film surface quality of preparing is good, can reach very thin thickness, and technology is simple, uses common rolling can the realization fully.
The invention provides a kind of preparation method of copper film, it is characterized in that: is starting material with grain-size less than the nano metal Cu of 100nm, and purity is higher than 99.995wt%, and density is 8.91 ± 0.03g/cm
3, at cold rolling at room temperature, rate of deformation: 1 * 10
-5～1 * 10
1/ s.
The present invention is by carrying out rolling deformation under the room temperature to nano metal Cu material, need not any annealing and other treating processes that eliminates stress in the operation of rolling, obtain the Cu mould material of aximal deformation value high-elongation, and the grain-size of Cu film remains unchanged in the operation of rolling, does not also have tangible work-hardening effect in the material.The excellent properties of nano material is combined with Materials Processing Engineering, utilize the nano metal material particular structure, need not stress relieving by annealing with the rolling method of room temperature first, and obtain the Cu film about 20 μ m.The rolling Cu of the obtaining film of the room temperature of nano metal Cu means that metallic substance nanometer after-processing technology process can simplify greatly, this will have significant values to manufacturing of retrofit, electron device and the micromachine of material etc., simultaneously, also be a challenge of system being expected traditional deformation mechanism.Below by embodiment in detail the present invention is described in detail.
Description of drawings
The photomacrograph of the nanocrystalline Cu sample of rolling attitude of different distortion amount under accompanying drawing 1 room temperature condition.
The microstrain (empty circle) of accompanying drawing 2 electrolytic deposition nanometer Cu samples and the microstrain (real circle) of average grain size (short side piece) and the thick Cu sample of annealed state are with the variation tendency of cold rolling reduction.
Accompanying drawing 3 high-resolution electron microscopies are observed the microtexture of rolling back Cu film.
The micro-hardness of accompanying drawing 4 electrolytic deposition nanometer Cu samples, the thick Cu sample of annealed state and common thick Cu sample is with the variation tendency of cold rolling reduction.
Embodiment
Embodiment 1:
The nanometer Cu sample that one section grain-size of 16mm * 4mm * 1mm is 30nm is cold rolling at ambient temperature, find that sample constantly increases along rolling direction length, the thickness direction size constantly reduces, and sample width almost constant (＜5%).Through constantly rolling, sample is more and more longer, and last nanocrystalline Cu sample becomes the film band that a smooth surface does not have any crackle all around, and this moment, total deformation was about 5100%, as shown in Figure 1.Cu membrane sample thickness is about 20 μ m (this is the thickness limit of this milling train) during rolling end, further rollingly still can carry out.
Embodiment 2:
Quantitatively the x-ray measurement result shows, nanocrystalline Cu The grain size is all the time about 30nm in cold-rolled process, and the microstrain in the material raise greatly in the starting stage (ε＜1000%), this principal reaction the variation of dislocation desity in the sample.And when ε 〉=1000%, its microstrain reaches a saturation value and is about 0.16% (see figure 2).And in the thick Cu sample of annealed state, the version of microstrain but with the microstrain Changing Pattern completely different (as shown in Figure 2) of nanocrystalline Cu.
Embodiment 3:
High-resolution electron microscope is observed the microtexture of cold rolling back nanometer Cu sample and is found that in the operation of rolling, the grain size in the nanocrystalline Cu sample does not almost change, and grain shape still is an equiax crystal.But in the nanocrystalline Cu sample of rolling attitude, dislocation desity (mainly concentrating on the crystal boundary place) obviously increases, the misorientation of crystal grain and intergranule has also obviously increased, statistics shows, the misorientation of intergranule is approximately 6～18 ° in the nanocrystalline Cu sample in abundant rolling back, and this will be apparently higher than the grain orientation in the nanocrystalline Cu sample of electrolytic deposition attitude poor (1～10 °).As shown in Figure 3.
Embodiment 4:
The micro-hardness experimental result shows that in cold-rolled process the hardness of electrolytic deposition nanometer Cu sample is increased to 1.20GPa (ε=800%) in the starting stage from 1.05GPa (deposition attitude), as shown in Figure 4.Continue cold rollingly, then do not have work-hardening effect (ε＞800%) in the nanometer Cu sample.
Embodiment 5:
With grain-size is that the nanometer Cu sample of 70nm is cold rolling at ambient temperature, finds that equally this sample can be about 20 μ m Cu films by at room temperature cold rolling one-tenth thickness.
Comparative example 1:
The pure Cu sample of cold rolling common coarse-grain is found under same condition, and when deflection was approximately 800%, existing tangible crackle produced.
Comparative example 2:
The nanocrystalline Cu sample of 30nm was annealed 48 hours under 500 ℃ of vacuum conditions, make its crystal grain fully grow up (grain-size is greater than 100 μ m).Cold rolled annealed attitude Cu sample under identical condition is found equally when deflection is about 700%, and existing obvious crackle produces around the sample.Can get rid of the influence of purity by above experiment contrast to the sample temperature-room type plasticity.
Comparative example 3:
Under same cold rolling condition, then exist tangible work-hardening effect in the common thick Cu sample of cold rolling attitude: as can be seen from Figure 4, the hardness of common thick Cu sample is increased to 1.57GPa (ε=800%, crackle produces) from the 0.61GPa of former primary state; The hardness of annealed state Cu sample is increased to 1.45GPa (ε=650%, crackle produces) from 0.51GPa (annealed state).The different trend of changes in hardness have illustrated deformation mechanisms different between the two in this coarse-grain Cu sample and the nanocrystalline Cu sample.
Claims (1)
1, a kind of preparation method of copper film is characterized in that: is starting material with grain-size less than the nano metal Cu of 100nm, and purity is higher than 99.995wt%, and density is 8.91 ± 0.03g/cm
3, at cold rolling at room temperature, rate of deformation: 1 * 10
-5～1 * 10
1/ s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110288 CN1116130C (en) | 2000-04-05 | 2000-04-05 | Process for preparing copper film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110288 CN1116130C (en) | 2000-04-05 | 2000-04-05 | Process for preparing copper film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1316304A CN1316304A (en) | 2001-10-10 |
| CN1116130C true CN1116130C (en) | 2003-07-30 |
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|---|---|---|---|
| CN 00110288 Expired - Fee Related CN1116130C (en) | 2000-04-05 | 2000-04-05 | Process for preparing copper film |
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| CN (1) | CN1116130C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430512C (en) * | 2005-10-26 | 2008-11-05 | 中国科学院金属研究所 | Superhigh strength high conduction block pure copper material and preparation method |
| CN101323937B (en) * | 2007-06-15 | 2010-05-19 | 中国科学院金属研究所 | Method for preparing high strength high conductivity copper thin slab by severe plastic deformation |
| CN104056870A (en) * | 2013-03-22 | 2014-09-24 | 中色奥博特铜铝业有限公司 | Production method of ultrathin broad-width soft red copper belt |
| CN105470383A (en) * | 2015-12-31 | 2016-04-06 | 江苏森尼克电子科技有限公司 | Magnetic-sensitive device with pre-embedded electrode and manufacturing process |
| CN110424053B (en) * | 2019-07-22 | 2021-01-15 | 四川大学 | Method for preparing nano-structure block material |
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2000
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| CN1316304A (en) | 2001-10-10 |
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Granted publication date: 20030730 Termination date: 20130405 |