CN108998692A - No-oxygen copper plate and ceramic wiring board - Google Patents
No-oxygen copper plate and ceramic wiring board Download PDFInfo
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- CN108998692A CN108998692A CN201810564074.6A CN201810564074A CN108998692A CN 108998692 A CN108998692 A CN 108998692A CN 201810564074 A CN201810564074 A CN 201810564074A CN 108998692 A CN108998692 A CN 108998692A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/492—Bases or plates or solder therefor
- H01L23/4924—Bases or plates or solder therefor characterised by the materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
The present invention provides no-oxygen copper plate and ceramic wiring board, even if being also able to suppress the coarsening of crystal in the case where high-temperature heating.The no-oxygen copper plate is formed as tabular by rolling, it is the crystal in { 022 } face, { 002 } face, { 113 } face, { 111 } face and { 133 } face with the crystal face parallel with rolling surface, heat under conditions of 900 DEG C the average crystal particle diameter after heat treatment in 10 minutes is 0.4mm or less.
Description
Technical field
The present invention relates to no-oxygen copper plate and ceramic wiring boards.
Background technique
As the substrate of installation semiconductor element, ceramic wiring board (see, for example patent document 1,2) is used sometimes.Pottery
Porcelain wiring substrate is engaged with no-oxygen copper plate by ceramic substrate and is formed, and any interarea of ceramic substrate is arranged in the no-oxygen copper plate
It above and for example, by etching removes predetermined position and becomes Wiring pattern (copper wiring).As connecing for ceramic substrate and no-oxygen copper plate
Conjunction method is melted using the Cu oxide layer for making to be formed on the joint surface with ceramic substrate of no-oxygen copper plate and engages the two
Direct bonding method, active metal welding etc. using the solder for being added to titanium (Ti) isoreactivity metal and by the two engagement.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 61-296788 bulletin
Patent document 2: Japanese Unexamined Patent Publication 9-36540 bulletin
Summary of the invention
Problems to be solved by the invention
In above-mentioned joint method, due to making the metal meltings such as copper (Cu), Ti, with the temperature of high temperature in joint technology
The heating of degree band (such as 800~1080 DEG C).If constituting no-oxygen copper plate sometimes however, no-oxygen copper plate is heated in high temperature
Copper crystal (crystal grain of copper) growth and coarsening.
Even if being also able to suppress the coarsening of crystal the object of the present invention is to provide in the case where being heated at high temperature
No-oxygen copper plate and its relevant technologies.
The method used for solving the problem
A scheme according to the present invention, provides no-oxygen copper plate and its relevant technologies, and above-mentioned no-oxygen copper plate passes through rolling
Be formed as tabular,
And having the crystal face parallel with rolling surface is { 022 } face, { 002 } face, { 113 } face, { 111 } face and { 133 } face
Crystal,
The diffraction peak intensity of above-mentioned each crystal face obtained by X-ray diffraction measure will be carried out to the rolling face using 2 θ/θ method
It is set to I{022}、I{002}、I{113}、I{111}、I{133}When,
I{022}/(I{022}+I{002}+I{113}+I{111}+I{133})≤0.3,
(I{002}+I{113})/(I{111}+I{133}) >=1.0,
I{002}/I{022}>=1.0,
I{113}/I{022}>=0.5,
I{111}/I{022}>=0.15,
I{133}/I{022}>=0.02,
0.5≤I{002}/I{113}≤ 5.0,
0.2≤I{133}/I{111}≤ 0.5,
1.0≤I{113}/I{111}≤ 10,
1.0≤I{002}/I{111}≤ 20,
1.0≤I{002}/I{133}≤ 75,
1.0≤I{113}/I{133}≤ 30,
Heat under conditions of 900 DEG C the average crystal particle diameter after heat treatment in 10 minutes is 0.4mm or less.
The effect of invention
According to the present invention, even if in the case where no-oxygen copper plate is in order to engage and be heated at high temperature with ceramic substrate etc.,
Also it is able to suppress the coarsening for constituting the crystal of no-oxygen copper plate.
Detailed description of the invention
Fig. 1 is the explanatory diagram of the position for the neutral point that the embodiment of the present invention is related to.
Specific embodiment
The opinion > of the acquisitions such as < inventor
Before illustrating embodiments of the present invention, the opinion obtained to the present inventor is illustrated.
No-oxygen copper plate is made by carrying out cold rolling, final cold rolling etc. to ingot bar.If carrying out cold rolling, it is rolled in material
Copper crystal rotated to { 022 } face, therefore in rolled material, the crystal face parallel with rolling surface is that the crystal in { 022 } face is easy to
It is flourishing.Therefore, in the no-oxygen copper plate after final cold rolling, the crystal in { 022 } face becomes more, and the crystal of other crystal faces tails off.
If no-oxygen copper plate is heated at high temperature, the crystal in no-oxygen copper plate is recrystallized, to generate new crystal
(recrystal grain).The recrystal grain has particular orientation relevant to the crystal orientation of the crystal before recrystallization.For example, nothing
The crystal in { 022 } face in oxygen copper sheet is recrystallized by high-temperature heating, to be changing into the crystal face parallel with rolling surface and be
{ 002 } crystal in face.
When crystal in no-oxygen copper plate is recrystallized, the crystal with same crystal orientation is easy to merge collection each other
It closes, as a result, the crystal in no-oxygen copper plate is easy to coarsening.For example, if the crystal in { 022 } face as described above is more
No-oxygen copper plate is heated at high temperature, then the crystal in { 022 } face is changing into the crystal in { 002 } face by recrystallizing, and the crystal is each other
Merge and gathers and coarsening.In this way, the coarsening of the crystal in no-oxygen copper plate caused by being heated at high temperature largely relies on
The crystal orientation of crystal present in no-oxygen copper plate after final cold rolling.
Therefore, in order to inhibit { 022 } face in final cold rolling crystal prosperity, it may be considered that by final cold rolling total plus
Work degree inhibits low.However, being accumulated in the rolled material (anaerobic finally obtained if reducing total degree of finish of final cold rolling
Copper sheet) internal strain energy can reduce, therefore when being recrystallized by high-temperature heating, lead to the generation frequency for recrystallizing nucleus
The reduction of rate.As a result, the number of crystals that will lead in the no-oxygen copper plate after high-temperature heating reduces, that is, lead to crystal coarsening.
Accordingly, with respect to no-oxygen copper plate, the inventors of the present invention inhibit high temperature to add in order not to reduce total degree of finish of final cold rolling
Thermally-induced crystal coarsening, has made intensive studies.Itself as a result, it has been found that, by reduce high-temperature heating before no-oxygen copper plate in
{ 022 } crystal in face, and make crystal face { 022 } face parallel with rolling surface in no-oxygen copper plate there are a certain amount of (fixed number)
The crystal in face in addition, is able to solve the above problem.The present invention is based on the above-mentioned opinions of the discoveries such as inventor.
< an embodiment of the invention >
Hereinafter, being illustrated to an embodiment of the invention.
(1) composition of no-oxygen copper plate
Firstly, the composition to no-oxygen copper plate is illustrated.
No-oxygen copper plate of the present embodiment for example by carry out rolling processing and along predetermined direction roll, be formed as flat
Plate (plate).In addition, the rolling surface of no-oxygen copper plate becomes interarea (main surface).No-oxygen copper plate with a thickness of such as 100 μm with
On.
No-oxygen copper plate made of rolling is made of a variety of crystal, as polycrystalline.No-oxygen copper plate has parallel with rolling surface
Crystal face is the crystal in { 022 } face, { 002 } face, { 113 } face, { 111 } face and { 133 } face.Expose in the rolling surface of no-oxygen copper plate more
Kind crystal, since no-oxygen copper plate as described above is polycrystalline, rolling surface will not be only made of a crystal face.
In this specification, the crystal face parallel with rolling surface is that the crystal in { 022 } face can also be referred to as the crystal in { 022 } face.
The crystal face parallel with rolling surface is that the crystal in { 002 } face, { 113 } face, { 111 } face and { 133 } face is also the same.It is parallel with rolling surface
Crystal face be { 002 } face, { 113 } face, { 111 } face and { 133 } face crystal can also be collectively referred to as the " crystalline substance of each crystal face in secondary orientation
Body ".In addition, the main azimuth plane of the copper crystal in no-oxygen copper plate made of rolling is { 022 } face.
As described above, the crystal in { 022 } face in no-oxygen copper plate by tying again if no-oxygen copper plate is heated at high temperature
It is brilliant and when changing to the crystal in { 002 } face, which combines with each other set, makes the crystal coarsening in no-oxygen copper plate.Therefore, it is
Inhibit to cause crystal in no-oxygen copper plate to become thick (hereinafter also referred to as " crystal caused by being heated at high temperature by high-temperature heating
Coarsening "), it is desirable to reduce the crystal in { 022 } face present in no-oxygen copper plate.2 θ/θ method pair is used for example, it is desired to sufficiently reduce
The rolling surface of no-oxygen copper plate carries out the diffraction peak intensity in { 022 } face obtained by X-ray diffraction measure.
Even if the crystal of each crystal face in secondary orientation in the case where no-oxygen copper plate has been heated at high temperature, also hardly to roll
The parallel face in face processed is that the crystal of other crystal faces changes.Therefore, it in order to inhibit to be heated at high temperature caused crystal coarsening, needs to make
There are the crystal of each crystal face in a certain amount of secondary orientation in no-oxygen copper plate.For example, it is desired to make to carry out X to rolling surface using 2 θ/θ method
Ray diffraction determination and the diffraction peak intensity of each crystal face in secondary orientation obtained are respectively in predetermined range.
As described above, the crystal and secondary orientation in crystal coarsening caused by being heated at high temperature and { 022 } face in no-oxygen copper plate
Each crystal face crystal between observe substantial connection.Crystal coarsening, needs to adjust caused by order to inhibit to be heated at high temperature
{ 022 } balance of the above-mentioned diffraction peak intensity of each crystal face in face and secondary orientation.
About no-oxygen copper plate, will use 2 θ/θ method to rolling surface carry out { 022 } face obtained by X-ray diffraction measure,
{ 002 } diffraction peak intensity in face, { 113 } face, { 111 } face and { 133 } face is set to I{022}、I{002}、I{113}、I{111}、
I{133}When, meet following formula (1)~formula (12) whole.
Formula (1): I{022}/(I{022}+I{002}+I{113}+I{111}+I{133})≤0.3
Formula (2): (I{002}+I{113})/(I{111}+I{133})≥1.0
Formula (3): I{002}/I{022}≥1.0
Formula (4): I{113}/I{022}≥0.5
Formula (5): I{111}/I{022}≥0.15
Formula (6): I{133}/I{022}≥0.02
Formula (7): 0.5≤I{002}/I{113}≤5.0
Formula (8): 0.2≤I{133}/I{111}≤0.5
Formula (9): 1.0≤I{113}/I{111}≤10
Formula (10): 1.0≤I{002}/I{111}≤20
Formula (11): 1.0≤I{002}/I{133}≤75
Formula (12): 1.0≤I{113}/I{133}≤30
Above-mentioned formula (1) indicates that the diffraction peak intensity in { 022 } face is sufficiently low to each crystal face in secondary orientation (other than { 022 } face
Crystal face) 3 the one-tenth or less of diffraction peak intensity.This means that the crystal in { 022 } face in no-oxygen copper plate is sufficiently few.
Above-mentioned formula (2) indicates total (I of the diffraction peak intensity in { 002 } face and the diffraction peak intensity in { 113 } face{002}+
I{113}) ratio ratio { 111 } face diffraction peak intensity and { 133 } face diffraction peak intensity total (I{111}+I{133}) ratio
It is high.This indicates that the compression component that rolled material is applied in aftermentioned final cold rolling is higher than stretching ingredient, i.e., in final cold rolling
Middle compression stress is than tensile stress dominance.
Above-mentioned formula (3)~(6) respectively indicate do not rotated to by aftermentioned final cold rolling { 022 } face copper crystal it is opposite
In the ratio of the copper crystal of rotation (variation) to { 022 } face.
Above-mentioned formula (7), (8) be illustrated respectively in copper crystal by aftermentioned final cold rolling to { 022 } face rotate when, rear
The ratio for the mutual diffraction peak intensity of crystal face that the approach 1,2 stated is observed respectively.
Above-mentioned formula (9)~(12) be illustrated respectively in copper crystal by aftermentioned final cold rolling to { 022 } face rotate when,
The ratio for the mutual diffraction peak intensity of crystal face that approach other than aftermentioned approach 1,2 is observed.
By considering formula (9)~(12) and formula (7), (8) together, illustrates and do not rotated to by aftermentioned final cold rolling
{ 022 } whole of the ratio of the mutual diffraction peak intensity of the crystal face in face.
The relationship of the diffraction peak intensity of each crystal face shown in above-mentioned formula (1)~(12), if need to pay attention to one or
The range of the range of multiple formulas then other formulas also interlocks variation.For example, in order to increase the range of the lower limit of formula (3), as long as
Increase I{002}Value, but in this case, it is more likely that the molecule of formula (7) also becomes larger, and the value of formula (7) is more than upper limit value
5.0.Such relationship is suitable for above-mentioned formula (1)~(12) whole.
Raw material (base material) as no-oxygen copper plate are, it is preferable to use the excellent oxygen-free copper (Oxygen of thermal conductance, resistance to hydrogen embrittlement
Free Copper:OFC).As the oxygen-free copper, from the viewpoint of inhibiting conductivity (electric conductivity) to reduce, it is preferable to use
The oxygen-free copper that purity specified in JIS C1020, H3100 etc. is 99.96% or more.
About no-oxygen copper plate, from the viewpoint of inhibiting conductivity to reduce, preferably its oxygen (O) concentration is 0ppm, i.e. oxygen contains
Amount is zero.However, can inevitably be mixed into impurity in no-oxygen copper plate in the manufacturing process of no-oxygen copper plate, therefore, it is difficult to make
O concentration in no-oxygen copper plate is zero, can generally include the oxygen of the ppm of several ppm~tens or so.In present embodiment, as long as anaerobic
O concentration in copper sheet is 10ppm or less, thus, it is possible to be suitable for aftermentioned ceramic wiring board.
In no-oxygen copper plate, preferably comprise selected from the group being made of tin (Sn), zirconium (Zr), magnesium (Mg), titanium (Ti) and calcium (Ca)
One or more of element (hereinafter, they can be also referred to as to " elements such as Sn ").
The atomic radius of above-mentioned element is respectively Sn:158pm, Zr:160pm, Mg:160pm, Ti:147pm, Ca:197pm,
It is very big if compared with the atomic radius 128pm of copper (Cu).Therefore, by make the element solid solutions such as Sn in the parent phase of copper from
And lattice (atom lattice) substantially deformation can be made.When no-oxygen copper plate is heated at high temperature, which becomes the obstruction of crystal boundary migration,
As a result, it is possible to inhibit crystal coarsening caused by being heated at high temperature.
The concentration (content) of the elements such as Sn is preferably such as 150ppm hereinafter, more preferably 50ppm or more 150ppm or less.
In addition, in the case where containing two or more element in the group being made of Sn etc. in making no-oxygen copper plate, two or more element
Total concentration (total concentration) be preferably 150ppm or less.
If the concentration (total concentration) of the elements such as Sn is more than 150ppm, the reduction of the conductivity of no-oxygen copper plate becomes larger.Example
Such as, the conductivity of the no-oxygen copper plate containing elements such as Sn is compared with the conductivity of the no-oxygen copper plate without elements such as (not adding) Sn
It is low more than 3%IACS.By making the concentration 150ppm of the elements such as Sn hereinafter, the elements bring crystal such as above-mentioned Sn can be obtained
Coarsening inhibitory effect, while being able to suppress the reduction of conductivity.It can make the conductivity such as 100%IACS of no-oxygen copper plate
More than.
If the concentration of the elements such as Sn is less than 50ppm, the abundant deformation of lattice cannot be made sometimes, cannot sufficiently be obtained above-mentioned
The elements bring crystal coarsening inhibitory effect such as Sn.By making the concentration 50ppm or more of the elements such as Sn, can sufficiently obtain
The elements bring crystal coarsening inhibitory effect such as above-mentioned Sn.
(2) manufacturing method of no-oxygen copper plate
Next, by successively implementing step 1 as shown below~5, to manufacture no-oxygen copper plate of the present embodiment
Method be illustrated.
(step 1: casting)
Use high frequency melting furnace etc. that will melt and generate the melt of oxygen-free copper as the oxygen-free copper of raw material.In the oxygen-free copper
Melt in, the elements such as Sn, Zr, Mg, Ti, Ca of predetermined amount can be added.In this case, with finally formed oxygen-free copper
The concentration (total concentration) of the elements such as the Sn in plate is such as 150ppm hereinafter, preferably 50ppm or more 150ppm mode below,
Adjust the additive amount of the elements such as Sn.Melted oxygen-free copper (melt of oxygen-free copper) is injected into mold and is cooled down, is cast
Ingot bar (ingot) with predetermined thickness, preset width.
(step 2: hot rolling)
Ingot bar is heated to predetermined temperature (such as 900 DEG C or more 1000 DEG C or less), the ingot bar of predetermined temperature is carried out pre-
Determine the hot rolling of degree of finish, obtains the hot rolling material of predetermined thickness (such as 10~15mm).Hot rolling material in this specification, which refers to, to be passed through
The plate of oxygen-free copper for carrying out hot rolling and being formed.
(step 3: cold rolling)
For hot rolling material, heated under conditions of predetermined temperature by the cold rolling of predetermined degree of finish and by material processed predetermined
Pre-determined number is alternately repeated in the annealing (intermediate annealing) of time respectively.The intermediate annealing is will to be added by cold rolling
The material processed of work hardening is annealed, to mitigate the processing of processing hardening.In step 3, cold rolling is replaced with intermediate annealing
After ground respectively carries out pre-determined number, terminated with cold rolling.By carrying out step 3, the cold rolling material of predetermined thickness can get.Cold rolling material
Thickness be adjusted to have carried out the no-oxygen copper plate after subsequent steps 5 (final cold rolling) and become the thickness of predetermined thickness.In addition, this
Oxygen-free copper (after the cold rolling and annealing that have carried out pre-determined number) after cold rolling material in specification refers to this step
Plate, this is the copper bar of also referred to as so-called blank.
(step 4: blank anneal)
It carries out obtaining annealing base to cold rolling material, i.e. blank with the annealing (blank anneal) of predetermined temperature heating predetermined time
Material.Blank anneal for example can process the item for straining and sufficiently mitigating in cold rolling material for accumulating by above-mentioned hot rolling, cold rolling
Part is implemented under (temperature, time).
(step 5: final cold rolling)
To the cold rolling material (i.e. annealing blank) for having carried out blank anneal, carry out pre-determined number (preferably repeatedly) with it is above-mentioned
The different cold rolling of cold rolling in step 3 (final cold rolling finishes cold rolling), forms the flat of predetermined thickness (such as 100 μm or more)
The no-oxygen copper plate of plate.In this step, cold rolling is preferably repeatedly carried out continuously without sandwiching annealing (heat treatment).
When rolling processing, for the annealing rolled material (workpiece, material processed) such as blank, by make its from that
By subtracting thickness between this 1 pair of opposed Rolling roller (hereinafter also referred to as roller).It is being drawn from the speed of the rolled material passed through between roller
(roller entrance side) is slower than the rotation speed of roller before into roller, and (roller outlet side) is faster than the rotation speed of roller after pulling out from roller.Cause
This, for being rolled material, is easier to apply compression stress in roller entrance side, is easier to apply drawing in roller outlet side when rolling processing
Stretch stress.In order to which rolled material is subtracted thickness, the compression stress for needing to make to be applied to rolled material is higher than tensile stress (compression stress
> tensile stress).
In step 5, the degree of finish for repeatedly carrying out 1 time (1 passage) is the cold rolling (rolling pass) of predetermined degree of finish, so that always
Degree of finish is such as 40% or more, preferably 80% hereinafter, more preferably 50% or more 75% or less.
Total degree of finish is found out by following (numbers 1).In addition, TB is the material processed (annealing before final cold rolling in (number 1)
Blank) thickness, TA be final cold rolling after material processed (i.e. no-oxygen copper plate) thickness.
(number 1)
Total degree of finish (%)=[(TB-TA)/TB] × 100
If total degree of finish is less than 40%, being accumulated in the strain energy inside the no-oxygen copper plate finally obtained can become not fill
Point.Therefore, even if high temperature can not be inhibited to add sometimes in the case where no-oxygen copper plate meets above-mentioned formula (1)~(12) whole
Thermally-induced crystal coarsening.By making total 40% or more degree of finish, sufficient strain energy can be made to be accumulated in no-oxygen copper plate
Inside more strain energies can be made to be accumulated in the inside of no-oxygen copper plate, can be solved by making total 50% or more degree of finish
The certainly above problem.
Copper crystal in rolled material rotates phenomenon and being applied to the stress of rolled material in rolling, crystal face
It changes.For example, being rolled the copper crystal in material by cold rolling via { 002 } face, { 113 } face, { 111 } in this step
The crystal faces such as face, { 133 } face, such as (variation) is rotated to { 022 } face by following approach 1,2.It is applied to answering for rolled material
Power is bigger, i.e. total degree of finish is higher, then the crystal for rotating to { 022 } face can be more.
Approach 1:{ 113 } face → { 002 } face → { 022 } face
Approach 2:{ 111 } face → { 133 } face → { 022 } face
Therefore, if total degree of finish of the cold rolling in step 5 is more than 80%, the crystal for rotating to { 022 } face becomes more, because
This can largely have the crystal in { 022 } face in no-oxygen copper plate.Thus, for example, even if controlling every 1 passage as described later
In the case where degree of finish, the neutral position put, no-oxygen copper plate can also be unsatisfactory at least any in above-mentioned formula (1)~(12) sometimes
It is a.By making total degree of finish 80% hereinafter, can solve the above problem, by making total degree of finish 75% hereinafter, can be true
It solves the above problems on the spot.
In addition, other than total degree of finish, preferably adjusting the degree of finish of every 1 passage in this step.In addition, every 1 passage
Degree of finish is preferably such as 20% or more and is scheduled degree of finish.Rolled material is applied in each passage thus, it is possible to adjust
The intensity (size) of compression stress and the intensity (size) of tensile stress and make compression stress > tensile stress, while adjustment answer
The ratio of power ingredient (compression component and stretching ingredient).
By adjusting the ratio for the stress component for being applied to rolled material in each passage, thus it is possible to vary rolled by cold rolling
Approach when copper crystal in saw lumber changes to { 022 } face.If be applied to the compression component of rolled material ratio (hereinafter,
Also referred to as " compression component ratio ") it gets higher, then it is easy to through above-mentioned approach 1, if be applied to the stretching ingredient of rolled material
Ratio (hereinafter also referred to as " stretching component ratio ") is got higher, then is easy to through above-mentioned approach 2.
By being set as being easy to the condition by above-mentioned approach 1, such as while being set as compression component > and stretching ingredient, lead to
The degree of finish that every 1 passage is controlled in such a way that compression component ratio is got higher is crossed, so as to increase present in no-oxygen copper plate
{ 002 } amount (number) of the crystal in face, { 113 } face.Under conditions of being easy to through above-mentioned approach 1, by being set as compression component ratio
The condition that rate is got higher can increase the amount of the crystal in { 002 } face present in no-oxygen copper plate, stretch component ratio change by being set as
The condition of high (compression component ratio is lower), can increase the amount of the crystal in { 113 } face present in no-oxygen copper plate.
By being set as being easy to the condition by above-mentioned approach 2, such as while being set as compression component > and stretching ingredient, lead to
The degree of finish that every 1 passage is controlled in a manner of stretching component ratio and get higher is crossed, so as to increase present in no-oxygen copper plate
{ 111 } amount (number) of the crystal in face, { 133 } face.Under conditions of being easy to through above-mentioned approach 2, ingredient ratio is stretched by being set as
The condition that rate is got higher can increase the amount of the crystal in { 111 } face present in no-oxygen copper plate, be become by being set as compression component ratio
The condition of high (stretching component ratio to be lower), can increase the amount of the crystal in { 133 } face present in no-oxygen copper plate.
About the direction of variation, such as using the document of following (a) as reference.
(a) author's Long Island Shanxi one is compiled, " set tissue (set tissue) ", Wan Shan limited liability company, 59 year January 20 of Showa
Day, Fig. 2 .52 of p96
In addition, preferably controlling the position of the neutral point in each passage in step 5.Such as the thickness of preferably rolled material is got over
Thin, the i.e. passage of back segment (lower section), then be more set in roller outlet side for the position of neutrality point.So-called neutrality point, is from roller
Between the speed of rolled material that the passes through position equal with the rotation speed of roller.In addition, as described above, being rolled from what is passed through between roller
The speed of saw lumber is slower than the rotation speed of roller in roller entrance side, faster than the rotation speed of roller in roller outlet side.In neutral point, apply
Become maximum in the pressure of rolled material.
By the position of the neutral point of control, the intensity of adjustable compression stress, the intensity of tensile stress, stress component
Ratio.The intensity for being applied to the compression stress of rolled material is more improved, then the copper crystal being rolled in material is more easy to rotate to
{ 022 } face.Furthermore as described above, no-oxygen copper plate can be increased if improving the compression component ratio for being applied to rolled material
Present in { 002 } face, { 113 } face crystal amount, if reduce compression component ratio, can increase in no-oxygen copper plate and deposit
{ 111 } face, { 133 } face crystal amount.
By the way that the position of neutrality point is set in roller outlet side, the intensity for being applied to the compression stress of rolled material can be made
It is higher, or improve compression component ratio.By the way that the position of neutrality point is set in roller entrance side, can make to be applied to rolled material
Compression stress intensity it is lower, or reduce compression component ratio.
The position of neutrality point can be controlled for example, by adjustment mill speed (rotation speed of roller).For example by every 1
The other conditions such as secondary degree of finish are set as a timing, can make the neutral position put relative to traveling if improving mill speed
Direction is mobile rearward (entrance side), can make if reducing mill speed the position of neutral point relative to direction of travel to
Front side (outlet side) is mobile.
The control of position about neutrality point can also be with front tension, rear tension, roller other than mill speed
Diameter, degree of finish, the surface roughness of roller, rolling loading etc. are carried out as controlling elements.It can make in these controlling elements
The only one factor it is variable, multiple factors can also be made variable.That is, the control of the position for neutrality point, it may be considered that a variety of
Method.
In addition, above-mentioned controlling elements are related with the composition of roll mill.For example, according to the group of the number of segment of roller, the sum of roller, roller
Close the difference of configuration, the diameter of each roller, material, the composition of rollers such as surface state (surface roughness) etc., compression stress is to being rolled
Applying mode, coefficient of friction of saw lumber etc. generate different.Therefore, for each roll mill, the absolute value of above-mentioned controlling elements is all
It is different.In this way, the control of the position of neutral point depends on the specification of roll mill mostly, therefore preferably each roll mill is fitted
Work as adjustment.
The position of neutrality point is referred to such as bibliography (b) calculating and finds out.
(b) Japanese plastic processing association compiles, " Technology of Plastic Processing 7 plate rollings of series (Technology of Plastic Processing シ リ ー ズ 7
Plate calendering) ", CORONA company, p14, p27 formula (3.3), p28
In addition, in each roller, the position of neutral point is moved in the progress of cold rolling in order to prevent, preferably for example in step 5
It is controlled in such a way that the position of neutrality point is mobile not to the outlet side of roller.
(3) composition and its manufacturing method of ceramic wiring board
Composition and its manufacturer to the ceramic wiring board for having used above-mentioned no-oxygen copper plate of the present embodiment
Method is illustrated.
Ceramic wiring board of the present embodiment has the ceramic substrate of predetermined thickness (such as 0.5mm), Yi Jishe
Set on ceramic substrate be made of above-mentioned no-oxygen copper plate with wire rod.Ceramic substrate is for example bonded via solder with wire rod
(engagement).The predetermined position of no-oxygen copper plate is removed for example, by etching and forms Wiring pattern (copper wiring).As ceramic base
Plate can be used such as with the ceramic sintered bodies aluminium nitride (AlN), silicon nitride (SiN) for principal component.It, can be with as solder
Using the metals such as example silver-colored (Ag), Cu, Sn, indium (In), Ti, molybdenum (Mo), carbon (C) or comprising at least one kind of in these metals
Metal alloy.
Above-mentioned ceramic wiring board can make for example, by following steps.Firstly, carrying out the clear of ceramic base plate surface
Clean processing.For example, ceramic substrate is heated to predetermined temperature (such as 800 DEG C~1080 DEG C), removing is attached to ceramic substrate
The organic matter on surface, residual carbon.In turn, for example, by silk screen print method, paste is coated on any interarea of ceramic substrate
Solder.Then, no-oxygen copper plate is configured on solder, by the laminated body of no-oxygen copper plate and ceramic substrate and solder in predetermined temperature
(such as 800 DEG C or more 1080 DEG C or less) heat predetermined time (such as 5 minutes or more), make no-oxygen copper plate and ceramic substrate via
Solder and be bonded.The heating preferably carries out in a vacuum or in reducing gas atmosphere or in non-active gas atmosphere.
(4) effect of the present embodiment
According to the present embodiment, one or more effects as shown below are played.
(a) no-oxygen copper plate of the present embodiment, have passed through no-oxygen copper plate after step 5 and before being heated at high temperature
Meet above-mentioned formula (1)~(12) whole.That is, no-oxygen copper plate of the present embodiment be { 022 } face crystal it is few, secondary orientation
Each crystal face crystal respectively with a certain amount of existing no-oxygen copper plate.Even if as a result, the case where no-oxygen copper plate is heated at high temperature
Under, the mutual merging set of the crystal grain (recrystal grain) being also able to suppress in no-oxygen copper plate is able to suppress the coarsening of crystal.
In the case that even if no-oxygen copper plate of the present embodiment is heated at high temperature in the engagement for example with ceramic substrate, also can
Inhibit the coarsening of crystal.Even if for example, no-oxygen copper plate of the present embodiment heats under conditions of having carried out at 900 DEG C
After heat treatment in 10 minutes, average crystal particle diameter is also 0.4mm or less.
Even (b) the few copper sheet of impurity, i.e. no-oxygen copper plate, can also by meeting above-mentioned formula (1)~(12) whole,
To inhibit to be heated at high temperature caused crystal coarsening.
(c) by making certainly inhibit crystal caused by being heated at high temperature coarse comprising elements such as Sn in no-oxygen copper plate
Change.
(d) by inhibiting crystal coarsening, no-oxygen copper plate caused by being heated at high temperature that can especially be suitably adapted to ceramics
The purposes with wire rod of wiring substrate.
By inhibiting crystal coarsening caused by being heated at high temperature, it is related to using CCD camera etc. to present embodiment
The ceramic wiring board of no-oxygen copper plate when being checked, be easy to crystal crystal boundary and the check surface for being located at ceramic wiring board
Foreign matter, scar etc. distinguish.It is thus possible to improve checking precision.
In addition, being able to suppress by inhibiting crystal coarsening caused by being heated at high temperature because coarsening recrystal grain is led
It causes to increase in the concave-convex surface of no-oxygen copper plate, i.e. the numerical value of the surface roughness of no-oxygen copper plate becomes larger.Therefore, it is able to suppress and is making pottery
The bond strength of the wire and ceramic wiring board that use when installing semiconductor element on porcelain wiring substrate reduces.
(e) by no-oxygen copper plate with a thickness of such as 100 μm or more, so as to suitably be applicable in no-oxygen copper plate as pottery
Porcelain wiring substrate matches wire rod.
(f) by making 99.96% or more the purity of the copper of no-oxygen copper plate, or make the O concentration 10ppm of no-oxygen copper plate with
Under, or make the concentration 150ppm of the elements such as Sn hereinafter, the conductivity such as 100%IACS or more of no-oxygen copper plate can be made.
Thus, it is possible to which being suitably applicable in no-oxygen copper plate as ceramic wiring board matches wire rod.From certainly preventing leading for no-oxygen copper plate
From the viewpoint of electric rate reduces, the concentration of the elements such as purity, O concentration and Sn of preferably above-mentioned copper is all met the above range.
(g) pass through the rate-determining steps 5 (final cold rolling) in such a way that no-oxygen copper plate meets above-mentioned formula (1)~(12) whole
Treatment conditions (processing conditions), to even if in the case where making 40% or more total degree of finish of the cold rolling of step 5, not drop
In the case where low total degree of finish, it can also obtain crystal coarsening caused by high-temperature heating and be able to the no-oxygen copper plate inhibited.
(h) by making 40% or more total degree of finish of the cold rolling of step 5, sufficient strain energy can be made to be accumulated in anaerobic
The inside of copper sheet, as a result, the generation of recrystallization nucleus can be improved when no-oxygen copper plate is recrystallized by high-temperature heating
Frequency (the generation number of recrystallization nucleus increases).Even if can also make nothing in the case where no-oxygen copper plate is heated at high temperature as a result,
There are the desired number of crystal in oxygen copper sheet, can certainly inhibit the coarsening of crystal.
(i) by making total degree of finish 80% of the cold rolling of step 5 hereinafter, can reduce the crystal for rotating to { 022 } face,
As a result, it is possible to make the crystal of each crystal face in the secondary orientation in no-oxygen copper plate in the presence of (residual) desirable amount (desired quantity).
Thus, it is easy to carry out the rate control of the crystal of each crystal face in the secondary orientation in no-oxygen copper plate, can be readily available in satisfaction
State formula (1)~(12) no-oxygen copper plate.
(j) by controlling the degree of finish of every 1 passage in steps of 5, can adjust the copper crystal in rolled material pass through it is cold
Approach when rolling and changing to { 022 } face.As a result, it is possible to carry out the ratio of the crystal of each crystal face in the secondary orientation in no-oxygen copper plate
Rate control.That is, the crystal in { 022 } face in no-oxygen copper plate can be reduced, while by the crystal face in the secondary orientation in no-oxygen copper plate
Crystal is easily adapted to for optimum value.
(k) position put by controlling the neutrality of each passage in steps of 5, can reduce the crystal for rotating to { 022 } face,
And carry out the rate control of the crystal of each crystal face in secondary orientation.That is, { 022 } so that in no-oxygen copper plate can be easily adjusted
The ratio of the crystal of the crystal face in face and secondary orientation becomes optimum value.As a result, it is possible to more easily obtain meet above-mentioned formula (1)~
(12) whole no-oxygen copper plates.
It (l) in steps of 5, can by carrying out the control of the position of the degree of finish of every 1 passage and the neutral point of each passage
Critically control the ratio of the crystal of each crystal face in { 022 } face and secondary orientation in no-oxygen copper plate.
(m) in steps of 5, by being controlled to prevent the position of the neutral point in each roller from moving in the progress of cold rolling
It is dynamic, it can certainly carry out the intensity, the intensity of tensile stress, the ratio of stress component that are applied to the compression stress of rolled material
Control.
< other embodiments >
More than, an embodiment of the invention is specifically illustrated, but the present invention is not limited to above embodiment, it can
It is suitably changed in the range of not departing from the purport.
In above embodiment, it is illustrated in case where implementation steps 1~5 make no-oxygen copper plate, but not
It is defined in this.Such as step 1~4 can omit depending on the application and suitably.
Furthermore for example, after step 5, as step 6, can carry out to the no-oxygen copper plate obtained in step 5 with predetermined
The heat treatment (dynamic recrystallization treatment) of temperature heating predetermined time.Even if no-oxygen copper plate of the present invention carried out it is such
In the case where dynamic recrystallization treatment, the crystal being also able to suppress in no-oxygen copper plate is become thick.Even in addition, having carried out step
No-oxygen copper plate after 6 is also able to suppress the coarsening of crystal in the case where high-temperature heating in the engagement with ceramic substrate.
In above embodiment, in the production of ceramic wiring board, to carry out oxygen-free copper by active metal welding
It is illustrated in case where the engagement of plate and ceramic substrate, however, not limited to this, can also be for example, by direct bonding method
They are engaged.
In addition, no-oxygen copper plate of the present invention is not limited to using with wire rod as ceramic wiring board as described above
The case where.In addition, no-oxygen copper plate of the present invention can be suitably adapted to require to inhibit brilliant in 800 DEG C or more of heating
The coarsening purposes of body.
Embodiment
Next, illustrating the embodiment of the present invention, but the present invention is not limited thereto.
The production > of < sample
(sample 1)
Firstly, casting the billet of predetermined shape by continuous casting process.Specifically, using melting furnace will be as raw material
Oxygen-free copper fusing and generate the melt of oxygen-free copper.In the melt, with the dense of the Sn in finally formed no-oxygen copper plate
Degree becomes the mode of 80ppm, adds the Sn of predetermined amount and melt is melted.The melt is injected into the mold of predetermined shape and is cast
With a thickness of 150mm, the ingot bar that width is 500mm.Hot rolling is carried out to resulting ingot bar, obtains the plate (hot rolling with a thickness of 8mm
Material).For resulting hot rolling material, by scheduled cold rolling and by material processed 650~750 DEG C at a temperature of kept for 2 minutes and
The intermediate annealing of heating alternately respectively carries out pre-determined number, obtains cold rolling material (blank).The thickness of blank is set as implementing below
Final cold rolling at the end of no-oxygen copper plate become desired thickness thickness.The adjustment of the thickness of blank is by adjusting cold rolling
Degree of finish carries out.Then, to resulting blank carry out 700 DEG C at a temperature of keep 1 minute and heat annealing (blank moves back
Fire), obtain annealing blank.
For blank of annealing, implement not sandwich the final cold rolling for annealing and being carried out continuously multiple (multiple passages) cold rolling.It will
The condition of each passage of final cold rolling is shown in following tables 1." position (mm) of neutrality point " so-called shown in table 1, for such as Fig. 1 institute
Show that point is from outlet side end portion to neutrality in the contact surface from the rolled material (workpiece) and roller that pass through between a pair of rolls
Length L only.That is, the value of the position of neutrality point shown in table 1 is smaller, then neutral point is located roller outlet side.
[table 1]
Whenever passing through rolling pass, rolled material is all subtracted thickness.Therefore, in final cold rolling, as shown in table 1, according to thickness
For the thickness of 1mm rolled material below, the degree of finish of every 1 passage and the position of neutral point are had adjusted for each passage.
At this point, the position of the neutral point of control is so that closer to lower section (back segment), then the neutral position put is located from upper section (leading portion)
Roller outlet side.By carrying out such final cold rolling, the no-oxygen copper plate with a thickness of 0.3mm is obtained.It is set to sample 1.
(sample 2~20)
For sample 2~20, the additive amount of the elements such as the Sn being added in melt is adjusted so that choosing in no-oxygen copper plate
The concentration of element in the group of free Sn, Zr, Mg, Ti and Ca composition becomes as shown in table 2.In addition, making each road of final cold rolling
Secondary condition is as shown in table 1, keeps total degree of finish of final cold rolling as shown in table 2.In addition, sample 2~20 is respectively in Tables 1 and 2
In shown range, makes the degree of finish of every 1 passage and the change in location of neutral point, make to be applied to rolled material when final cold rolling
The intensity of compression stress, the intensity of tensile stress, stress component (i.e. the ratio of compression component and stretching ingredient) variation.Except this it
Outside, no-oxygen copper plate is made with preparation method same as said sample 1, condition.They are set to sample 2~20.
Total degree of finish of the composition of the no-oxygen copper plate of sample 1~20, final cold rolling is summarized and is shown in following tables 2.2 institute of table
The addition element concentration shown is the concentration point of the addition element obtained by high-frequency induction coupled plasma ICP Atomic Emission Spectrophotometer method
Analyse result.
[table 2]
<evaluation>
For sample 1~20, carry out respectively thick using the crystal after 2 θ/θ method X-ray diffraction measure, high-temperature heating
The evaluation of electric conductivity after the evaluation changed greatly, high-temperature heating.
(using 2 θ/θ method X-ray diffraction measure)
In each sample of sample 1~20, the rolling surface of each sample is carried out using 2 θ/θ method X-ray diffraction measure.
Said determination uses the X-ray diffraction device (type: Ultima IV) of Co., Ltd. Rigaku, the item shown in following table 3
It is carried out under part.
[table 3]
| Setting item | Condition |
| To cathode | Cu |
| Tube voltage | 40kV |
| Tube current | 40kA |
| Mode determination | 2θ/θ |
| It measures angular range (2 θ) | 40 °~140 ° |
| Measure step width | 0.01° |
| Finding speed | 2 °/minute |
| Divergent slit | 2/3° |
| Scatter slit | 2/3° |
| Dissipate longitudinal slit | 10mm |
| By optical slits | 0.6mm |
| Specimen size | 50mm×50mm |
Each sample is shown in table 4 measures { 022 } face, { 002 } by using 2 θ/θ method X-ray diffraction measure
Diffraction peak intensity (the I in face, { 113 } face, { 111 } face and { 133 } face{022}、I{002}、I{113}、I{111}、I{133}).In addition, using
The value of these diffraction peak intensities calculates the various value in above-mentioned formula (1)~(12).These calculating results are shown in Table 4.
[table 4]
As shown in table 4, for sample 1~20, it can be confirmed that the diffraction peak intensity of each crystal face is respectively different.Thus, it can be known that
By making the degree of finish of every 1 passage and the change in location of neutral point, make the compression stress that rolled material is applied to when final cold rolling
Intensity, the intensity of tensile stress, stress component variation, each crystalline substance in { 022 } face in no-oxygen copper plate and secondary orientation can be changed
The ratio of the crystal in face.
(the coarsening evaluation of crystal after high-temperature heating)
The coarsening evaluation of crystal after high-temperature heating is carried out by following steps.Firstly, being cut out respectively from sample 1~20
The test film of 20mm square heats these test films 10 minutes in nitrogen atmosphere under the conditions of 900 DEG C of temperature.Using grinding
Until the rolling surface that mill paper and alumina abrasive grain are ground each sample after heating becomes mirror surface, then had with addition
The ammonium hydroxide of hydrogen oxide is etched the surface of each sample and the rolling surface of each sample is made crystal crystal boundary occur.About there is crystalline substance
Each sample of body crystal boundary measures crystal particle diameter (average crystal particle diameter) using the process of chopping of JISH0501 defined.By crystal grain
The measurement result of diameter is shown in following tables 5.In addition, be that 0.4mm sample below is determined as qualified (zero) by crystal particle diameter, it will
Crystal particle diameter is more than that the sample of 0.4mm is determined as unqualified (×), which is also depicted in following tables 5.
[table 5]
By sample 1~12,16~20 it has been confirmed that being able to suppress high-temperature heating by meeting formula (1)~(12) whole
Caused crystal coarsening.
The sample 2 of (almost without elements such as addition Sn) low for the concentration of the elements such as Sn, can be confirmed and the elements such as Sn
Concentration be 50ppm or more sample 1,3~12,16~20 compare, the crystal particle diameter after high-temperature heating becomes larger.It therefore can be true
Recognize, can certainly inhibit crystal coarsening caused by being heated at high temperature when being added to the elements such as Sn.
For sample 13, can be confirmed due to being unsatisfactory for formula (1)~(12) whole, by being heated at high temperature crystal
Coarsening.For sample 13, it is known that due to I{022}、I{002}、I{113}Value it is high, therefore be applied in final cold rolling rolled
Intensity, the compression component ratio of the compression stress of material are high.Can confirm, though total degree of finish of final cold rolling be 80% with
Under, according to the condition of the position of the degree of finish of every 1 passage of final cold rolling and neutral point, it is applied to the compression stress of rolled material
Intensity, the intensity of tensile stress, the ratio of stress component can also change, as a result, being unsatisfactory for formula (1)~(12) sometimes.
By sample 14 it has been confirmed that if total degree of finish of final cold rolling less than 40%, even if meeting above-mentioned formula (1)
In the case where the whole of~(12), it cannot also inhibit crystal coarsening caused by being heated at high temperature sometimes.It is thought that because, anaerobic
The generation frequency for the recrystallization nucleus that copper sheet is generated by high-temperature heating and when recrystallizing is low.
By sample 15 it has been confirmed that being unsatisfactory for above-mentioned formula (1) sometimes if total degree of finish of final cold rolling is more than 80%
The whole of~(12), or crystal coarsening caused by being heated at high temperature cannot be inhibited sometimes.It knows in this case, due to I{022}'s
Value is high, therefore passes through a large amount of Crystal Rotations of final cold rolling to { 022 } face.
(evaluation of the electric conductivity after high-temperature heating)
The evaluation of electric conductivity after high-temperature heating is carried out by following steps.Firstly, cutting out 50mm respectively from sample 1~20
The test film of square heats these test films 10 minutes in nitrogen atmosphere under the conditions of 900 DEG C of temperature.Moreover, using
The overflow-type conductivity meter Sigmatest of Foerster corporation, the conductivity of each test film after measurement heating.By conductivity
Measurement result be shown in above-mentioned table 5.In addition, the sample that conductivity is 100%IACS or more is determined as excellent (◎), it will be conductive
Rate is determined as good (zero) more than and less than the sample of 100%IACS for 95%IACS, which is also depicted in above-mentioned table 5.
By table 5 it has been confirmed that for sample 1~15, if the concentration of the elements such as Sn in no-oxygen copper plate be 150ppm with
Under, then the electric conductivity for being able to suppress no-oxygen copper plate reduces.Can be confirmed such as no-oxygen copper plate conductivity become 100%IACS with
On.Such no-oxygen copper plate is preferred as the conductor of ceramic wiring board.
By table 5 it has been confirmed that for sample 16~20, if the concentration of the elements such as Sn in no-oxygen copper plate is more than
150ppm, then the conductivity of no-oxygen copper plate, which becomes, is less than 100%IACS, and the electric conductivity of no-oxygen copper plate reduces.
< preferred embodiment >
Hereinafter, being attached to preferred embodiment of the invention.
[note 1]
A scheme according to the present invention, provides a kind of no-oxygen copper plate, is formed as tabular by rolling,
And having the crystal face parallel with rolling surface is { 022 } face, { 002 } face, { 113 } face, { 111 } face and { 133 } face
Crystal,
The diffraction peak intensity of above-mentioned each crystal face obtained by X-ray diffraction measure will be carried out to the rolling face using 2 θ/θ method
It is set to I{022}、I{002}、I{113}、I{111}、I{133}When,
I{022}/(I{022}+I{002}+I{113}+I{111}+I{133})≤0.3,
(I{002}+I{113})/(I{111}+I{133}) >=1.0,
I{002}/I{022}>=1.0,
I{113}/I{022}>=0.5,
I{111}/I{022}>=0.15,
I{133}/I{022}>=0.02,
0.5≤I{002}/I{113}≤ 5.0,
0.2≤I{133}/I{111}≤ 0.5,
1.0≤I{113}/I{111}≤ 10,
1.0≤I{002}/I{111}≤ 20,
1.0≤I{002}/I{133}≤ 75,
1.0≤I{113}/I{133}≤ 30,
Heat under conditions of 900 DEG C the average crystal particle diameter after heat treatment in 10 minutes is 0.4mm or less.
[note 2]
The no-oxygen copper plate of note 1 is preferably comprised selected from by one or more of Sn, Zr, Mg, Ti and Ca group formed, residue
Part is made of copper and inevitable impurity.
[note 3]
The no-oxygen copper plate of note 1 or 2 is preferably 150ppm or less, preferably 50ppm or more 150ppm or less with total concentration
Mode include selected from by one or more of Sn, Zr, Mg, Ti and Ca group formed.
[note 4]
The no-oxygen copper plate of any one of note 1~3, preferably conductivity are 100%IACS or more.
[note 5]
According to another aspect of the present invention, a kind of manufacturing method of no-oxygen copper plate is provided, with following processes:
For material processed, pre-determined number is repeated in cold rolling and annealing and forms the cold rolling process of cold rolling material, and
The cold rolling that total degree of finish is 40% or more is carried out to above-mentioned cold rolling material, forms the final cold of flat no-oxygen copper plate
Roll process.
[note 6]
The method of note 5, preferably in above-mentioned final cold rolling process, carrying out total degree of finish is 40% or more 80% below
Cold rolling.
[note 7]
The method of note 5 or 6, preferably in above-mentioned final cold rolling process, by adjusting the degree of finish of each passage, to adjust
The intensity of the compression stress of rolled material, the intensity of tensile stress, the ratio of stress component are applied to by each passage.
[note 8]
The method of note 7 makes 20% or more the degree of finish of each passage preferably in above-mentioned final cold rolling process.
[note 9]
The method of any one of note 5~8, preferably in above-mentioned final cold rolling process, by adjusting the position of neutrality point
In at least any one, come adjust by each passage be applied to the intensity of compression stress of rolled material, tensile stress it is strong
The ratio of degree, stress component.
[note 10]
The method of note 9, preferably in above-mentioned final cold rolling process, the more thin then neutral point of thickness to be rolled material is offside
It is controlled in the mode of the outlet side of a pair of of Rolling roller.
[note 11]
The method of any one of note 5~10 forms no-oxygen copper plate preferably in above-mentioned final cold rolling process,
Above-mentioned no-oxygen copper plate have the crystal face parallel with rolling surface be { 022 } face, { 002 } face, { 113 } face, { 111 } face and
{ 133 } crystal in face,
The diffraction peak intensity of above-mentioned each crystal face obtained by X-ray diffraction measure will be carried out to the rolling face using 2 θ/θ method
It is set to I{022}、I{002}、I{113}、I{111}And I{133}When,
I{022}/(I{022}+I{002}+I{113}+I{111}+I{133})≤0.3,
(I{002}+I{113})/(I{111}+I{133}) >=1.0,
I{002}/I{022}>=1.0,
I{113}/I{022}>=0.5,
I{111}/I{022}>=0.15,
I{133}/I{022}>=0.02,
0.5≤I{002}/I{113}≤ 5.0,
0.2≤I{133}/I{111}≤ 0.5,
1.0≤I{113}/I{111}≤ 10,
1.0≤I{002}/I{111}≤ 20,
1.0≤I{002}/I{133}≤ 75,
1.0≤I{113}/I{133}≤ 30,
Heat under conditions of 900 DEG C the average crystal particle diameter after heat treatment in 10 minutes is 0.4mm or less.
[note 12]
The method of any one of note 5~11, preferably further with the process of cast billets, the ingot bar includes to be selected from
By one or more of Sn, Zr, Mg, Ti and Ca group formed.
[note 13]
The method of note 12 is 150ppm or less, preferably with concentration preferably in the process for casting above-mentioned ingot bar
50ppm or more 150ppm mode below is added selected from by one or more of Sn, Zr, Mg, Ti and Ca group formed.
[note 14]
According to the present invention and another scheme, provides a kind of ceramic wiring board, has:
Ceramic substrate and
As match wire rod no-oxygen copper plate,
The no-oxygen copper plate is formed as tabular and carrying out rolling processing to oxygen-free copper, and is arranged in above-mentioned ceramic base
On plate,
Above-mentioned no-oxygen copper plate have the crystal face parallel with rolling surface be { 022 } face, { 002 } face, { 113 } face, { 111 } face and
{ 133 } crystal in face,
The diffraction peak intensity of above-mentioned each crystal face obtained by X-ray diffraction measure will be carried out to the rolling face using 2 θ/θ method
It is set to I{022}、I{002}、I{113}、I{111}、I{133}When,
I{022}/(I{022}+I{002}+I{113}+I{111}+I{133})≤0.3,
(I{002}+I{113})/(I{111}+I{133}) >=1.0,
I{002}/I{022}>=1.0,
I{113}/I{022}>=0.5,
I{111}/I{022}>=0.15,
I{133}/I{022}>=0.02,
0.5≤I{002}/I{113}≤ 5.0,
0.2≤I{133}/I{111}≤ 0.5,
1.0≤I{113}/I{111}≤ 10,
1.0≤I{002}/I{111}≤ 20,
1.0≤I{002}/I{133}≤ 75,
1.0≤I{113}/I{133}≤ 30,
Average crystal particle diameter is 0.4mm or less.
Claims (5)
1. a kind of no-oxygen copper plate is formed as tabular by rolling,
And having the crystal face parallel with rolling surface is the crystal in { 022 } face, { 002 } face, { 113 } face, { 111 } face and { 133 } face,
The diffraction peak intensity for carrying out each crystal face obtained by X-ray diffraction measure to the rolling surface using 2 θ/θ method is distinguished
It is set as I{022}、I{002}、I{113}、I{111}、I{133}When,
I{022}/(I{022}+I{002}+I{113}+I{111}+I{133})≤0.3,
(I{002}+I{113})/(I{111}+I{133}) >=1.0,
I{002}/I{022}>=1.0,
I{113}/I{022}>=0.5,
I{111}/I{022}>=0.15,
I{133}/I{022}>=0.02,
0.5≤I{002}/I{113}≤ 5.0,
0.2≤I{133}/I{111}≤ 0.5,
1.0≤I{113}/I{111}≤ 10,
1.0≤I{002}/I{111}≤ 20,
1.0≤I{002}/I{133}≤ 75,
1.0≤I{113}/I{133}≤ 30,
Heat under conditions of 900 DEG C the average crystal particle diameter after heat treatment in 10 minutes is 0.4mm or less.
2. no-oxygen copper plate according to claim 1, it includes 1 kinds in the group being made of Sn, Zr, Mg, Ti and Ca
More than, remainder is made of copper and inevitable impurity.
3. no-oxygen copper plate according to claim 1 or 2, by total concentration be in a manner of 150ppm is below comprising selected from by
One or more of the group of Sn, Zr, Mg, Ti and Ca composition.
4. no-oxygen copper plate according to claim 1 or 2, by total concentration be packet in a manner of 50ppm or more 150ppm is below
Containing selected from by one or more of Sn, Zr, Mg, Ti and Ca group formed.
5. a kind of ceramic wiring board, has:
Ceramic substrate and
As match wire rod no-oxygen copper plate,
The no-oxygen copper plate is formed as tabular and carrying out rolling processing to oxygen-free copper, and is arranged in the ceramic substrate
On,
The no-oxygen copper plate have the crystal face parallel with rolling surface be { 022 } face, { 002 } face, { 113 } face, { 111 } face and
{ 133 } crystal in face,
The diffraction peak intensity for carrying out each crystal face obtained by X-ray diffraction measure to the rolling surface using 2 θ/θ method is distinguished
It is set as I{022}、I{002}、I{113}、I{111}、I{133}When,
I{022}/(I{022}+I{002}+I{113}+I{111}+I{133})≤0.3,
(I{002}+I{113})/(I{111}+I{133}) >=1.0,
I{002}/I{022}>=1.0,
I{113}/I{022}>=0.5,
I{111}/I{022}>=0.15,
I{133}/I{022}>=0.02,
0.5≤I{002}/I{113}≤ 5.0,
0.2≤I{133}/I{111}≤ 0.5,
1.0≤I{113}/I{111}≤ 10,
1.0≤I{002}/I{111}≤ 20,
1.0≤I{002}/I{133}≤ 75,
1.0≤I{113}/I{133}≤ 30,
Average crystal particle diameter is 0.4mm or less.
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| CN110241326A (en) * | 2019-06-05 | 2019-09-17 | 中南大学 | Alloying oxygen-free copper and preparation method thereof |
| CN111440962A (en) * | 2019-01-16 | 2020-07-24 | 日立金属株式会社 | Cu alloy sheet and method for producing same |
| CN115279929A (en) * | 2020-03-06 | 2022-11-01 | 三菱综合材料株式会社 | Pure copper plate, copper-ceramic junction body, and insulated circuit board |
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| WO2020162445A1 (en) | 2019-02-04 | 2020-08-13 | 三菱マテリアル株式会社 | Production method for copper/ceramic joined body, production method for insulated circuit board, copper/ceramic joined body, and insulated circuit board |
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Also Published As
| Publication number | Publication date |
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| CN108998692B (en) | 2020-10-30 |
| KR102104252B1 (en) | 2020-04-24 |
| JP2018204108A (en) | 2018-12-27 |
| KR20180133796A (en) | 2018-12-17 |
| JP7094151B2 (en) | 2022-07-01 |
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