CN105679683A - Copper nanorod based copper-tin-copper bonding process and structure - Google Patents

Copper nanorod based copper-tin-copper bonding process and structure Download PDF

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CN105679683A
CN105679683A CN201610024230.0A CN201610024230A CN105679683A CN 105679683 A CN105679683 A CN 105679683A CN 201610024230 A CN201610024230 A CN 201610024230A CN 105679683 A CN105679683 A CN 105679683A
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copper
photoresist
nanometer rods
bonding
bump
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CN105679683B (en
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廖广兰
独莉
史铁林
汤自荣
陈鹏飞
沈俊杰
邵杰
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Huazhong University of Science and Technology
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • 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
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
    • H01L23/49816—Spherical bumps on the substrate for external connection, e.g. ball grid arrays [BGA]
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    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods
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    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/8134—Bonding interfaces of the bump connector
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    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/818—Bonding techniques
    • H01L2224/81894—Direct bonding, i.e. joining surfaces by means of intermolecular attracting interactions at their interfaces, e.g. covalent bonds, van der Waals forces
    • H01L2224/81895—Direct bonding, i.e. joining surfaces by means of intermolecular attracting interactions at their interfaces, e.g. covalent bonds, van der Waals forces between electrically conductive surfaces, e.g. copper-copper direct bonding, surface activated bonding
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    • H01L2924/0105—Tin [Sn]

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Abstract

The invention discloses a copper nanorod based copper-tin-copper bonding process and structure. The process comprises the following steps of sequentially depositing an insulation layer, an adhesion layer and a seed layer on the surface of a substrate; spin-coating a layer of photoresist on the seed layer, and fabricating round holes in the photoresist; electroplating copper in the round holes to obtain copper convex points; removing the photoresist, and removing the exposed seed layer and the exposed adhesive layer; spin-coating the photoresist on the surfaces and the peripheries of the copper convex points, and exposing the upper surfaces of the copper convex points; electroplating tin convex points on the copper convex points of one of two substrate units obtained according to the above steps, and removing the photoresist; depositing copper nanorods on the copper convex points of the other substrate unit, and removing the photoresist; and bonding the two substrate units by a hot-pressing mode. The copper-tin-copper bonding structure is acquired according to the bonding process. According to the bonding process and the bonding structure, the copper nanorods are applied to copper-tin-copper bonding, the bonding temperature can be effectively reduced, and a tight bonding surface is obtained; and the preparation process is simple and controllable, is low in cost, and has great application value.

Description

A kind of copper stannum copper bonding technology based on copper nanometer rods and structure
Technical field
The invention belongs to technical field of micro-nano manufacture, more particularly, to a kind of copper stannum copper bonding technology based on copper nanometer rods and structure.
Background technology
The change constantly causing each field product create society's new demand of growing continuously and fast of integrated circuit (IC), plays the supporting role of key at key areas such as national security, high-end manufacture, network communications. Along with characteristic size enters into 20/14nm technology node, it is clear that IC manufactures the front road technique technology path based on extreme ultraviolet photolithographic, interconnecting microchannel intensive in a large number occurs, trigger the comprehensive change in post-channel interconnection mode and encapsulation technology, the three-dimensionally integrated inevitable choice becoming boost device performance and cost performance.
Three-dimensionally integrated is by the integrated chip of difference in functionality a to system, realizes three dimensions perpendicular interconnection by intensive microchannel between chip, and wherein, micro convex point interconnection is three-dimensionally integrated key technology. Along with the increase of packaging density and the further of characteristic size reduce, micro convex point size constantly reduces, bonded interface thickness is also required to further reduction, low-temperature bonding technology is owing to can reduce bonding temperature and pressure, the demand of satisfied temperature Sensitive Apparatus, the development trend new by becoming three-dimensionally integrated interconnection.
Copper stannum copper eutectic bonding is a kind of mode of low temperature interconnection, and it utilizes refractory metal (copper) and low-melting-point metal (stannum) and solidifying for alloy lower than fusion under eutectic temperature, is bonded together needing the device connected. Above-mentioned connected mode, due to the prescription on para-linkage surface when the existence of low-melting-point metal reduces bonding, without the need for high vacuum environment and annealing process, is therefore used widely in three-dimensionally integrated. But, the bonding temperature of this technology is generally 260～320 DEG C at present, slightly above the fusing point of stannum, how to improve this technology and is still a challenge with the further requirement reducing interconnection temperature and para-linkage environment.
Summary of the invention
Disadvantages described above or Improvement requirement for prior art, the invention provides a kind of copper stannum copper bonding technology based on copper nanometer rods and structure, wherein obtain copper nanometer rods by oblique sputtering in copper bump surface deposition, this copper nanometer rods is directly applied to copper stannum copper bonding, utilize the low melting point of copper nanometer rods and stannum, and the surface high activity of copper nanometer rods, to reduce bonding temperature, and reduce the requirement of para-linkage environment, this technique and structure preparation technology are simply controlled, favorable repeatability, it is not necessary to complicated equipment, cost is low, has great using value.
For achieving the above object, according to one aspect of the present invention, it is proposed that a kind of copper stannum copper bonding technology based on copper nanometer rods, this technique comprises the steps:
1) it is sequentially depositing insulating barrier, adhesion layer and Seed Layer at substrate surface;
2) spin coating one layer photoetching glue in described Seed Layer, and on described photoresist, make circular hole;
3) electro-coppering in described circular hole, obtains copper bump;
4) remove described photoresist, utilize wet method or dry corrosion process to remove the Seed Layer and adhesion layer exposed;
5) at copper bump surface and surrounding spin coating one layer photoetching glue, photoetching process is utilized to expose the upper surface of copper bump;
6) step 1 is utilized)～5) obtain two groups of identical substrate unit of structure, the copper bump upper surface electrotinning salient point of one group of substrate unit wherein, and remove photoresist; Copper bump upper surface in another group substrate unit utilizes oblique sputtering method deposition copper nanometer rods, and removes photoresist;
7) by hot pressing mode, described stannum salient point is bonded with described copper nanometer rods; In this way, it is achieved the bonding of two groups of substrate unit.
As it is further preferred that described circular hole is one or more, the diameter of single circular hole is 5 μm～200 μm.
As it is further preferred that described step 3) in, the height of copper bump is not more than photoresist thickness.
As it is further preferred that described step 5) in, photoresist thickness is more than copper bump height.
As it is further preferred that described step 6) in, during deposition copper nanometer rods, the angle of substrate and target is 85 °, and sputtering time is 20min～40min; The diameter of described copper nanometer rods is 100nm～200nm, and vertical direction height is 300nm～600nm.
As it is further preferred that described step 7) in, the temperature of bonding is 60 DEG C～400 DEG C, and pressure is 0.1MPa～20MPa, and the time is 1min～60min, and bonding environment is vacuum, noble gas or air ambient.
According to another aspect of the present invention, provide a kind of copper stannum copper bonding structure based on copper nanometer rods, described bonding structure includes two groups of identical substrate unit of structure, described substrate unit includes substrate and is sequentially deposited at the insulating barrier of described substrate surface, adhesion layer and Seed Layer, and described Seed Layer is electroplate with copper bump; Being electroplate with stannum salient point on the described copper bump of one of which substrate unit, the described copper bump of another group substrate unit utilizes oblique sputtering method deposition have copper nanometer rods, described stannum salient point and copper nanometer rods are bonded by hot pressing mode.
As it is further preferred that described copper bump obtains in the following way: spin coating one layer photoetching glue in described Seed Layer, and on described photoresist, make circular hole; Electro-coppering in described circular hole, obtains described copper bump.
As it is further preferred that electrotinning salient point on described copper bump in the following way: first, remove described photoresist, utilize wet method or dry corrosion process to remove the Seed Layer and adhesion layer exposed; Then, at described copper bump surface and surrounding spin coating one layer photoetching glue, utilize photoetching process to expose the upper surface of copper bump; Finally, at the upper surface electrotinning salient point of described copper bump, and photoresist is removed.
As it is further preferred that deposit copper nanometer rods in the following way on described copper bump: first, remove described photoresist, utilize wet method or dry corrosion process to remove the Seed Layer and adhesion layer exposed; Then, at described copper bump surface and surrounding spin coating one layer photoetching glue, utilize photoetching process to expose the upper surface of copper bump; Finally, described copper bump deposits copper nanometer rods, and removes photoresist.
In general, by the contemplated above technical scheme of the present invention compared with prior art, copper nanometer rods is applied to the copper stannum copper towards three-dimensional micro-interconnection and is bonded, significantly reduce bonding temperature and for being bonded the requirement of environment, have the advantages that
1. utilize electroplating technology to prepare copper/stannum salient point, salient point pitch, diameter and highly controllable, process window width, it is advantageously implemented the micro convex point interconnection of three-dimensional high-density ultra fine-pitch.
2. utilizing magnetron sputtering method to prepare copper nanometer rods in the way of oblique sputtering, compare traditional preparation nanostructured technique (such as chemical vapour deposition (CVD), femto-second laser pulse deposition, hydro-thermal method etc.), technique is simpler controlled, reproducible.
3. utilize special nature such as low melting point, high surface etc. that nano material shows; copper nanometer rods is applied to copper stannum copper bonding technology; compared with traditional copper stannum copper eutectic bonding technique; the temperature that can significantly reduce bonding (is down to below the fusing point of stannum and still can be obtained close bonded interface; minimum it is down to 60 DEG C); and the requirement for being bonded environment also becomes more loose (being down to air ambient from traditional vacuum or noble gas); thus reduce thermal deformation and thermal stress that bonding process produces, be conducive to protection device.
4. the copper nanorod surfaces that prepared by the present invention has more small copper nanostructured (diameter is about 10nm-20nm), small size nanostructured contributes to reducing further the fusing point of copper nanometer rods, improve surface activity, promote the diffusion of copper atom and tin atom in bonding process, be conducive to obtaining bonded interface more closely, improve bonding quality.
Accompanying drawing explanation
Fig. 1 (a) has on the substrate of insulating barrier, adhesion layer, Seed Layer spin coating photoresist making borehole structure schematic diagram on a photoresist in deposition;
Fig. 1 (b) is electro-coppering micro convex point remove unnecessary adhesion layer and seed layer structure schematic diagram in borehole structure;
Fig. 1 (c) is at copper bump surface spin coating one layer photoetching glue, utilizes photoetching process to expose copper bump schematic diagram;
Fig. 1 (d) is at one group of tin plating salient point of copper bump surface electrical the schematic diagram that removes photoresist;
Fig. 1 (e) is at another group copper bump surface sputtering copper nanometer rods the schematic diagram that removes photoresist;
Fig. 1 (f) is the schematic diagram that two groups of substrates carry out thermocompression bonding;
Fig. 2 (a) and (b) are the SEM figure of the copper nanometer rods that magnetron sputtering obtains.
Fig. 3 is bonding temperature be the bonded interface obtained at 60 DEG C SEM figure.
Fig. 4 is bonding temperature be the bonded interface obtained at 200 DEG C SEM figure.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated. Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention. As long as just can be mutually combined additionally, technical characteristic involved in each embodiment of invention described below does not constitute conflict each other.
As shown in Fig. 1 (a)～(f), the copper stannum copper bonding technology based on copper nanometer rods of the embodiment of the present invention, comprise the steps:
(1) insulating barrier 2, adhesion layer 3 and Seed Layer 4 it are sequentially depositing on the surface of substrate 1.
Wherein, the material of insulating barrier 2 is selected from silicon dioxide, silicon nitride, aluminium sesquioxide, polyimides, Parylene, polybenzocyclobutene or photoresist, and the mixture of above-mentioned material or complex, and the mode preferably employing thermal oxide, physical vapor deposition (PVD) or chemical vapor deposition (CVD) formed; The material of adhesion layer 3 is titanium, titanium-tungsten (Ti-W), titanium-titanium nitride (Ti-TiN) or tantalum-tantalum nitride (Ta-TaN), and the modes such as atomic layer deposition (ALD), physical vapor deposition (PVD) or chemical vapor deposition (CVD) that preferably employ are formed; Seed Layer 4 is that the material such as copper (Cu) or gold (Au) is constituted, and the mode preferably employing chemical plating, electrochemistry grafting, atomic layer deposition (ALD), physical vapor deposition (PVD) or chemical vapor deposition (CVD) is formed.
(2) spin coating one layer photoetching glue 5 in Seed Layer 4, and on photoresist 5, make circular hole.
Wherein, circular hole can be one or more, and the arrangement on photoresist 5 can be face formation, surrounding type, external or arbitrarily arrange. Preferably, the diameter of circular hole is 5 μm～200 μm, and photoresist height is 5 μm～100 μm.
(3) electro-coppering in circular hole, obtains copper bump 6, and the height of copper bump 6 is not more than the thickness of photoresist 4. Preferably, the height of copper bump 6 is 5 μm～50 μm.
(4) Seed Layer and the adhesion layer of remaining photoresist and exposure are removed.
Wherein, the removal of photoresist is preferably removed photoresist the mode of liquid or acetone soak; The mode removing preferred wet etching or dry etching of Seed Layer and adhesion layer, the so-called Seed Layer exposed and adhesion layer refer to the part that Seed Layer and adhesion layer are not covered by copper bump, after the Seed Layer exposed and adhesion layer are removed, remaining Seed Layer is identical with the horizontal cross-sectional area of copper bump with the horizontal cross-sectional area of adhesion layer part.
(5) at copper bump surface and surrounding spin coating one layer photoetching glue, utilizing photoetching process to expose the upper surface of copper bump, protect all the other regions simultaneously, namely only remove the photoresist of copper bump upper surface, the photoresist at other positions is not removed; Wherein, photoresist thickness is more than copper bump height.
Preferably, the thickness of photoresist 5 is 7 μm～100 μm.
(6) utilizing above-mentioned steps (1)～(5) to obtain two groups of identical substrate unit of structure, the tin plating salient point of copper bump surface electrical of one group of substrate unit also removes the photoresist of remnants; Another group substrate unit utilizes magnetron sputtering method in copper bump copper-depositing on surface nanometer rods in the way of oblique sputtering, and removes the photoresist of remnants.
Preferably, the height of stannum salient point 7 is 2 μm～20 μm; During sputtering copper nanometer rods, substrate to be sputtered is 85 ° with cathode targets angle (upper surface of copper bump 6 and the angle of target), its be different from conventional magnetron sputtering in substrate parallel with target, sputtering time 20min～40min, nanorod diameter 100nm～the 200nm obtained, vertical direction height 300nm～600nm.
(7) by hot pressing mode, two groups of substrate unit are bonded.
Preferably, bonding technology is as follows: bonding temperature is 60 DEG C～400 DEG C, and pressure is 0.1MPa～20MPa, and the time is 1min～60min, and bonding environment is vacuum environment, inert gas environment or air ambient.
Such as Fig. 1 (f), a kind of copper stannum copper bonding structure based on copper nanometer rods of the embodiment of the present invention, it includes two groups of identical substrate unit of structure, this substrate unit includes substrate 1 and is sequentially deposited at the insulating barrier 2 on substrate 1 surface, adhesion layer 3 and Seed Layer 4, and Seed Layer 4 is electroplate with copper bump 6; The copper bump 6 of one of which substrate unit is electroplate with stannum salient point 7, the copper bump 6 of another group substrate unit utilizes oblique sputtering method deposition have copper nanometer rods 8, stannum salient point 7 and copper nanometer rods 8 to be bonded by hot pressing mode.
Preferably, copper bump 6 obtains in the following way:
Spin coating one layer photoetching glue 5 in Seed Layer 4, and on photoresist 5, make circular hole; Electro-coppering in circular hole, obtains copper bump 6.
Preferably, electrotinning salient point 7 on copper bump 6 in the following way:
First, remove photoresist, utilize wet method or dry corrosion process to remove the Seed Layer 4 and adhesion layer 3 exposed; Then, at copper bump 6 surface and surrounding spin coating one layer photoetching glue, utilize photoetching process to expose the upper surface of copper bump 6;Finally, at the upper surface electrotinning salient point 7 of copper bump 6, and photoresist is removed.
Preferably, on copper bump 6, copper nanometer rods 8 is deposited in the following way:
First, remove photoresist, utilize wet method or dry corrosion process to remove the Seed Layer 4 and adhesion layer 3 exposed; Then, at copper bump 6 surface and surrounding spin coating one layer photoetching glue, utilize photoetching process to expose the upper surface of copper bump 6; Finally, copper bump 6 deposits copper nanometer rods 8, and removes photoresist.
It is below specific embodiment:
Embodiment 1
Copper stannum copper bonding technology based on copper nanometer rods comprises the steps:
(1) thermal oxide is utilized to deposit a layer insulating SiO at clean substrate surface2, thickness is 50nm; Be sequentially depositing adhesion layer Ti and Seed Layer Cu followed by magnetron sputtering, thickness is 20nm and 50nm respectively.
(2) at the PR1-4000A positive photoresist that spin coating thickness in Seed Layer surface is 5 μm, use the pattern mask containing face formation circular hole, circular hole region printing opacity, the diameter of circular hole is 5 μm, center of circular hole is from for 10 μm, adopt MA6 contact photoetching machine to carry out photoetching, and dry up with deionized water rinsing and by nitrogen gun after using RD6 developer solution to develop.
(3) being put in plating solution for copper-plating used by the figure being lithographically derived and electroplate, plating solution for copper-plating used selects Xin Yang company SYSB2210 salient point plating solution for copper-plating used, and electroplating current density is 10ASD, and obtaining is highly the copper bump of 5 μm.
(4) substrate of electro-coppering is put into the photoresist removing remnants in acetone, dries up with deionized water rinsing and by nitrogen gun after photoresist is removed completely; Wet etching method is utilized to remove the Seed Layer (Cu) and adhesion layer (Ti) exposed, including the substrate that will obtain at Ti corrosive liquid (HF:H2O2: H2O=1:1:20) 20s is stopped in, then with deionized water rinsing; Put it into (H in Cu etching liquid subsequently2O2: HCl:H2O=1:3:6) stop 40s, then dry up with deionized water rinsing and by nitrogen gun.
(5) it is being electroplate with the PR1-4000A positive photoresist that spin coating thickness in surface is 7 μm of copper bump, is adopting MA6 contact photoetching machine to carry out alignment, and drying up with deionized water rinsing and by nitrogen gun after using RD6 developer solution to develop.
(6) substrate unit utilizing above-mentioned steps to obtain is divided into two groups, one of which substrate unit is put in Tin plating electrolyte and is electroplated, Tin plating electrolyte selects Xin Yang company SYSB2250 salient point Tin plating electrolyte, electroplating current density is 3ASD, obtaining is highly the stannum salient point of 2 μm, put it in acetone the photoresist removing remnants afterwards, dry up with deionized water rinsing and by nitrogen gun after photoresist is removed completely; Another group substrate unit utilizes magnetron sputtering in copper bump upper surface inclined sputter deposition copper nanometer rods, and during sputtering copper nanometer rods, print and target angle are 85 °, sputtering time 40min. Fig. 2 (a) and (b) respectively sputter surface and the transverse section SEM figure of the copper nanometer rods obtained, can be seen that nanometer rods and substrate are certain angle of inclination, nanorod diameter is about 200nm, vertical direction height is about 600nm, and nanorod surfaces is covered with the small Cu nanostructured of diameter 10nm～20nm simultaneously.
(7) by hot pressing mode, two groups of substrate unit being bonded, the temperature of bonding is 60 DEG C, and pressure is 20MPa, and the time is 60min, and bonding environment is vacuum. As it is shown on figure 3, as seen from the figure, upper and lower two substrates achieve compact siro spinning technology to bonded interface, and bonded interface does not have the defects such as obvious hole or crackle.Owing to bonding temperature is relatively low, only part Sn and Cu reacts and generates intermetallic compound Cu6Sn5, therefore the structure of bonded interface is Cu/Cu6Sn5/Sn/Cu6Sn5/Cu。
Embodiment 2
Copper stannum copper bonding technology based on copper nanometer rods comprises the steps:
(1) thermal oxide is utilized to deposit a layer insulating SiO at clean substrate surface2, thickness is 50nm; Be sequentially depositing adhesion layer TiW and Seed Layer Cu followed by magnetron sputtering, thickness is 50nm and 100nm respectively.
(2) at the PR1-12000A positive photoresist that spin coating thickness in Seed Layer surface is 20 μm, use the pattern mask containing face formation circular hole, circular hole region printing opacity, the diameter of circular hole is 50 μm, center of circular hole is from for 100 μm, adopt MA6 contact photoetching machine to carry out photoetching, and dry up with deionized water rinsing and by nitrogen gun after using RD6 developer solution to develop.
(3) being put in plating solution for copper-plating used by the figure being lithographically derived and electroplate, plating solution for copper-plating used selects Xin Yang company SYSB2210 salient point plating solution for copper-plating used, and electroplating current density is 10ASD, and obtaining is highly the copper bump of 15 μm.
(4) substrate of electro-coppering is put into the photoresist removing remnants in acetone, dries up with deionized water rinsing and by nitrogen gun after photoresist is removed completely; Wet etching method is utilized to remove the Seed Layer (Cu) and adhesion layer (TiW) exposed, including the substrate that will obtain at TiW corrosive liquid (HF:HNO3: H2O=1:1:50) 30s is stopped in, then with deionized water rinsing; Put it into (H in Cu etching liquid subsequently2O2: HCl:H2O=1:3:6) stop 40s, then dry up with deionized water rinsing and by nitrogen gun.
(5) it is being electroplate with the PR1-12000A positive photoresist that spin coating thickness in surface is 20 μm of copper bump, is adopting MA6 contact photoetching machine to carry out alignment, and drying up with deionized water rinsing and by nitrogen gun after using RD6 developer solution to develop.
(6) above-mentioned steps is utilized to obtain two groups of substrate unit, one of which substrate unit is put in Tin plating electrolyte and is electroplated, Tin plating electrolyte selects Xin Yang company SYSB2250 salient point Tin plating electrolyte, electroplating current density is 3ASD, obtaining is highly the stannum salient point of 5 μm, put it in acetone the photoresist removing remnants afterwards, dry up with deionized water rinsing and by nitrogen gun after photoresist is removed completely; Another group substrate unit utilizes magnetron sputtering in copper bump surface inclined deposition copper nanometer rods, and during sputtering copper nanometer rods, print and target angle are 85 °, and sputtering time 30min, the nanorod diameter obtained is about 150nm, and vertical direction height is 500nm.
(7) by hot pressing mode, two groups of substrates being bonded, the temperature of bonding is 200 DEG C, and pressure is 10MPa, and the time is 30min, and bonding environment is nitrogen atmosphere. As shown in Figure 4, upper and lower two substrates achieve compact siro spinning technology to bonded interface, and bonded interface does not have the defect such as hole or crackle. At this temperature, Sn and Cu fully reacts generation intermetallic compound Cu3Sn, therefore bonded interface structure is Cu/Cu3Sn/Cu。
Embodiment 3
Copper stannum copper bonding technology based on copper nanometer rods comprises the steps:
(1) chemical vapour deposition (CVD) (CVD) is utilized to deposit a layer insulating Si at clean substrate surface3N4, thickness is 100nm; Be sequentially depositing adhesion layer Ti and Seed Layer Cu followed by magnetron sputtering, thickness is 50nm and 200nm respectively.
(2) at the NR26-25000P negative photoresist that spin coating thickness in Seed Layer surface is 50 μm, use the pattern mask containing surrounding type circular hole, circular hole region is light tight, the diameter of circular hole is 100 μm, center of circular hole is from for 400 μm, adopt MA6 contact photoetching machine to carry out photoetching, and dry up with deionized water rinsing and by nitrogen gun after using RD6 developer solution to develop.
(3) being put in plating solution for copper-plating used by the figure being lithographically derived and electroplate, plating solution for copper-plating used selects Xin Yang company SYSB2210 salient point plating solution for copper-plating used, and electroplating current density is 10ASD, and obtaining is highly the copper bump of 30 μm.
(4) substrate of electro-coppering is put into the photoresist removing remnants in acetone, dries up with deionized water rinsing and by nitrogen gun after photoresist is removed completely; Wet etching method is utilized to remove the Seed Layer (Cu) and adhesion layer (Ti) exposed, including the substrate that will obtain at Ti corrosive liquid (HF:H2O2: H2O=1:1:20) 40s is stopped in, then with deionized water rinsing; Put it into (H in Cu etching liquid subsequently2O2: HCl:H2O=1:3:6) stop 60s, then dry up with deionized water rinsing and by nitrogen gun.
(5) it is being electroplate with the NR26-25000P negative photoresist that spin coating thickness in surface is 50 μm of copper bump, is adopting MA6 contact photoetching machine to carry out alignment, and drying up with deionized water rinsing and by nitrogen gun after using RD6 developer solution to develop.
(6) substrate utilizing above-mentioned steps to obtain is divided into two groups, one of which substrate is put in Tin plating electrolyte and is electroplated, Tin plating electrolyte selects Xin Yang company SYSB2250 salient point Tin plating electrolyte, electroplating current density is 3ASD, obtaining is highly the stannum salient point of 10 μm, put it in acetone the photoresist removing remnants afterwards, dry up with deionized water rinsing and by nitrogen gun after photoresist is removed completely; Another group substrate utilizes magnetron sputtering deposition copper nanometer rods, and during sputtering copper nanometer rods, print and target angle are 85 °, and sputtering time 30min, the nanorod diameter obtained is about 150nm, and vertical direction height is 500nm.
(7) by hot pressing mode, two groups of substrates being bonded, the temperature of bonding is 300 DEG C, and pressure is 0.1MPa, and the time is 10min, and bonding environment is nitrogen protection.
Embodiment 4
Copper stannum copper bonding technology based on copper nanometer rods comprises the steps:
(1) chemical vapour deposition (CVD) (CVD) is utilized to deposit a layer insulating Si at clean substrate surface3N4, thickness is 100nm; Be sequentially depositing adhesion layer Ti and Seed Layer Cu followed by magnetron sputtering, thickness is 50nm and 200nm respectively.
(2) at the NR26-25000P negative photoresist that spin coating thickness in Seed Layer surface is 100 μm, use the pattern mask containing surrounding type circular hole, circular hole region is light tight, the diameter of circular hole is 200 μm, center of circular hole is from for 600 μm, adopt MA6 contact photoetching machine to carry out photoetching, and dry up with deionized water rinsing and by nitrogen gun after using RD6 developer solution to develop.
(3) being put in plating solution for copper-plating used by the figure being lithographically derived and electroplate, plating solution for copper-plating used selects Xin Yang company SYSB2210 salient point plating solution for copper-plating used, and electroplating current density is 10ASD, and obtaining is highly the copper bump of 50 μm.
(4) substrate of electro-coppering is put into the photoresist removing remnants in acetone, dries up with deionized water rinsing and by nitrogen gun after photoresist is removed completely; The method utilizing dry etching removes the Seed Layer (Cu) and adhesion layer (Ti) that expose.
(5) it is being electroplate with the NR26-25000P negative photoresist that spin coating thickness in surface is 100 μm of copper bump, is adopting MA6 contact photoetching machine to carry out alignment, and drying up with deionized water rinsing and by nitrogen gun after using RD6 developer solution to develop.
(6) substrate utilizing above-mentioned steps to obtain is divided into two groups, one of which substrate is put in Tin plating electrolyte and is electroplated, Tin plating electrolyte selects Xin Yang company SYSB2250 salient point Tin plating electrolyte, electroplating current density is 3ASD, obtaining is highly the stannum salient point of 20 μm, put it in acetone the photoresist removing remnants afterwards, dry up with deionized water rinsing and by nitrogen gun after photoresist is removed completely;Another group substrate utilizes magnetron sputtering inclined sputter deposition copper nanometer rods, and during sputtering copper nanometer rods, print and target angle are 85 °, and sputtering time is 20min, and the nanorod diameter obtained is about 100nm, and vertical direction height is 300nm.
(7) by hot pressing mode, two groups of substrates being bonded, the temperature of bonding is 400 DEG C, and pressure is 1MPa, and the time is 1min, and bonding environment is air.
In sum, the present invention utilizes special nature such as low melting point, the high surface etc. that nano material shows, oblique sputtering method deposition copper nanometer rods is utilized on copper micro convex point surface, the requirement of interconnecting parts fusing point and para-linkage coplanarity is reduced again, it is achieved the low temperature copper stannum copper towards three-dimensional micro-interconnection is bonded based on copper nanometer rods. Compared with traditional copper stannum copper eutectic bonding technique, the temperature that can significantly reduce bonding (is down to below the fusing point of stannum and still can be obtained close bonded interface, minimum it is down to 60 DEG C), and the requirement for being bonded environment also becomes more loose (being down to air ambient from traditional vacuum or noble gas). Thus reduce thermal deformation and thermal stress that bonding process produces, be conducive to protection device. Simultaneously, owing to copper nanometer rods and the less nanostructured of surface size thereof have bigger surface activity, be conducive to promoting the diffusion of copper atom and tin atom in bonding process further, even if therefore at relatively low temperatures and pressures, also can realize high-quality bonding effect, towards the low-temperature bonding field of three-dimensional micro-interconnection, there is great using value.
Those skilled in the art will readily understand; the foregoing is only presently preferred embodiments of the present invention; not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.

Claims (10)

1. the copper stannum copper bonding technology based on copper nanometer rods, it is characterised in that this technique comprises the steps:
1) it is sequentially depositing insulating barrier, adhesion layer and Seed Layer at substrate surface;
2) spin coating one layer photoetching glue in described Seed Layer, and on described photoresist, make circular hole;
3) electro-coppering in described circular hole, obtains copper bump;
4) remove described photoresist, utilize wet method or dry corrosion process to remove the Seed Layer and adhesion layer exposed;
5) at copper bump surface and surrounding spin coating one layer photoetching glue, photoetching process is utilized to expose the upper surface of copper bump;
6) step 1 is utilized)～5) obtain two groups of identical substrate unit of structure, the copper bump upper surface electrotinning salient point of one group of substrate unit wherein, and remove photoresist; Copper bump upper surface in another group substrate unit utilizes oblique sputtering method deposition copper nanometer rods, and removes photoresist;
7) by hot pressing mode, described stannum salient point is bonded with described copper nanometer rods; In this way, it is achieved the bonding of two groups of substrate unit.
2. the copper stannum copper bonding technology based on copper nanometer rods as claimed in claim 1, it is characterised in that described circular hole is one or more, and the diameter of single circular hole is 5 μm～200 μm.
3. the copper stannum copper bonding technology based on copper nanometer rods as claimed in claim 1 or 2, it is characterised in that described step 3) in, the height of copper bump is not more than photoresist thickness.
4. the copper stannum copper bonding technology based on copper nanometer rods as described in any one of claims 1 to 3, it is characterised in that described step 5) in, photoresist thickness is more than copper bump height.
5. the copper stannum copper bonding technology based on copper nanometer rods as claimed in claim 4, it is characterised in that described step 6) in, during deposition copper nanometer rods, the angle of substrate and target is 85 °, and sputtering time is 20min～40min;The diameter of described copper nanometer rods is 100nm～200nm, and vertical direction height is 300nm～600nm.
6. the copper stannum copper bonding technology based on copper nanometer rods as claimed in claim 5, it is characterised in that described step 7) in, the temperature of bonding is 60 DEG C～400 DEG C, pressure is 0.1MPa～20MPa, and the time is 1min～60min, and bonding environment is vacuum, noble gas or air ambient.
7. the copper stannum copper bonding structure based on copper nanometer rods, it is characterized in that, described bonding structure includes two groups of identical substrate unit of structure, described substrate unit includes substrate (1) and is sequentially deposited at the insulating barrier (2) on described substrate (1) surface, adhesion layer (3) and Seed Layer (4), and described Seed Layer (4) is electroplate with copper bump (6); The described copper bump (6) of one of which substrate unit is electroplate with stannum salient point (7), utilizing oblique sputtering method deposition to have copper nanometer rods (8) on the described copper bump (6) of another group substrate unit, described stannum salient point (7) and copper nanometer rods (8) are bonded by hot pressing mode.
8. the copper stannum copper bonding structure based on copper nanometer rods as claimed in claim 7, it is characterized in that, described copper bump (6) obtains in the following way: in the upper spin coating one layer photoetching glue (5) of described Seed Layer (4), and make circular hole on described photoresist (5); Electro-coppering in described circular hole, obtains described copper bump (6).
9. the copper stannum copper bonding structure based on copper nanometer rods as claimed in claim 8, it is characterized in that, in the following way at the upper electrotinning salient point (7) of described copper bump (6): first, remove described photoresist, utilize wet method or dry corrosion process to remove the Seed Layer (4) and adhesion layer (3) exposed; Then, at described copper bump (6) surface and surrounding spin coating one layer photoetching glue, utilize photoetching process to expose the upper surface of copper bump (6); Finally, at upper surface electrotinning salient point (7) of described copper bump (6), and photoresist is removed.
10. the copper stannum copper bonding structure based on copper nanometer rods as claimed in claim 8, it is characterized in that, in the following way at described copper bump (6) upper deposition copper nanometer rods (8): first, remove described photoresist, utilize wet method or dry corrosion process to remove the Seed Layer (4) and adhesion layer (3) exposed; Then, at described copper bump (6) surface and surrounding spin coating one layer photoetching glue, utilize photoetching process to expose the upper surface of copper bump (6); Finally, at described copper bump (6) upper deposition copper nanometer rods (8), and photoresist is removed.
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