CN111816608B - Glass blind hole processing method - Google Patents
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- CN111816608B CN111816608B CN202010654067.2A CN202010654067A CN111816608B CN 111816608 B CN111816608 B CN 111816608B CN 202010654067 A CN202010654067 A CN 202010654067A CN 111816608 B CN111816608 B CN 111816608B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
- H01L21/76831—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers in via holes or trenches, e.g. non-conductive sidewall liners
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
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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
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/5329—Insulating materials
Abstract
The invention provides a glass blind hole processing method, which comprises a, deep hole etching; b. depositing an adhesion layer on the side wall of the deep hole: b1, dripping the high polymer solution on the surface of the glass substrate to ensure that the high polymer solution covers the surface of the glass substrate; b2, transferring the glass substrate to an environment with the pressure higher than the atmospheric pressure, and standing to fill the deep hole with the high polymer solution; b3, fixing the glass substrate on the turntable, wherein the center of the glass substrate deviates from the rotation center of the turntable, driving the turntable to rotate, and throwing away the high polymer solution on the surface of the glass substrate and in the deep hole; b4, drying to solidify the polymer solution remained on the surface of the glass substrate and the side wall of the deep hole, so as to form a polymer adhesion film; c. depositing a seed layer on the side wall; d. copper filling in the deep hole; e. surface CMP and RDL wiring fabrication. The TSV prepared by the method has high thermal-mechanical reliability and excellent electrical performance, can process deep holes with the aperture of 3 mu m and the depth of 45 mu m, and accords with the development trend of miniaturization of the TSV.
Description
Technical Field
The invention relates to the technical field of manufacturing of three-dimensional integrated packaging adapter plates, in particular to a method for processing blind holes in glass.
Background
3D packaging is the most mature type of integration in the industry today, mostly stacking bare chips or individually packaged chips together by packaging, and currently includes many different technologies, most of which are extensions of existing single chip packaging technologies to three dimensions. Interposer (Interposer), also known as Interposer or intermediate layer, is a new type of electronic substrate that enables interconnection between fine pitch I/O at the top die level and larger-sized large pitch I/O at the bottom package level. The glass adapter plate is a novel adapter plate, a plurality of glass blind holes are formed in the glass adapter plate, the glass blind holes (TGV) penetrate through a glass substrate to extend and interconnect, vertical integration is achieved, and meanwhile, the interconnection length is shortened, so that the size, the weight and the power consumption are reduced, and the glass adapter plate is the basis and the core of the existing 2.5D/3D integration technology.
Currently, large enterprises, universities or research institutions have conducted intensive research on various aspects of TGV, mainly focused on TGV manufacturing processes, TGV related electrical, thermo-mechanical reliability analysis, and proximity effects of TGV and CMOS devices, in order to control the cost of TGV and improve yield and productivity. Copper TGV has gained the most widespread use and attention for its excellent electrical properties, fast fill rate and excellent process compatibility, with a typical manufacturing process flow comprising the following steps: (a) deep hole etching on a glass substrate; (b) depositing an adhesion layer on the side wall of the deep hole; (c) depositing a copper barrier/copper seed layer on the sidewalls; (d) copper electroplating filling in the deep hole; (e) surface CMP and RDL wiring fabrication. As commercial applications of 2.5D/3D integration technology mature, the integration density of devices becomes higher, the integration number of TGVs becomes larger, the size becomes smaller, and the aspect ratio becomes higher. The size, especially the diameter, of the TGV greatly affects the electrical and mechanical reliability of the 3D interconnect and stack, and the smaller the diameter of the TGV, the shorter the delay, the smaller the stress from copper bumps, and the smaller the corresponding KOZ (Keep-out zone). Currently, challenges presented by TGV processing include: ultra-small diameter blind via sidewall adhesion layer deposition, ultra-small diameter blind via sidewall uniform copper barrier/copper seed layer deposition, and TGV studies with excellent high frequency transmission performance.
Aiming at the challenges of small-size and high-aspect-ratio TGV roughening, metallization and coaxial structure research and preparation, researchers at home and abroad develop related researches from material selection to process scheme and the like. In the aspect of sidewall insulation, the high polymer material has been widely focused and studied because of low dielectric loss, good insulation performance and conformality, and low elastic modulus property so that the high polymer material can be used as a stress buffer layer between a glass substrate and a metal conductor; in terms of metallization, research institutions focus on exploring deposition methods that meet the TGV miniaturization requirements starting from new deposition schemes such as wet processes; in the aspect of coaxial structure preparation, a research institution mainly adopts a novel central conductor structure to reduce the process difficulty and the cost.
In 2009, d.s.tezcan et al, IMEC (microelectronics research center) proposed a TGV fabrication process using high polymer deep trench isolation that provided us with new considerations for better implementation of the TGV filling process: the method comprises the steps of forming an annular channel on a substrate, then completing the complete filling of Epoxy resin (Epoxy) in the annular channel and the exposure of an etching window of a central silicon column respectively by using a traditional spin coating technology twice, then etching the silicon column, completing the filling of a central conductor and the patterning of a surface RDL, wherein a thick polymer adhesion layer can obviously reduce a coupling capacitance to improve electrical performance, and can absorb some stress caused by CTE mismatch between Cu in TGV and surrounding Si, so that the reliability of the TGV is improved. However, this flow scheme presents challenges in achieving complete filling of the glass annular grooves, requiring high surface roughness of the glass substrate and high glass TGV array density.
In order to solve the difficulty of completely filling the annular groove, in 2015, the electronic science industry adopts a grinder to polish the glass substrate, so that the roughness of the glass surface is increased, and the complete filling of the annular groove of the glass substrate is realized.
Compared with the manufacturing process of the adhesion layer of the TSV, the TGV is an insulating material, so that the process of growing the adhesion layer is completely omitted.
In 2014, to overcome the challenges of miniaturization of TGV faced by the conventional spin-coating process, the university of northeast japan and industry technology (AIST) integrated research institute sequentially proposed CVD technology to achieve TGV sidewall deposition of high polymer materials with low k and low Coefficient of Thermal Expansion (CTE). T.Fukushima at North China university utilizes two monomer gases of polyimide acid, namely 4, 4' -oxydianiline and Pyromellitic anhydride (Pyromellitic-anhydride) to carry out copolymerization reaction under high vacuum condition to form polyimide film. In addition, the film deposited by the method has low CTE, can well relieve copper bulges, has uniform bulge height, and is favorable for the follow-up CMP process. It is notable that the copolymerization reaction needs to be carried out under high vacuum conditions of 0.05 to 0.1Pa, the process cost is too high and the deposition rate is slow.
In 2015, in order to solve the challenges of depositing an adhesion layer/a seed layer in TGV and preparing a back adhesion layer caused by the reduction of size and the increase of depth-to-width ratio in the future TGV development process, the applicant provides a preparation method of an adapter plate containing high depth-to-width ratio TGV. The specific preparation process comprises the following steps: etching through holes on the front surface of the glass; side wall SiO 2 Or a polymer attachment layer deposition; preparing a front RDL; bonding the front surface of the glass with a carrier sheet with a release layer and a seed layer deposited on the surface; filling the through hole conductor by electroplating; preparing RDL and micro-bumps on the back surface of the glass; and finally scribing and debonding. The method can realize TGV preparation with the diameter ranging from 5 to 150 to 1 and the depth-to-width ratio ranging from 1:1 to 50:1, and can realize excellent electricityAnd (3) preparing the adapter plate with high mechanical property and high reliability. But this approach is difficult to implement in a post-via process because of the need to bond with the carrier to complete the conductor plating fill.
Therefore, the preparation scheme which not only meets the development trend of future TGV miniaturization and high-frequency application, but also has the advantages of high universality, low process temperature, compatibility with the traditional CMOS process and low cost is still lacking at present.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a glass blind hole processing method for realizing TGV preparation with high thermal-mechanical reliability, excellent electrical property and high aspect ratio.
The technical scheme adopted for solving the technical problems is as follows: the method for processing the blind hole of the glass comprises the following steps of
a. Deep hole etching;
b. depositing an adhesion layer on the side wall of the deep hole:
b1, dripping the high polymer solution on the surface of the glass substrate to ensure that the high polymer solution covers the surface of the glass substrate;
b2, transferring the glass substrate to an environment with the pressure lower than the atmospheric pressure, and standing to enable the polymer solution to fill the deep hole;
b3, fixing the glass substrate on the turntable, and driving the turntable to rotate by deviating the center of the glass from the rotation center of the turntable so as to throw away the high polymer solution on the surface of the glass substrate and in the deep hole;
b4, drying to solidify the polymer solution remained on the surface of the glass substrate and the side wall of the deep hole, so as to form a polymer adhesion film;
c. depositing a seed layer on the side wall;
d. copper filling in the deep hole;
e. surface CMP and RDL wiring fabrication.
Further, in the step b2, the glass substrate is transferred to an environment with the pressure of 50-150Pa, and is kept stand for 8-15min.
Further, in step b2, the glass substrate was transferred to an atmosphere at a pressure of 100Pa and allowed to stand for 10 minutes.
Further, in the step b1, the polymer solution is a PI-5J polyimide solution.
Further, step c comprises:
c1, adopting a tetramethyl ammonium hydroxide solution to carry out surface cleaning on the high polymer adhesion layer, then transferring the glass substrate into the tetramethyl ammonium hydroxide solution for infiltration, and carrying out cleavage reaction on polyimide rings on the surface layer of the adhesion layer to form a polyamic acid layer;
c2, transferring the glass substrate into a catalyst solution to perform ion adsorption and exchange reaction, wherein palladium ions in the catalyst solution and (CH) in the polyamic acid layer 3 ) 4 N + Ion reaction replacement is carried out, so that palladium ions are uniformly adsorbed on the surface of the adhesion layer to form a palladium catalytic layer;
and c3, electroless plating, and forming a nickel layer on the surface of the palladium catalytic layer.
Further, in step c3, the pH of the electroless nickel plating solution is 4.2-4.8.
Further, in step c1, after transferring the glass substrate to the tetramethylammonium hydroxide solution, the tetramethylammonium hydroxide solution is left to stand in an atmosphere of 50 to 300Pa for 5 to 10 minutes.
Further, in the step c3, the electroless plating temperature is 65-80 ℃.
In the step d, copper is filled in the deep hole in an electroplating mode, wherein the concentration of an accelerator in the electroplating solution is 11.5-15 mL/L, the concentration of an inhibitor is 9.5-15.5mL/L, and the concentration of a leveler is 4.7-5.4mL/L.
The beneficial effects of the invention are as follows: the high polymer material has the advantages of low dielectric constant, low Young's modulus, low cost and the like, has higher adhesion degree, higher deposition quality of a seed layer, lower parasitic capacitance, lower electric leakage, higher thermo-mechanical reliability and the like compared with the material without an adhesion layer, and can form a uniform adhesion layer on the TGV side wall through a simple process mode such as spin coating and the like. By standing in an environment lower than atmospheric pressure, the polymer solution can be promoted to fully enter the deep hole, then the excessive polymer solution is thrown away by utilizing centrifugal force, and a polymer adhesion layer is formed on the side wall of the deep hole and the surface of the glass substrate after the residual polymer solution is dried. The TGV prepared by the invention has high thermal-mechanical reliability and excellent electrical property, can process deep holes with the aperture of 3 mu m and the depth of 45 mu m, and accords with the development trend of miniaturization of the TGV.
Drawings
FIG. 1 shows the distribution of polymer solution on the surface of a sample after vacuum treatment under different conditions;
FIG. 2 shows the deposition results of the polymer on the side wall of each diameter glass blind hole after the vacuum treatment condition of 25Pa/10 min;
FIG. 3 shows the deposition results of high polymers on the side walls of glass blind holes with different diameters after 100Pa/10min vacuum treatment;
FIG. 4 shows the deposition results of the high polymer on the side wall of each diameter glass blind hole after the vacuum treatment condition of 200Pa/10 min;
FIG. 5 shows the deposition results of the high polymer on the side wall of each glass blind hole with the diameter after the vacuum treatment condition of 100Pa/20 min;
FIG. 6 is a flow chart of electroless nickel plating;
FIG. 7 is a deposition result of electroless nickel on the surface of a polyamide attachment layer;
FIG. 8 shows electroless nickel deposition results for a 4 inch glass PI surface under various conditions;
FIG. 9 is a graph showing the results of nickel deposition in blind glass holes at atmospheric pressure;
FIG. 10 is a graph showing the results of nickel deposition in blind glass holes under vacuum;
FIG. 11 shows the deposition results of nickel on the surface of the PI adhesion layer at different deposition reaction temperatures;
FIG. 12 is a schematic view of bottom-up copper plating;
FIG. 13 shows the results of bottom-up copper plating of 5 μm diameter blind holes for 10min at various additive concentrations;
FIG. 14 shows the results of bottom-up copper plating of 3 μm diameter blind holes for 10min at various additive concentrations;
FIG. 15 is a cross-sectional view of a glass substrate after plating according to the present invention;
FIG. 16 is a schematic view of a glass substrate made in accordance with the present invention;
Detailed Description
The invention will be further described with reference to the drawings and examples.
The invention relates to a method for processing a blind hole of glass, which comprises the following steps of
a. Deep hole etching, namely etching blind holes with high depth-to-width ratio on the glass substrate with the BEOL finished by using a dry method or a wet method. Deep holes herein refer to blind holes of relatively large depth and diameter, such as blind holes of 3 μm diameter, 45 μm depth, or 4 μm diameter, 50 μm depth, 5 μm diameter, 55 μm depth.
b. And depositing an adhesion layer on the side wall of the deep hole.
b1, dripping the high polymer solution on the surface of the glass to ensure that the high polymer solution covers the surface of the glass substrate.
The high polymer material has the advantages of low dielectric constant, low Young's modulus, low cost and the like, and a uniform adhesion layer can be formed on the TGV side wall through a simple process mode such as spin coating and the like. Preferably, the high polymer solution is specifically PI-5J polyimide solution, the PI-5J polyimide solution has lower dielectric constant and excellent electrical property, and a uniform adhesion layer can be formed on the side wall of the TGV through simple process modes such as spin coating, so that the rough degree of the TGV and the adhesion degree of a seed layer are increased, the preparation difficulty can be reduced, and the cost is saved.
And b2, transferring the glass substrate into an environment with the pressure lower than the atmospheric pressure, and standing to fill the deep hole with the high polymer solution.
Because the deep hole is filled with air and the diameter of the deep hole is small, after the high polymer solution is dripped on the surface of the glass, the high polymer solution is difficult to flow into the hole bottom of the deep hole under the normal air pressure condition, so that bubbles and the like appear at the hole bottom, and the thickness is difficult to form uniformly. And the adhesion layer is used for covering the whole surface of the wall of the deep hole. However, in an environment with the pressure lower than the atmospheric pressure, because a large pressure difference exists between the inside and the outside of the deep hole, air in the deep hole can be rapidly discharged under the action of the pressure difference, so that the high polymer solution rapidly enters the deep hole, and the high polymer solution can reach the bottom of the deep hole, and finally a high polymer adhesion layer with uniform thickness and covering the inner wall of the deep hole on the whole surface is formed.
And b3, fixing the glass substrate on the turntable, specifically adhering and fixing the glass substrate on the turntable, deviating the center of the glass substrate from the rotation center of the turntable, driving the turntable to rotate, and throwing away the high polymer solution on the surface of the glass substrate and in the deep hole. The glass substrate may be fixed to the turntable at the beginning, and then the polymer solution may be applied to the surface of the glass substrate, or the glass substrate may be fixed to the turntable after the step b2 is completed.
When the turntable rotates, the glass substrate is driven to rotate, and because the glass substrate is eccentrically arranged relative to the turntable, when the turntable drives the glass substrate to rotate, the glass substrate and the high polymer solution are subjected to larger centrifugal force, and under the action of the centrifugal force, the superfluous high polymer solution on the surface of the glass substrate and in the deep hole can be thrown away, and because the high polymer solution has certain viscosity, part of the high polymer solution remains on the side wall of the deep hole and the surface of the glass substrate, and the residual high polymer solution can form the high polymer insulating film after being dried.
In addition, because the glass substrate is eccentrically arranged relative to the turntable, a plurality of glass substrates can be arranged on the turntable at one time, so that the plurality of glass substrates can be treated at one time, and the processing efficiency is improved.
The turntable can rotate in the environment of subatmospheric pressure to reduce
And b4, drying to solidify the polymer solution remained on the surface of the glass substrate and the side wall of the deep hole to form a polymer insulating film, wherein the drying temperature is about 200 ℃, and the polymer solution can be quickly dried to form a film. Because the drying temperature is lower, the energy consumption can be reduced, and the manufacturing cost is saved.
In the step b2, the key point of influencing the deposition effect of the polymer film is that the environmental pressure is insufficient to discharge bubbles in the deep hole when the pressure is high, and bottom residues are easily caused; because atmospheric pressure can influence the boiling point of solvent, the solvent boiling point of polymer solution can be lower when pressure is too low, leads to polymer solution boiling, and solvent in the solution volatilizes in a large number, and then leads to the concentration increase of polymer, and after the concentration increase of polymer, the mobility of solution worsens, and the viscosity increases, and unnecessary polymer is difficult to be thrown away in the follow-up spin-coating process, also can influence the quality of polymer insulating film.
Thus, in step b2, the glass substrate is transferred to an atmosphere at a pressure of 50 to 150Pa and allowed to stand for 8 to 15 minutes. A further preferred embodiment is: in step b2, the glass substrate is transferred to an environment with a pressure of 100Pa and allowed to stand for 10 minutes.
To investigate the effect of vacuum treatment on the deposited film in the spin-on process, PI-5J polyimide solutions of the same viscosity were prepared and control experiments were performed using different vacuum levels and treatment times.
And (3) dripping polyimide solutions with the same amount of viscosity of 1200cP on three groups of two-inch glass substrates subjected to deep hole etching, respectively adopting four vacuum treatment conditions of 25Pa/10min,100Pa/10min,200Pa/10min and 100Pa/20min for experiments, then adopting the speed of 2000rpm for 30s for treatment, and observing deposition conditions of blind hole side wall films with different sizes after polyimide pre-curing. In order to verify the adaptability of the centrifugal spin coating process to ultra-small diameter and high aspect ratio TGV, the corresponding geometric dimensions of the blind holes used in this section are 3, 4 and 5 μm in diameter and 45, 50 and 55 μm in depth respectively.
The polyimide solution condition on the surface of the sample after the treatment in the step b2 under different conditions is shown in fig. 1, wherein in fig. 1, a is a schematic diagram of the pressure of 25Pa and the treatment of 10mins, b is a schematic diagram of the pressure of 100Pa and the treatment of 10mins, c is a schematic diagram of the pressure of 100Pa and the treatment of 20 mins. It can be seen that under three vacuum treatment conditions, the sample surface solutions exhibited different conditions: under the condition of 25Pa/10min, the surface solution of the glass substrate is gelatinous and has a plurality of pits and discontinuities; under the condition of 100Pa/10mins, the surface solution of the glass substrate still has good liquid fluidity and good overall uniformity; under the condition of 100Pa/20min, the surface solution is uneven in convexity and thickness. The three results are caused by that under the condition of 25Pa, the surface solution of the glass substrate directly boils to accelerate the volatilization of the solvent in the surface solution and the discharge of bubbles in the surface solution, and the surface fluidity of the solution is poor due to the fact that a large amount of solvent volatilizes, and the surface is hollow due to the fact that the bubbles are rapidly discharged and ruptured. Similarly, the vacuum treatment for a long period of time under 100Pa also causes a large amount of solvent volatilization, which results in poor fluidity and slow discharge of bubbles, which makes the surface uneven. Therefore, reasonable vacuum degree and treatment time can only obtain the results of good uniformity and strong flowability of the surface solution in FIG. 1 (b).
FIG. 2 shows the deposition results of the polymer on the side walls of blind glass holes with dimensions of 3 μm/45 μm, 4 μm/50 μm and 5 μm/55 μm, respectively, under vacuum treatment conditions of 25Pa/10 min. As can be seen from the figure, no uniform film was formed on each size, most polyimide remained on the surface of the glass substrate and at the openings, and even in the case of a diameter of 3 μm, polyimide remained completely in the holes and was not thrown out. As described above, too low vacuum conditions result in increased viscosity of the surface solution and poor flowability, which results in increased adhesion of the solution to silica at the surface and blind hole openings, thereby preventing the polyimide solution from being thrown out with centrifugal force during spin-coating. For smaller diameter holes, the greater the local polyimide viscosity is, the greater the barrier effect is, and therefore the more remains in the blind holes.
The sidewall deposition results obtained under 100Pa/10mins vacuum treatment conditions are shown in FIG. 3. Under this condition, the centrifugal spin coating technology was used to successfully achieve uniform polyimide film deposition on the sidewalls of glass blind holes having diameters of 3 μm (part a in the figure), 4 μm (part b in the figure) and 5 μm (part c in the figure). It can also be seen that the polyimide thickness is also substantially uniform in the surface field region near the respective diameter blind via openings. The fact that the surface of the glass substrate keeps good fluidity is beneficial to driving solution in the blind holes to be thrown out in the subsequent spin coating process, and finally, uniform films are formed on the surface and the side walls.
The sidewall deposition results obtained under the vacuum treatment conditions of 200Pa/10mins are shown in FIG. 4. Under the condition, the centrifugal spin coating technology is adopted to successfully realize uniform polyimide film deposition on the side wall of the glass hole with the diameter of 3 mu m (part a in the figure), 4 mu m (part b in the figure) and 5 mu m (part c in the figure), but bubbles still remain at the bottom of the glass blind hole with the diameter of mu m and are not discharged due to insufficient vacuum degree.
The sidewall deposition results obtained under 100Pa/20mins vacuum treatment conditions are shown in FIG. 5. Under this condition, it can be seen from the deposition results of the blind hole side walls of 3 μm (part a in the figure), 4 μm (part b in the figure) and 5 μm (part c in the figure) that, although a large amount of polyimide residue did not appear at the blind hole openings for the cases of 4 μm and 5 μm in diameter, and the film forming effect was slightly better at the blind hole opening portions with large diameters, a part of residue still appeared inside the blind holes. This means that too long a vacuum treatment also causes excessive solvent evaporation, locally increases the viscosity of the solution surface, and deteriorates the fluidity, and it is difficult to form uniform polymer deposition in blind holes of small diameter and high aspect ratio (> 12:1). In addition, in the case of the diameter of 3 μm, the same situation as in fig. 2 (a) occurs, indicating that the ultra-small diameter blind via adhesion layer has a higher requirement for the flowability of the polymer.
In combination with the above four conditions, the vacuum treatment conditions affect the viscosity and fluidity of the glass surface polymer in the centrifugal spin coating process, and ultimately affect the formation of a uniform film on the sidewall. Too low a vacuum or too long a vacuum treatment time can lead to a large amount of solvent volatilization, so that the local viscosity of the solution is increased, the fluidity is poor, and the final surface deposition polymer is too much, thereby preventing the formation of a uniform film inside the side wall. Through further tests and experiments, in the step b2, glass is transferred to an environment with the pressure of 50-150Pa, and the glass is kept stand for 8-15min, so that the deposition requirements can be met. Meanwhile, the pressure is 100Pa, and the treatment condition is the best after standing for 10min.
c. The sidewalls deposit a seed layer. The seed layer may be copper or the like, and is deposited by using existing methods, such as chemical vapor deposition, physical vapor deposition, atomic layer deposition, etc., which have good deposition effects but are very costly. Thus, the present invention specifically employs the following manner of seed layer deposition, the process flow is shown in FIG. 6:
and c1, cleaning the surface of the high polymer adhesion layer by adopting a tetramethyl ammonium hydroxide solution, wherein the aim of the cleaning process is to remove impurities and dirt on the surface of the glass, so that the surface of the glass can be uniformly contacted with the solution in the subsequent process. Then transferring the glass into a tetramethylammonium hydroxide solution for infiltration, and then carrying out cleavage reaction on the polyimide ring on the surface layer of the adhesion layer to form a polyamic acid layer. And the surface of the adhesion layer is modified by adopting a tetramethylammonium hydroxide (TMAH) solution, the deposition of palladium ions on the surface is enhanced by ion replacement reaction on the basis of the original adsorption effect, and the adsorption effect on the palladium ions is enhanced.
c2, transferring the glass into a catalyst solution to perform ion adsorption and exchange reaction, wherein palladium ions in the catalyst solution and (CH) in the polyamic acid layer 3 ) 4 N + Ion exchange to make the surface of the adhesion layer adsorb palladium ion uniformly to form palladium catalytic layer.
And c3, electroless plating, and forming a nickel layer on the surface of the palladium catalytic layer. Nickel metal, which has excellent barrier and soldering properties, is commonly used in the electronics industry for the preparation of under bump metallization (UnderBumpMetallization, UBM) in flip chip technology to prevent diffusion of copper layers between solder balls and circuit substrates. UBM can be generally prepared by two modes of PVD sputtering and electroless plating, but compared with PVD technology, electroless nickel has the characteristics of low cost, low temperature, good film forming coverage, and the like, and the nickel layer prepared by electroless plating has good corrosion resistance.
The difference with the traditional chemical nickel plating process is that after the surface of the polyamide adhesive layer is cleaned, the polyamide adhesive layer is modified by adopting TMAH solution, and the deposition of palladium ions on the surface is enhanced by ion displacement reaction on the basis of the original adsorption effect. And after Pd atoms are separated out by the reducing agent, a Pd nano layer is formed on the surface of the polyamide adhesion layer and used as a subsequent Pd deposited catalytic layer, and finally, a uniform Pd catalytic layer is formed. FIG. 7 shows the electroless nickel deposition results, wherein the deposition coverage of nickel on the surface of the Polyamide (PI) adhesion layer reaches 100%, and the electroless nickel plating scheme of the invention can effectively realize uniform deposition of the nickel layer on the surface of the Polyamide (PI).
In step c3, the pH of the electroless nickel plating solution is 4.2-4.8.
Because of the various sizes of glass, in order to explore the applicability of the improved electroless plating process to large area glass, experiments were performed on 4 inch sample glass with PI adhesion layer deposited on the surface using the process shown in fig. 6, and the experimental results are shown in fig. 8 (a), which shows that the process can only form complete nickel film deposition in the center area of the 4 inch glass, indicating that the process has problems for large area electroless nickel deposition of glass. Considering that the Pd nano-layer deposited on the PI surface can be distributed more uniformly and finely in the environment of the high pH value solution, and the fine catalytic center can lead the Ni to be reduced more quickly and the deposited nickel layer to be distributed more uniformly, the invention improves the chemical plating process by adjusting the pH value of the chemical nickel reaction solution.
Specifically, an appropriate amount of ammonia water was added to the electroless nickel plating solution in advance to prepare electroless plating solutions having PH values of 4.6 and 4.7, respectively, and a 4-inch sample was put into the two new solutions prepared for comparative experiments, and the results are shown in fig. 8 (b) and (c). Comparing FIGS. 8 (a), (b) and (c), it can be seen that the greater the deposition area of the electroless nickel on the PI surface, the more the thickness remains, but the pH is generally in the range of 4.2-4.8, considering other factors such as side reactions during the process. Therefore, the improved electroless nickel plating process can be suitable for large-area glass, and the PH value can be adjusted according to the actual glass size in the application process.
In order to solve the problem that the solution in the small-diameter blind hole is difficult to enter and the ion exchange is difficult to realize due to low ion concentration, in the step c1, after the glass is transferred to the tetramethylammonium hydroxide solution, the tetramethylammonium hydroxide solution is kept stand for 5-10min in an environment of 50-300 Pa. Under the condition of low vacuum, the solution is easier to enter the bottom of the blind hole under the action of the pressure difference between the inside and the outside of the blind hole, so that the PI surface of each part can smoothly carry out ion exchange reaction to finish modification.
In order to facilitate comparison of the nickel deposition results in the blind holes, SEM section observation and energy spectrum analysis (EDS) are carried out on the nickel layers deposited in the blind holes, the nickel deposition results in the blind holes with the diameter of 5 μm (depth of 55 μm) under the vacuum treatment condition are respectively shown in FIG. 9 and FIG. 10, and other conditions are the same.
FIG. 9 is a graph showing the results of nickel deposition in blind glass holes at atmospheric pressure, (a) cross-sectional SEM results; (b) EDS analysis results. As shown in fig. 9 (a), the thickness of the Ni layer at the top position of the blind hole is 90nm, the thickness at the middle position is 30nm, and the thickness at the bottom is zero; fig. 9 (b) shows EDS scan results of corresponding Ni elements, and specific gravities of the Ni elements at three positions in fig. 9 (a) are 1.4, 0.8, and 0.1, respectively. It can be seen that under this experimental condition, for a blind hole of diameter 5 μm and depth 55 μm, deposition of a nickel layer was achieved only in the upper half of the blind hole, with little nickel deposition in the lower half and bottom. Therefore, it can be verified that the electroless plating solution is difficult to enter the bottom of the blind hole with large depth-to-width ratio in the traditional processing mode, and finally the bottom cannot realize nickel barrier/seed layer deposition.
FIG. 10 shows the results of sidewall nickel deposition after PI surface modification and treatment at a vacuum pressure of 200Pa for 5 minutes. The right side of FIG. 10 (a) shows the Ni layer thickness at the top of the blind via at 120nm, at the middle at 90nm and at the bottom at 79nm; fig. 10 (b) shows EDS scan results of corresponding Ni elements, and specific gravities of Ni elements at three positions in fig. 10 (a) are 7.6, 7.1, 2.4, respectively. As can be seen from fig. 10, this experimental condition enables the deposition of nickel on the adhesion layer of the inner sidewall of the blind hole having a diameter of 5 μm and a depth of 55 μm, but the thickness of the nickel layer is thinner as the position is closer to the bottom. Combining fig. 9 and fig. 10 can prove that the solution can be truly promoted to enter the bottom of the blind hole with high depth-to-width ratio under the condition of low vacuum to finish the modification experiment of the PI surface, so that the whole PI surface including the bottom position of the blind hole can realize the deposition of the nickel layer. The actual low vacuum processing conditions can be adjusted according to the glass sample size.
In the nickel reduction deposition process, the reaction temperature can influence the deposition reaction to a certain extent, plays a key role in the thickness of the finally deposited nickel layer, and the electroless plating temperature is 65-80 ℃.
FIG. 11 shows the results of electroless nickel deposition reactions performed on PI surfaces using the process flow shown in FIG. 6, with a vacuum of 200Pa for 5 minutes during PI surface modification. It can be seen that the deposition reaction time is 5min, under the conditions of three temperatures of 65 ℃ (a), 70 ℃ (b) and 80 ℃ (c), the nickel layer can be uniformly deposited on the PI surface, and the deposition thickness of the nickel layer gradually increases with the increase of the temperature.
SEM scanning and EDS analysis were performed on the Ni layer obtained at a deposition temperature of 70 ℃, resulting in: the thickness of the nickel layer on the adhesion layer on the inner side wall of the blind hole with the diameter of 5 μm and the depth of 55 μm is thinner as the position is closer to the bottom, but the nickel layer in the whole blind hole is deposited uniformly, and the step coverage rate is about 90%. It can be seen that, under the same deposition time, the thickness of the nickel layer in the blind hole is thickened along with the increase of the deposition temperature, and the thickness increase value is larger at the position closer to the bottom of the blind hole. This occurs because as the temperature increases, the hypophosphite and nickel ions react faster and eventually the thicker the layer of nickel that is reductively deposited in the same time. Meanwhile, in the electroless nickel plating process, the hypophosphite ions and water molecules can undergo the following side reactions:
the hydrogen is released continuously in the side reaction process, and the hydrogen is flushed from the bottom of the blind hole to the opening under the action of external air pressure, and finally cracks on the surface. Along with the rise of temperature, side reaction can also accelerate, release a large amount of hydrogen, and the fracture of hydrogen on the surface is slow, and the hydrogen of not timely breaking can gather in opening position department to the concentration of opening part solution has been reduced to a certain extent, makes the deposition rate of opening part gradually reduce, is close with bottom rate, finally leads to the bottom and opening difference less. Therefore, the deposition of the nickel layer can be accelerated by increasing the temperature of the electroless nickel deposition reduction reaction, and the deposited nickel layer in the blind holes is more uniformly distributed, but the actual process temperature range is set between 65 ℃ and 80 ℃ in consideration of the fact that the hypophosphite ions are unstable and are easy to decompose harmful gases under the high-temperature condition.
In order to smoothly carry out the subsequent bottom-up copper filling process in the TGV preparation process, a strong binding force between the nickel barrier layer/seed layer and the PI adhesion layer needs to be ensured, otherwise, the phenomenon that the nickel layer is peeled off from the surface of the PI adhesion layer easily occurs in the copper filling process. The invention adopts the hundred grid test conforming to the American Society of Testing and Materials (ASTM) D3359-09 and international ISO2409 standard to verify the adhesion of a nickel layer deposited by electroless plating on the PI surface, and firstly, electroless plating is carried out on the surface of glass on which a PI adhesion layer is deposited to deposit a nickel layer with a certain thickness; secondly, a hundred-grid knife is utilized to scratch the surface of the nickel layer to form a cross lattice pattern; finally, pressing the adhesive tape meeting the standard on the surface of the nickel layer and rapidly pulling down; and selecting a plurality of different positions on the sample to carry out repeated test and observation results. It can be seen that the kerf edges are perfectly smooth and that all square edges of the cross lattice have no lift-off separation, conforming to astm d3359-09 standard grade 5B and ISO2409 standard grade 0. Therefore, the adhesion force between the PI adhesion layer and the surface electroless plating deposited nickel layer meets the requirement of the subsequent process standard.
d. Copper in the deep hole is filled, copper is filled in the deep hole in an electroplating mode, the concentration of an accelerator in electroplating solution is 11.5-15 mL/L, the concentration of an inhibitor is 9.5-15.5mL/L, and the concentration of a leveler is 4.7-5.4mL/L.
The small diameter, high aspect ratio nature of TGV changes the ion distribution of the solution and the electromotive force of the various parts within the blind via in conventional copper plating, and wetting of the bottom of the TGV via is also problematic. Thus, the small diameter, high aspect ratio TGV plating is prone to the appearance of central voids and bottom voids after completion. In order to solve the above problems, it is necessary to introduce a suitable additive to optimally control the electroplating process.
The bottom-up plating process performs bottom-up copper fill by using different concentrations of inhibitors, levelers, and accelerators between the wafer surface and the interior of the via as shown in fig. 12. Inhibitors are relatively high in molecular weight and slow to diffuse, preferentially adsorbing on the wafer surface and via edges, and slowing copper deposition at those locations. The accelerator is relatively small in molecular mass and high in diffusion speed, preferentially adsorbs the inside of the through hole and enhances rapid deposition of copper at the bottom thereof, as shown in fig. 12 (b). The flattening agent is adsorbed on the surface through mass transportation, so that the exertion of the accelerating agent is inhibited to a certain extent, and the flattening of the copper layer on the surface is ensured. Based on the principle, the optimization experiment is carried out on the high aspect ratio blind hole electroplating with the diameter of 3 mu m and 5 mu m by adopting blue magic-T145 (BM-T145) commercial electroplating filling liquid, and the composition and approximate reference concentration are as follows:
the sample preparation procedure was as follows: etching blind hole arrays with diameters of 3 μm and 5 μm and corresponding depths of 45 μm and 55 μm respectively on the surface of the glass substrate by using a DRIE technology; forming PI adhesion layers on the surface and the side wall of the substrate by a centrifugal spin coating technology; then depositing a Ni seed/barrier layer with the thickness of 100nm on the surface of the PI adhesive layer through an electroless plating wet process; finally, experiments were performed by using a bottom-up plating process, and the relevant results are shown in fig. 13 and 14.
FIG. 13 shows the results of an experiment for electroplating a blind hole having a diameter of 5 μm with different additive concentrations, wherein the corresponding electroplating conditions were a current density of 0.1A/dm 2 The electroplating time was 10mins. The concentrations of the three additives corresponding to FIG. 13 (a) are shown in the above table, and the concentrations of the three additives in FIG. 13 (b) are 10mL/L of accelerator, 10mL/L of inhibitor and 5mL/L of leveler, respectively. It can be seen from the figure that the growth of copper layer is realized on the surface of the electroless Ni plating barrier/seed layer under both conditions, the thickness of the copper layer on the side wall of the blind hole is uniformly distributed, and the thickness of the bottom is slightly larger than that of the side wall. However, the thickness of copper at the surface of the glass shown in fig. 13 (a) is 4.5 μm and much greater than that at other positions, and the thickness of copper at the opening is 1.51 μm and also greater than that at the side wall by 1.25 μm, so that early sealing is easily formed in the subsequent electroplating process to generate voids, and the thickness of copper at the surface is too thick, thereby greatly increasing the cost of copper CMP. In the same experimental condition after only increasing the inhibitor concentration, the inner side wall and bottom thickness of the blind hole in fig. 13 (b) are kept unchanged relative to those in fig. 13 (a), the thickness of the copper layer on the surface is reduced by half by only 2.03 μm, the thickness of the copper layer on the opening is also reduced to be basically close to that of the side wall, and the super-conformal growth trend is shown on the whole. This demonstrates that high aspect ratio blind via plating requires a higher concentration of inhibitor for small diameter to inhibit copper growth at the opening and surface.
FIG. 14 shows the results of an experiment for electroplating blind holes of 3 μm diameter using different additive solubilities, wherein the corresponding electroplating conditions are a current density of 0.1A/dm 2 The electroplating time is 10min. The concentrations of the corresponding three additives in FIG. 14 (a) are the same as those in FIG. 13 (a), the graph14 The concentrations of the three additives in the (b) are respectively 12mL/L of accelerator, 10mL/L of inhibitor and 5mL/L of flatting agent. The result of FIG. 14 (a) is similar to that of FIG. 13 (a), with a large portion of the blind holes being uniform, the openings being slightly thicker, and the surface being too thick, except that the copper thickness is approximately 1.15 μm near the bottom of the blind holes at a position of 6 μm, exhibiting a tendency to seal in advance. In view of the above, in combination with the plating results of 5 μm holes, improvement by increasing the inhibitor and accelerator concentrations was proposed, and the experimental results are shown in fig. 14 (b). It can be seen that the final deposition results show a significant decrease in surface thickness and that the bottom has formed a seamless copper fill of 3.8 μm, exhibiting a good super conformal growth trend. Therefore, for small diameter, high aspect ratio blind hole electroplating, higher accelerator concentration can increase the deposition rate of the bottom of the blind hole, prevent the occurrence of bottom partial advanced sealing and promote the bottom-up growth of copper.
Based on the experimental results in fig. 13 and 14, in order to achieve seamless electroplating of blind holes with a diameter of 3 μm and a depth of 46 μm, the present invention finally employs three additive concentrations: accelerator 12mL/L, inhibitor 10mL/L, leveler 5mL/L, current density 0.1A/dm 2 Experiments are carried out, and fig. 15 is a cross-sectional view of the electroplated glass, and it can be seen from the graph that the bottom-up electroplating of the blind holes with ultra-small diameter and high aspect ratio is successfully realized by adopting the experimental conditions, the blind holes have no holes or gaps, and the surface thickness is uniform and proper.
e. Surface CMP and RDL wiring fabrication. And thinning the back of the glass by a thinning and polishing process to expose copper columns in the deep holes, then carrying out RDL or bump manufacture on the back, and finally carrying out glass stacking.
Example 1
The glass-based blind hole is prepared by the following steps:
a. etching blind holes with the diameter of 3 microns and the depth of 45 microns on the front surface of the glass, wherein the number of the blind holes is 25 x 25;
b. depositing an adhesion layer on the side wall of the deep hole:
b1, dripping PI-5J polyimide solution with the viscosity of 1200cP on the surface of glass, and ensuring that the high polymer solution covers the surface of the glass;
b2, transferring the glass into an environment with the air pressure of 100Pa, and standing for 10min to fill the deep hole with the high polymer solution;
b3, fixing the glass on the turntable, wherein the center of the glass deviates from the rotation center of the turntable, driving the turntable to rotate, and throwing away the high polymer solution on the surface of the glass and in the deep hole at the speed of 2000rpm for 30 s;
b4, drying to solidify the polymer solution remained on the surface of the glass and the side wall of the deep hole, so as to form a polymer insulating film;
c. sidewall deposition seed layer:
c1, adopting a tetramethyl ammonium hydroxide solution to carry out surface cleaning on the polymer adhesion layer, transferring the glass to the tetramethyl ammonium hydroxide solution, and standing the tetramethyl ammonium hydroxide solution in an environment of 200Pa for 10min;
c2, transferring the glass into a catalyst solution to perform ion adsorption and exchange reaction, wherein palladium ions in the catalyst solution and (CH) in the polyamic acid layer 3 ) 4 N + Ion reaction replacement is carried out, so that palladium ions are uniformly adsorbed on the surface of the adhesion layer to form a palladium catalytic layer;
and c3, electroless plating, and forming a nickel layer on the surface of the palladium catalytic layer. The pH of the electroless nickel plating solution was 4.5 at 70 ℃.
d. Copper is filled in the deep hole in an electroplating mode, the concentration of an accelerator in electroplating solution is 11.5-15 mL/L, the concentration of an inhibitor in electroplating solution is 9.5-15.5mL/L, the concentration of a leveler in electroplating solution is 4.7-5.4mL/L, and the current density is 0.1A/dm 2 The electroplating time is 10min.
e. Surface CMP and RDL wiring fabrication.
As shown in FIG. 16, the prepared glass has problems at only 1 position in the 25×25 array of blind holes with the diameter of 3 μm, so that the blind hole filling rate by adopting the preparation process is close to 100%.
The electrical reliability test is carried out on the glass by using the semiconductor parameter analyzer B1500A, and the result shows that the prepared ultra-small diameter PI-TGV adhesion layer is complete, no pinhole phenomenon occurs, the leakage characteristic is excellent, and the electrical reliability is high. A TDDB test platform is built through a B1500A and a Cascade probe platform to test and analyze dielectric breakdown characteristics of high polymer PI, and as a result, the average failure life of the PI insulating medium layer can be maintained for more than 10 years under the condition that the TGV is not annealed or annealed at 300 ℃ for one hour.
The thermo-mechanical reliability associated with the PI-TGV attachment layer was analyzed by FEA simulation. Comparing the same size PI-TGV and SiO 2 The magnitude of the equivalent von-Mises stress value of the TGV gives rise to the adoption of PI as an effective stress buffer layer between the copper and barrier layers and the glass substrate, improving the thermo-mechanical reliability of the TGV.
Cu diffusion phenomena with unobstructed PI-TGV structure were analyzed by SIMS test and C-T test to evaluate the reliability of PI-TGV. The results show that the PI adhesion layer and the Ni barrier layer can still act as effective copper diffusion barriers even at 400 ℃.
In summary, the invention can prepare the high aspect ratio TGV with the diameter of 3 mu m and the depth of 45 mu m, ensures that the electrical property and the mechanical property of the TGV meet the requirements, simultaneously can reduce the manufacturing cost, is beneficial to realizing large-scale production and is suitable for the development trend of miniaturization of the adapter plate.
Claims (6)
1. The method for processing the blind glass hole is characterized by comprising the following steps of:
a. deep hole etching;
b. depositing a polymer adhesion layer on the side wall of the deep hole:
b1, dripping the high polymer solution on the surface of the glass substrate to ensure that the high polymer solution covers the surface of the glass substrate;
b2, transferring the glass substrate to an environment with the pressure lower than the atmospheric pressure, and standing to enable the polymer solution to fill the deep hole;
b3, fixing the glass substrate on the turntable, and driving the turntable to rotate by deviating the center of the glass from the rotation center of the turntable so as to throw away the high polymer solution on the surface of the glass substrate and in the deep hole;
b4, drying to solidify the polymer solution remained on the surface of the glass substrate and the side wall of the deep hole, so as to form a polymer adhesion layer; the high polymer adhesion layer is used for increasing the roughness of the blind holes of the glass and the adhesion strength of the seed layer;
the high polymer solution is PI-5J polyimide solution;
c. sidewall deposition seed layer:
c1, adopting a tetramethyl ammonium hydroxide solution to clean the surface of the high polymer adhesion layer, transferring the glass substrate into the tetramethyl ammonium hydroxide solution for infiltration, and performing cleavage reaction on polyimide rings on the surface layer of the high polymer adhesion layer to form a polyamic acid layer;
c2, transferring the glass substrate into a catalyst solution for ion adsorption and exchange reaction, and carrying out the reactive substitution of palladium ions in the catalyst solution and (CH 3) 4N+ ions in the polyamic acid layer to enable the surface of the polymer adhesion layer to uniformly adsorb the palladium ions so as to form a palladium catalytic layer;
c3, electroless plating, forming a nickel layer on the surface of the palladium catalytic layer;
d. copper filling in the deep hole;
e. surface CMP and RDL wiring fabrication.
2. The method for processing a blind glass hole according to claim 1, wherein in the step b2, the glass substrate is transferred to an atmosphere having a pressure of 50 to 150Pa and allowed to stand for 8 to 15 minutes.
3. The method for processing a blind glass hole according to claim 2, wherein in the step b2, the glass substrate is transferred to an atmosphere having a pressure of 100Pa and allowed to stand for 10 minutes.
4. The method of claim 1, wherein in step c3, the electroless nickel plating solution has a PH of 4.2 to 4.8.
5. The method for processing blind glass holes according to claim 1, wherein in step c1, after transferring the glass substrate to a tetramethylammonium hydroxide solution, the tetramethylammonium hydroxide solution is allowed to stand in an atmosphere of 50 to 300Pa for 5 to 10 minutes.
6. The method for processing a blind glass hole according to claim 1, wherein in the step c3, the electroless plating temperature is 65-80 ℃.
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