CN117870529A - Method for measuring thickness of wafer level diffusion layer - Google Patents
Method for measuring thickness of wafer level diffusion layer Download PDFInfo
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- CN117870529A CN117870529A CN202410050829.6A CN202410050829A CN117870529A CN 117870529 A CN117870529 A CN 117870529A CN 202410050829 A CN202410050829 A CN 202410050829A CN 117870529 A CN117870529 A CN 117870529A
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
The wafer level diffusion layer thickness measuring method converts limit diffusion current into diffusion layer thickness, realizes the mass transfer performance evaluation of plating baths of different types under the same dimension, solves the problem that the electric field, the flow field, the concentration field and the like in a test electrolytic cell have larger difference with the wafer level copper plating process, is closer to the actual plating process, and can play a guiding role in understanding and understanding the TSV hole, the Bump, the RDL and other copper plating processes.
Description
Technical Field
The invention relates to the field of electrochemical technology application, in particular to a method for measuring the thickness of a wafer level diffusion layer.
Background
In the latter molar age, three-dimensional integration technology with Through-Silicon-Via (TSV) technology as a core is widely used, and the key point is the metallization filling of the TSV. The TSV hole metallization filling technology has three types: electroplating, electroless plating and filling electronic paste. The chemical plating and electronic paste filling scheme has the problems of filling efficiency, process difficulty, conductivity and the like, and is still under research and development. Copper has the characteristics of excellent ductility, resistivity, heat conductivity and the like, the electroplated copper filling process can be continuously accumulated by utilizing technologies such as PCB, silicon CMOS Damascus process and the like, the development difficulty is low, and the electroplated copper filling process has the advantages of both performance and cost, and is a mainstream metallization scheme at present.
In the electroplating field, electroplating equipment is one of factors influencing the electroplating effect of TSV holes, and the key point is how to provide uniform plating solution and current distribution on the surface of a wafer, and the improvement is usually carried out through plating tank design and stirring speed. For the mass transfer capacity of different electroplating baths, no clear characterization means can be evaluated at the same latitude in the industry at present.
Disclosure of Invention
Aiming at the defects existing in the background technology, the invention aims to provide a method for measuring the thickness of a wafer level diffusion layer.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for measuring the thickness of a wafer level diffusion layer comprises the following steps:
1. a method for measuring the thickness of a wafer level diffusion layer comprises the following steps:
s1, embedding a plurality of metal electrodes on a conductive substrate;
s2, the metal electrode is a working electrode, inert metal is a counter electrode, a saturated calomel electrode is a reference electrode, and copper electroplating solution is selected;
s3, electrifying the conductive substrate, and obtaining cathode polarization curves of the conductive substrate and cathode polarization curves at different sites on the working electrode through a multichannel electrochemical workstation;
s4, when the cathode polarization curve of the conductive substrate tends to be in a stable state, bringing the average value of limiting diffusion currents in the corresponding time interval which tends to be in a stable state in the cathode polarization curves corresponding to different positions of the working electrode into delta=nFADC/i, wherein the charge number of n-reaction, F-Faraday constant, A-electrode area and D-Cu 2+ Diffusion coefficient of C-Cu 2+ I-limiting diffusion current, delta-diffusion layer thickness, thereby calculating diffusion layer thicknesses at corresponding different sites by limiting diffusion current;
s5, applying the steps S1-S4 to plating tanks of different types, so that the mass transfer capacity of the plating tanks of different types is evaluated under the same dimension through the thickness of the diffusion layer.
Further, the cathodic polarization curve of the conductive substrate is at least within 500 seconds, and the maximum amplitude of the cathodic polarization curve of the conductive substrate is not more than +/-0.1A, namely the first stable state; and the maximum amplitude of the cathode polarization curve of the working electrode is not more than +/-1 mA, namely the second stable state, at least within 500 continuous seconds.
Further, the conductive substrate is made of conductive materials such as a PCB, a silicon chip, a copper sheet and the like.
Further, the metal electrode comprises a glassy carbon electrode, silver, gold, copper, ruthenium, rhodium, palladium, osmium, iridium or platinum metal and alloys thereof.
Further, the inert electrode comprises a carbon electrode, gold, titanium or platinum group metal.
Further, the copper plating solution comprises one or a combination of more than one of sulfate, pyrophosphate, sulfamate or alkyl sulfonate anions, 0-100 ppm chloride ions, 0.3-100 g/L copper ions, 0.001-2 mol/L hydrogen ions, 1-30ml/L brightening agent, 1-50ml/L inhibitor and 1-30ml/L leveling agent
Further, the brightening agent comprises one or more of sodium polydithio-dipropyl sulfonate, sodium alcohol thio-propane sulfonate, sodium phenyl dithiopropane sulfonate, sodium dimethyl methyl amino propane sulfonate, sodium 3- (benzo saliva-2-thio) propane sulfonate, sodium 3-thio-1-propane sulfonate and dimethyl-dithio methylamine sulfonic acid.
Further, the inhibitor comprises one or a combination of several of polyethylene glycol, fatty alcohol alkoxylate and ethylene oxide-propylene oxide block copolymer with molecular weight of 400, 1000, 6000 and 20000 respectively.
Further, the leveling agent is one or a combination of more of thiourea compounds, alkyl pyridine compounds and tabacco green, and one or a combination of more of fatty alcohol-polyoxyethylene ether series, ether series and emulsifier series with different molecular weights.
Further, the cathodic polarization curve is obtained by cyclic voltammetry, linear sweep voltammetry or chronoamperometry.
The beneficial effects of the invention are as follows:
according to the method for measuring the thickness of the wafer-level diffusion layer, the limiting diffusion current is converted into the thickness of the diffusion layer, the mass transfer performance of plating baths of different types is evaluated under the same dimension, the problem that the electric field, the flow field, the concentration field and the like in a test electrolytic cell are greatly different from the wafer-level copper electroplating process is solved, the method is closer to the actual electroplating process, and a guiding effect can be generated on understanding of TSV holes, the Bump, the RDL and other copper electroplating processes.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from these drawings without inventive effort for a person skilled in the art.
FIG. 1A is a schematic diagram of one of the working electrode arrangement patterns of a method for measuring the thickness of a wafer level diffusion layer according to the present invention;
FIG. 1B is a second schematic diagram of a working electrode layout pattern of a method for measuring the thickness of a wafer level diffusion layer according to the present invention;
FIG. 1C is a third schematic diagram of a working electrode layout pattern of a method for measuring the thickness of a wafer level diffusion layer according to the present invention;
FIG. 1D is a schematic diagram of a working electrode layout pattern of a method for measuring wafer level diffusion layer thickness according to the present invention;
FIG. 2 is a schematic diagram of a method for measuring TSV holes according to the method for measuring the thickness of a wafer level diffusion layer of the present invention;
FIG. 3 is a schematic view of a horizontal plating bath for a method of measuring the thickness of a wafer level diffusion layer according to the present invention;
FIG. 4 is a schematic view of a plating bath for a wafer level diffusion layer thickness measurement method according to the present invention;
FIG. 5A is a graph showing the cathode polarization curve of a copper sheet surface according to one embodiment of a method for measuring the thickness of a wafer level diffusion layer according to the present invention;
FIG. 5B is a graph showing the cathode polarization curve of the surface of a glassy carbon electrode according to the first embodiment of a method for measuring the thickness of a wafer level diffusion layer according to the present invention;
FIG. 6A is a graph showing the cathode polarization curve of a copper sheet surface according to a second embodiment of a method for measuring the thickness of a wafer level diffusion layer according to the present invention;
FIG. 6B is a graph showing the cathode polarization curve of a copper electrode according to a second embodiment of a method for measuring the thickness of a wafer level diffusion layer according to the present invention;
in the figure, 10, a conductive substrate; 20. a working electrode; 30. a counter electrode; 40. a reference electrode; 50. TSV holes; 60. measuring points.
Detailed Description
The invention is described in detail below in connection with fig. 1-6.
A method for measuring the thickness of a wafer level diffusion layer comprises the following steps:
s1, embedding a plurality of metal electrodes on a conductive substrate 10;
s2, a metal electrode is a working electrode 20, an inert metal electrode is a counter electrode 30, a saturated calomel electrode is a reference electrode 40, and copper electroplating solution is selected;
s3, electrifying the conductive substrate 10, and obtaining cathode polarization curves of the conductive substrate 10 and cathode polarization curves at different sites on the working electrode 20 through a multi-channel electrochemical workstation;
s4, when the cathode polarization curve of the conductive substrate 10 tends to be stable, the average value of the limiting diffusion current in the corresponding time interval of the cathode polarization curve corresponding to different positions of the working electrode 20, which tends to be stable, is brought into delta=nFADC/i, wherein n-reaction charge number, F-Faraday constant, A-electrode area, D-Cu 2+ Diffusion coefficient of C-Cu 2+ I-limiting diffusion current, delta-diffusion layer thickness, thereby calculating diffusion layer thicknesses at corresponding different sites by limiting diffusion current;
s5, applying the steps S1-S4 to plating tanks of different types, so that the mass transfer capacity of the plating tanks of different types is evaluated under the same dimension through the thickness of the diffusion layer.
In this embodiment, the maximum amplitude of the cathode polarization curve of the conductive substrate 10 is not more than ±0.1a, i.e. the first stable state, for at least 500 consecutive seconds; the maximum amplitude of the cathodic polarization curve of the working electrode 20 is not more than ±1mA, i.e. the second steady state, for at least 500 consecutive seconds. In this embodiment, the conductive substrate 10 is made of conductive materials such as a PCB board, a silicon wafer, a copper sheet, etc.
In this embodiment, the metal electrode includes a glassy carbon electrode, silver, gold, copper, ruthenium, rhodium, palladium, osmium, iridium, or platinum metal, and alloys thereof.
In this embodiment, the inert electrode comprises a carbon electrode, gold, titanium, or a platinum group metal.
In this embodiment, the copper plating solution includes one or a combination of several of anions of sulfate, pyrophosphate, sulfamate, or alkyl sulfonate, 0 to 100ppm of chloride ions, 0.3 to 100g/L of copper ions, 0.001 to 2mol/L of hydrogen ions, 1 to 30ml/L of brightening agent, 1 to 50ml/L of inhibitor, and 1 to 30ml/L of leveler.
In this embodiment, the brightening agent comprises one or more of sodium polydithio-dipropyl sulfonate, sodium alcohol thio-propane sulfonate, sodium phenyl dithiopropane sulfonate, sodium dimethyl methylamino propane sulfonate, sodium 3- (benzo saliva-2-thio) propane sulfonate, sodium 3-thio-1-propane sulfonate and dimethyl-dithio methylamine sulfonic acid.
In this example, the inhibitor comprises one or a combination of several of polyethylene glycol, fatty alcohol alkoxylate, ethylene oxide-propylene oxide block copolymer with molecular weight of 400, 1000, 6000 and 20000, respectively.
In this embodiment, the leveling agent is one or a combination of several of thiourea compounds, alkyl pyridine compounds and tabacco green, and one or a combination of several of fatty alcohol-polyoxyethylene ether series, ether series and emulsifier series with different molecular weights.
In this example, the cathodic polarization curve is obtained using cyclic voltammetry, linear sweep voltammetry, or chronoamperometry.
In this embodiment, plating bath types include horizontal plating baths and rack plating baths.
In this embodiment, as shown in fig. 2, a measuring point 60 is disposed at the bottom of the TSV hole 50, two measuring points 60 are disposed at the opening of the TSV hole 50, the measuring points are electrochemically tested by a multi-channel electrochemical workstation, and the limiting diffusion currents of the TSV opening and the bottom of the hole are extracted by the formula δ=nfacd/i, wherein n-the charge number of the reaction, F-faraday constant, a-electrode area, D-Cu 2+ Diffusion coefficient of C-Cu 2+ I-limiting diffusion current, delta-diffusion layer thickness, calculating the diffusion layer thickness at the corresponding measuring point of the limiting diffusion current;
to illustrate the above summary, the following examples are set forth.
Example 1
A 6/8/12 inch copper sheet is selected as the conductive substrate 10, a plurality of mounting holes are drilled on the surface of the copper sheet by an electric drill, and the copper sheet after the holes are drilled is respectively cleaned by acid, alkali and deionized water for 30 minutes. An L-shaped glassy carbon electrode with the diameter of 3mm is inlaid in the mounting hole and is insulated and fixed through epoxy resin. Before each electrochemical test, the glassy carbon electrode is soaked with Al 2 O 3 The pattern 8 was repeated 100 times on the powder and rinsed with deionized water after polishing.
The glassy carbon electrode is selected as a working electrode 20, the titanium mesh is a counter electrode 30, the saturated calomel electrode is a reference electrode 40, a three-electrode system is formed, and the copper electroplating solution is selected for electrochemical testing.
Based on the energizing of the copper sheet, measuring an LSV curve of the glassy carbon electrode by using the multi-channel electrochemical workstation, and obtaining the limit diffusion voltage for measuring the limit diffusion current of the glassy carbon electrode through the LSV curve. And extracting limiting diffusion currents at different sites according to a cathode polarization curve of the glassy carbon electrode, and calculating diffusion layer thicknesses at different corresponding sites through the limiting diffusion currents by the formula delta=nfacf/i.
The source of the plating solution is Shanghai Seiff's special Co., ltdHas 50g/L H as main component 2 SO 4 Cu of 40g/L 2+ 60ppm of chloride ions. The current range for multichannel electrochemical operation is 0.01. Mu.A-10A, and more preferably 0.01. Mu.A-5A. In this embodiment, a timing current method is used to obtain a cathode polarization curve of the surface of the copper sheet and a cathode polarization curve of a certain position of the surface of the glassy carbon electrode, as shown in fig. 5A and 5B. As can be seen from fig. 5A, the cathodic polarization curve of the copper sheet surface is from 500 to 1000 seconds, the change of the curve amplitude is less than 0.1A, and the cathodic polarization curve of the copper sheet surface is in a first stable state; as can be seen from fig. 5B, the cathode polarization curve of the glassy carbon electrode surface is from 1000 to 1600 seconds, the change of the curve amplitude is less than 1mA, and the cathode polarization curve of the glassy carbon electrode surface is in the second stable state.
Example two
In this embodiment, the difference from the first embodiment is that the glassy carbon electrode is changed to a copper electrode, and the other is unchanged. The cathode polarization curve of the copper sheet surface and the cathode polarization curve of the copper electrode surface are respectively obtained by adopting a chronoamperometry, as shown in fig. 6A and 6B. As can be seen from fig. 6A, the cathodic polarization curve of the copper sheet surface is at least within 1000-1600 seconds, the change of the curve amplitude is less than 0.1A, and the cathodic polarization curve of the copper sheet surface is in a first stable state; as can be seen from fig. 6B, the cathodic polarization curve of the copper electrode surface is from 1000 to 1600 seconds, the change in the amplitude of the curve is less than 1mA, and the cathodic polarization curve of the copper electrode surface is in the second stable state.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement it, and not to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (10)
1. The method for measuring the thickness of the wafer level diffusion layer is characterized by comprising the following steps of:
s1, embedding a plurality of metal electrodes on a conductive substrate;
s2, the metal electrode is a working electrode, inert metal is a counter electrode, a saturated calomel electrode is a reference electrode, and copper electroplating solution is selected;
s3, electrifying the conductive substrate, and obtaining cathode polarization curves of the conductive substrate and cathode polarization curves at different sites on the working electrode through a multichannel electrochemical workstation;
s4, when the cathode polarization curve of the conductive substrate tends to a first stable state, bringing the average value of limiting diffusion current in the corresponding time interval tending to a second stable state in the cathode polarization curve corresponding to different sites of the working electrode into delta=nFADC/i, wherein n-reaction charge number, F-Faraday constant, A-electrode area, D-Cu 2+ Diffusion coefficient of C-Cu 2+ I-limiting diffusion current, delta-diffusion layer thickness, thereby calculating diffusion layer thicknesses at corresponding different sites by limiting diffusion current;
s5, applying the steps S1-S4 to plating tanks of different types, so that the mass transfer capacity of the plating tanks of different types is evaluated under the same dimension through the thickness of the diffusion layer.
2. The method of claim 1, wherein the cathode polarization curve of the conductive substrate is at least in 500 seconds, and the maximum amplitude of the cathode polarization curve of the conductive substrate is not more than ±0.1a, which is the first stable state; and the maximum amplitude of the cathode polarization curve of the working electrode is not more than +/-1 mA, namely the second stable state, at least within 500 continuous seconds.
3. The method for measuring the thickness of a wafer level diffusion layer according to claim 1, wherein the conductive substrate is made of conductive materials such as a PCB, a silicon wafer, a copper sheet, and the like.
4. A method of measuring the thickness of a wafer level diffusion layer according to claim 1, wherein said metal electrode comprises a glassy carbon electrode, silver, gold, copper, ruthenium, rhodium, palladium, osmium, iridium or platinum metal, and alloys thereof.
5. A method of measuring the thickness of a wafer level diffusion layer as recited in claim 1, wherein said inert electrode comprises a carbon electrode, gold, titanium or platinum group metal.
6. The method of claim 1, wherein the copper plating solution comprises one or more of anions of sulfate, pyrophosphate, sulfamate, and alkyl sulfonate, 0-100 ppm chloride ion, 0.3-100 g/L copper ion, 0.001-2 mol/L hydrogen ion, 1-30ml/L brightener, 1-50ml/L inhibitor, and 1-30ml/L leveler.
7. The method of claim 6, wherein the brightening agent comprises one or more of sodium polydithio-propane sulfonate, sodium alcohol thio-propane sulfonate, sodium phenyl-dithiopropane sulfonate, sodium dimethyl-methylaminopropane sulfonate, sodium 3- (benzosaliva-2-thio) propane sulfonate, sodium 3-thio-1-propane sulfonate, and dimethyl-dithiomethylamine sulfonic acid.
8. The method of claim 6, wherein the inhibitor comprises one or more of polyethylene glycol, fatty alcohol alkoxylate, and ethylene oxide-propylene oxide block copolymer having molecular weights of 400, 1000, 6000, and 20000, respectively.
9. The method for measuring the thickness of a wafer level diffusion layer according to claim 5, wherein the leveling agent is one or a combination of several of thiourea compounds, alkylpyridine compounds and tabaci green, and one or a combination of several of fatty alcohol polyoxyethylene ether series, ether series and emulsifier series with different molecular weights.
10. A method of measuring the thickness of a wafer level diffusion layer as claimed in claim 1, wherein the cathodic polarization curve is obtained by cyclic voltammetry, linear sweep voltammetry or chronoamperometry.
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