CN116043286A - Plating solution with controllable grain size and orientation of copper plating layer and electroplating method - Google Patents
Plating solution with controllable grain size and orientation of copper plating layer and electroplating method Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 111
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 102
- 238000007747 plating Methods 0.000 title claims abstract description 102
- 238000009713 electroplating Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000654 additive Substances 0.000 claims abstract description 42
- 230000000996 additive effect Effects 0.000 claims abstract description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000004100 electronic packaging Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000002003 electron diffraction Methods 0.000 description 4
- 238000002524 electron diffraction data Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004969 ion scattering spectroscopy Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides a plating solution with controllable grain size and orientation of a copper plating layer and an electroplating method, wherein the plating solution is cyanide-free environment-friendly copper plating solution, and the main ions are Cu 2+ And P 2 O 7 4‑ The molar concentration ratio is 1: between 3 and 7, and Cu 2+ The content is less than or equal to 0.6mol/L; the content of the first additive is less than or equal to 1mol/L, and the content of the second additive is less than or equal to 0.1g/L; in the electroplating process, the pH of the plating solution is kept between 7 and 10, and the temperature is kept between 20 and 60 ℃. The electroplating method can regulate the grain size and orientation of the copper plating layer by adjusting the component content and the technological parameters of the plating solution, and has the advantages of safe and nontoxic formula of the plating solution, easy implementation of the electroplating process, strong compatibility with the existing integrated circuit manufacturing and electronic packaging processes and the like.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a plating solution with controllable grain size and orientation of a copper plating layer and an electroplating method.
Background
Copper plating technology is widely applied to the industrial fields of electronics, chemical industry and the like, and copper layers with different physical and mechanical properties can be obtained by regulating and controlling the grain size and orientation of the copper plating layers so as to be applied to more suitable application occasions.
The average grain size of copper plating layers prepared based on the existing electroplating process is more than 1-5 μm, and in the fields of integrated circuits and electronic packaging, the increase of the grain size of copper interconnects brings about a number of advantages: the resistance is reduced, the heating is reduced, the resistance-capacitance delay is reduced, and the electromigration resistance is stronger.
To obtain copper interconnects with large-sized grains, the invention patent of application publication No. CN103943556A discloses a method of increasing the size of copper grains by post-copper electroplating annealing. However, such high temperature long term anneals can cause damage to devices in the integrated circuit. Paper [ p. -f.chan, w. -p.dow, spontaneous potential oscillation resulting in copper deposit with ultra-large grains, journal of the Electrochemical Society 166 (16) (2019) D891-D897 ] proposes that large-grain copper be electroplated during the electroplating process using the potential oscillations of the power supply and the change/aging of the organic additives, but that large-grain copper can only begin to appear after 9600 seconds after the start of the electroplating, and that the method requires higher power supply equipment. In addition, the paper [ H.Lee, S.S.Wong, S.D.Lopatin, correlation of stress and texture evolution during self-and thermal annealing of electroplated Cu films, J.Appl. Phys.93 (7) (2003) 3796-3804 ] study shows that the thermal stability of the copper plating layer is best when the copper surface is the (001) plane, and is more suitable as a stable copper interconnect material.
As described above, copper-plated crystal grains are suitable as copper interconnect materials when they are large. However, when the copper grain size reaches the nanometer level, it is suitable as a structural material having good wear resistance and high strength. And the instability of the nanocrystalline copper under the annealing condition is utilized, nanocrystalline copper salient points can be prepared by electroplating on a wafer, and the low-temperature hot-press bonding between three-dimensional stacked chips is realized. Studies in paper [ C.H.Tseng, K.N.Tu, C.Chen, comparison of oxidation in uni-directionally and randomly oriented Cu films for low temperature Cu-to-Cu direct bonding, sci.Rep.8 (1) (2018) 10671] show that when the copper surface is the (111) crystal plane, the oxidation resistance and copper atom diffusion performance are stronger, which is more favorable for thermocompression bonding, but no report about the preferential nanocrystalline copper electroplating process of (111) is available at present.
Therefore, it is necessary to provide a plating solution and a plating method, which can adjust and control the grain size and orientation according to the applicable application fields.
Disclosure of Invention
According to the technical problems that when the existing large-size grain copper interconnection is provided, circuit devices are damaged due to overhigh temperature, the power supply requirements of the traditional electroplating method are overhigh, and the like, the plating solution and the electroplating method with controllable grain sizes and orientations of copper plating layers are provided. The cyanide-free environment-friendly copper plating solution disclosed by the invention has the advantages that the grain size and orientation of a copper plating layer are regulated and controlled cooperatively by adjusting the component content and the technological parameters, the copper plating solution is safe and nontoxic, the electroplating process is easy to implement, and the compatibility with the process in the prior art is strong.
The invention adopts the following technical means:
a plating solution with controllable grain size and orientation of copper plating layer is prepared by adopting cyanide-free electroplating copper solution, wherein the main ion is Cu 2+ And P 2 O 7 4- The molar concentration ratio is 1: between 3 and 7, and Cu 2+ The content is less than or equal to 0.6mol/L; the content of the first additive is less than or equal to 1mol/L, and the content of the second additive is less than or equal to 0.1g/L; in the electroplating process, the pH of the plating solution is kept between 7 and 10, and the temperature is kept between 20 and 60 ℃.
Further, the first type of additive is an aminocarboxylic acid complex; the second type of additive is one or more of gelatin, oxalic acid and polyethylene glycol.
The invention discloses an electroplating method of the plating solution with controllable grain size and orientation of a copper plating layer, which comprises the steps of preparing a cyanide-free electroplating copper solution, and electroplating the copper plating layer with micro-grains, nano-grains, micro-scale and nano-scale mixed grains or the copper plating layer with texture characteristics by adjusting the content of additives and cathode potential.
Further, when the content of the first type of additive is less than 0.05mol/L and the content of the second type of additive is less than or equal to 0.1g/L, the cathode potential is between-0.5 and-0.1V vs. RHE (reversible hydrogen electrode), the copper plating layer with nano crystal grains is prepared.
Further, when the content of the second type of additive is between 0.02g/L and 0.1g/L, the equivalent circle diameter d of the crystal grains is as follows: nm and electricityBit position
Units: v, satisfies the following formula: />
And the copper plating layer has random grain orientation.
Further, when the content of the second type of additive is less than 0.02g/L and the cathode potential is between-0.5 and-0.4V vs. RHE, a copper plating layer with nano-grains is prepared, wherein the average grain size of the copper plating layer is less than 200nm and has (111) preferred orientation.
Further, when the second type of additive content is less than 0.02g/L and the cathodic potential is between-0.4 and-0.1V vs. RHE, a copper plated layer having micron grains is produced, the average grain size of the copper plated layer is less than 200nm, and the grain orientation is random.
Further, when the content of the first type of additive is between 0.05mol/L and 1mol/L, the content of the second type of additive is less than 0.02g/L, the cathode potential is less than or equal to-0.4V vs. RHE, a copper plating layer with micron grains is prepared, and the average grain size of the copper plating layer is more than 10 mu m and has (001) preferred orientation.
Further, when the content of the first additive is between 0.05mol/L and 1mol/L and the content of the second additive is less than 0.02g/L, the cathode potential is between-0.4 and-0.3V vs. RHE, preparing a copper plating layer with micron-sized and nano-sized mixed crystal grains, wherein the average crystal grain size of micron-sized crystal grains in the copper plating layer is more than 10 mu m, and the copper plating layer has (001) preferred orientation; the nano-scale grains present in the copper plating layer have an average grain size of less than 200nm and are randomly oriented.
Compared with the prior art, the invention has the following advantages:
1. the invention can regulate the size and orientation of copper grains by adjusting the component content and the technological parameters of the additive in the plating solution.
2. The invention can directly electroplate copper plating with large-size grains, the average grain size is more than 10 mu m, and the copper plating has (001) preferred orientation with high thermal stability, which is not reported yet.
3. The invention can directly electroplate (111) preferential nanocrystalline copper, the grain size is less than 200nm, and the process is not reported yet.
4. The process disclosed by the invention has good compatibility with the existing semiconductor manufacturing technology, is environment-friendly and nontoxic, and has small damage to equipment due to the weakly alkaline plating solution.
For the reasons, the invention can be widely popularized in the electroplating field.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to the drawings without inventive effort to a person skilled in the art.
FIG. 1 is a back-scattered electron diffraction pattern of the copper plating layer of random nano-crystalline grains prepared in example 1 of the present invention.
FIG. 2 is a back-scattered electron diffraction pattern of the (111) preferred nanocrystalline copper plating prepared in example 2 of the present invention.
FIG. 3 is a focused ion beam ion scattering diagram of the nanocrystalline copper plating layer prepared in example 3 of the present invention.
FIG. 4 is a back-scattered electron diffraction pattern of the copper plating layer of micro-crystal grains prepared in example 4 of the present invention.
FIG. 5 is a back-scattered electron diffraction pattern of a copper plating layer of mixed crystal grains of micro-and nano-order prepared in example 5 of the present invention.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
Example 1
(1) 280g of potassium pyrophosphate was weighed into a vessel, added with an appropriate amount of deionized water, stirred for dissolution, and the solution was heated to 30℃and maintained at this temperature throughout the solution preparation and electroplating process.
(2) Adding 40g of copper sulfate, 0.03mol of a first additive and 0.01g of a second additive into the solution gradually, adding deionized water to the solution to be approximately 1L after the solute is completely dissolved, and then adding dilute sulfuric acid solution into the electroplating solution dropwise until the pH value of the electroplating solution is 9. And then the volume of the plating solution is fixed to be 1L, and the pH value is ensured to be 7-10 after the volume is fixed.
(4) The oxygen-free copper is used as an anode, the element to be plated is used as a cathode, the cathode potential is set to be-0.3V vs. RHE, the rotating speed of a stirring rotor is 300 revolutions per minute, and the nanocrystalline copper plating layer is electroplated at the constant temperature of 30 ℃.
(5) After plating under the condition, taking out the plated part, washing with distilled water, then ultrasonically cleaning with distilled water, and drying.
After the nanocrystalline copper plating is prepared, the sample is subjected to back-scattered electron diffraction characterization, as shown in fig. 1, with the average diameter of the copper grains being about 150nm and the grains being randomly oriented.
Example 2
(1) 250g of potassium pyrophosphate was weighed into a vessel, added with an appropriate amount of deionized water, then stirred to dissolve, and the solution was heated to 40℃and maintained at this temperature throughout the solution preparation and electroplating process.
(2) 50g of copper pyrophosphate, 0.03mol of a first additive and 0.01g of a second additive are gradually added into the solution, after the solute is completely dissolved, the solution is firstly mixed with deionized water to be approximately 1L, and then dilute sulfuric acid solution is added into the electroplating solution dropwise until the pH value of the electroplating solution is 8. And then the volume of the plating solution is fixed to be 1L, and the pH value is ensured to be 7-10 after the volume is fixed.
(4) The method comprises the steps of taking phosphor copper as an anode, taking a component to be plated as a cathode, setting the cathode potential to be-0.45V vs. RHE, stirring the rotor at the rotating speed of 200 revolutions per minute, and electroplating a copper layer at the constant temperature of 40 ℃.
(5) After plating under the condition, taking out the plated part, washing with distilled water, then ultrasonically cleaning with distilled water, and drying.
After the nanocrystalline copper plating is prepared, the sample is subjected to back-scattered electron diffraction characterization, as shown in fig. 2, with the average diameter of the copper grains being about 150nm and having a preferred orientation of (111).
Example 3
(1) 300g of potassium pyrophosphate was weighed into a vessel, added with an appropriate amount of deionized water, stirred for dissolution, and the solution was heated to 50℃and maintained at this temperature throughout the solution preparation and electroplating process.
(2) 70g of copper pyrophosphate, 0.02mol of first-class additive and 0.08g of second-class additive are gradually added into the solution, after the solute is completely dissolved, the solution is firstly mixed with deionized water to be approximately 1L, and then dilute sulfuric acid solution is added into the electroplating solution dropwise until the pH value of the electroplating solution is 7.5. And then the volume of the plating solution is fixed to be 1L, and the pH value is ensured to be 7-10 after the volume is fixed.
(4) The method comprises the steps of taking oxygen-free copper as an anode, taking a component to be plated as a cathode, setting the cathode potential to be-0.3V vs. RHE, stirring the rotor at 300 rpm, and electroplating a copper layer at a constant temperature of 50 ℃.
(5) After plating under the condition, taking out the plated part, washing with distilled water, then ultrasonically cleaning with distilled water, and drying.
After the nanocrystalline copper plating is prepared, the sample is characterized by focused ion beam ion scattering, as shown in FIG. 3, with the average diameter of the copper grains being about 50nm.
Example 4
(1) 200g of potassium pyrophosphate was weighed into a vessel, added with an appropriate amount of deionized water, stirred for dissolution, and the solution was heated to 45℃and maintained at this temperature throughout the solution preparation and electroplating process.
(2) 50g of copper pyrophosphate, 0.1mol of the first additive and 0.01g of the second additive are gradually added into the solution, after the solute is completely dissolved, the solution is firstly mixed with deionized water to be approximately 1L, and then dilute sulfuric acid solution is added into the electroplating solution dropwise until the pH value of the electroplating solution is 9. And then the volume of the plating solution is fixed to be 1L, and the pH value is ensured to be 7-10 after the volume is fixed.
(4) The method comprises the steps of taking oxygen-free copper as an anode, taking a component to be plated as a cathode, setting the cathode potential to be-0.5V vs. RHE, stirring the rotor at 300 rpm, and electroplating a copper layer at a constant temperature of 45 ℃.
(5) After plating under the condition, taking out the plated part, washing with distilled water, then ultrasonically cleaning with distilled water, and drying.
After preparing the copper plating, the sample was subjected to back-scattered electron diffraction characterization, as shown in fig. 4, with copper grains having an average diameter of about 30 μm and a preferred orientation of (001).
Example 5
(1) 350g of potassium pyrophosphate is weighed into a container, a proper amount of deionized water is added, then stirring is carried out for dissolution, the temperature of the solution is heated to 30 ℃, and the temperature is kept all the time in the preparation and electroplating process of the solution.
(2) 80g of copper pyrophosphate, 0.03mol of the first additive and 0.01g of the second additive are gradually added into the solution, after the solute is completely dissolved, the solution is firstly mixed with deionized water to be approximately 1L, and then dilute sulfuric acid solution is added into the electroplating solution dropwise until the pH value of the electroplating solution is 8. And then the volume of the plating solution is fixed to be 1L, and the pH value is ensured to be 7-10 after the volume is fixed.
(4) The method comprises the steps of taking oxygen-free copper as an anode, taking a component to be plated as a cathode, setting the cathode potential to be-0.35V vs. RHE, stirring the rotor at 300 revolutions per minute, and electroplating a copper layer at a constant temperature of 30 ℃.
(5) After plating under the condition, taking out the plated part, washing with distilled water, then ultrasonically cleaning with distilled water, and drying.
After preparing the copper plating layer, the sample is subjected to back-scattered electron diffraction characterization, as shown in fig. 5, wherein copper grains are mixed grains of micron-order and nano-order.
From the above examples, it can be seen that the present invention can regulate copper grain size and orientation by adjusting the component content and process parameters of additives in the plating bath. The copper layer with large-size grains can be directly electroplated, the average grain size is more than 10 mu m, and the copper layer has (001) preferred orientation with high thermal stability; the preferential nano-grain copper layer (111) can also be directly electroplated, and the grain size is smaller than 200nm.
The process disclosed by the invention has good compatibility with the existing semiconductor manufacturing technology, is environment-friendly and nontoxic, and has small damage to equipment due to the weakly alkaline plating solution.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. A plating solution with controllable grain size and orientation of copper plating layer is characterized in that cyanide-free electroplating copper solution is adopted, wherein the main ion is Cu 2+ And P 2 O 7 4- The molar concentration ratio is 1: between 3 and 7, and Cu 2+ The content is less than or equal to 0.6mol/L; the content of the first additive is less than or equal to 1mol/L, and the content of the second additive is less than or equal to 0.1g/L; after being electroplatedIn the process, the pH value of the plating solution is kept between 7 and 10, and the temperature is kept between 20 and 60 ℃.
2. The plating solution of claim 1, wherein said first type of additive is an aminocarboxylic acid complex; the second type of additive is one or more of gelatin, oxalic acid and polyethylene glycol.
3. A plating method of the plating solution according to claim 1 or 2, wherein a cyanide-free plating copper solution is prepared, and a copper plating layer having micro-grains, nano-grains, mixed micro-and nano-grains, or a copper plating layer having texture features is plated by adjusting the additive content and the cathodic potential.
4. The plating method of a plating solution having a controllable grain size and orientation of a copper plating layer according to claim 3, wherein when the content of the first type of additive is less than 0.05mol/L and the content of the second type of additive is less than or equal to 0.1g/L, the cathode potential is between-0.5 and-0.1V vs. RHE, a copper plating layer having nanocrystalline grains is produced.
5. The method for electroplating a copper-plated layer with a plating solution having a controllable grain size and orientation as claimed in claim 4, wherein the average grain size d of the copper-plated layer is prepared with a unit of the second type of additive content of 0.02g/L to 0.1 g/L: nm, and potential, units: v, satisfies the following formula: d= -15/phi, and the grain orientation of the copper plating layer is random.
6. The method for electroplating of a plating solution having a controlled grain size and orientation of copper plating layer according to claim 4, wherein when the second type of additive is contained in an amount of < 0.02g/L and the cathodic potential is between-0.5 and-0.4 vvs.rhe, a copper plating layer having nanocrystalline grains is produced, the copper plating layer having an average grain size of less than 200nm and a preferred orientation of (111).
7. The method for electroplating a plating solution having a controllable grain size and orientation of copper plating layer according to claim 4, wherein when the second type of additive content is less than 0.02g/L and the cathodic potential is between-0.4 to-0.1 vvs. Rhe, copper plating layers having micro-sized grains are prepared, the average grain size of the copper plating layers is less than 200nm, and the grain orientation is random.
8. A method for electroplating a plating solution having a controllable grain size and orientation of copper plating layer according to claim 3, wherein when the first type of additive is contained in an amount of 0.05mol/L to 1mol/L, the second type of additive is contained in an amount of < 0.02g/L, and the cathodic potential is less than or equal to-0.4 v vs. rhe, a copper plating layer having micro-sized grains is produced, the copper plating layer having an average grain size of more than 10 μm and a preferred orientation of (001).
9. A plating method of a plating solution with controllable grain size and orientation of copper plating layer according to claim 3, characterized in that when the first type of additive content is between 0.05mol/L and 1mol/L and the second type of additive content is less than 0.02g/L, the cathodic potential is between-0.4 to-0.3 v vs. rhe, copper plating layer with mixed micro-and nano-sized grains is prepared, the average grain size of micro-sized grains present in the copper plating layer is greater than 10 μm, and with (001) preferential orientation; the nano-scale grains present in the copper plating layer have an average grain size of less than 200nm and are randomly oriented.
Priority Applications (1)
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| CN106757191A (en) * | 2016-11-23 | 2017-05-31 | 苏州昕皓新材料科技有限公司 | A kind of copper crystal particle with preferred orientation high and preparation method thereof |
| CN109750333A (en) * | 2017-11-08 | 2019-05-14 | 罗门哈斯电子材料有限责任公司 | Electro-coppering |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106757191A (en) * | 2016-11-23 | 2017-05-31 | 苏州昕皓新材料科技有限公司 | A kind of copper crystal particle with preferred orientation high and preparation method thereof |
| CN109750333A (en) * | 2017-11-08 | 2019-05-14 | 罗门哈斯电子材料有限责任公司 | Electro-coppering |
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