The present invention relates to a manufacturing method of ultra-large copper grains, an electrolytic solution employed therein, and a copper film composed of the copper grains. More particularly, this method comprises an electrodeposition process without heat treatment. The copper grains have an average size of at least 10 μm.
In general, the copper film is made by depositing copper on a conductive substrate through the electroplating or sputtering process. Such copper film is composed of fine copper grains with an average size less than 100 nm. The copper films with larger grain sizes possess better conductivity or reliability and can be applied to different fields. Traditionally, the large copper grains are manufactured through the heat treatment or calendaring process.
The known technologies relating heat treatment include:
U.S. Pat. No. 6,126,761 (CN1056613C) discloses a process of controlling grain growth in metal films, which comprises: (a) depositing the metal film onto the substrate to form a film having a fine-grained microstructure, and (b) heating the metal film in a temperature range of 70-100° C. for at least five minutes, wherein the fine-grained microstructure is converted into a stable large-grained microstructure of an average crystallite size greater than 1 micron.
US20150064496 (TWI507569, CN104419983A) discloses a method for manufacturing a single crystal copper, in which an electroplating is performed to grow a nano-twinned crystal copper pillar on a surface of the cathode. The nano-twinned crystal copper pillar comprises a plurality of nano-twinned crystal copper grains. The cathode with the nano-twinned crystal copper pillar is then annealed at 350-600° C. for 0.5-3 hours to obtain a single crystal copper. The single crystal copper has a [100] orientation and a volume of 0.1 μm3-4.0×106 μm3.
US20160168746A1 (TWI545231) discloses a copper film with large grains. The grains are grown along a crystal axis direction [100], and an average size of the grains is 150-700 μm. A manufacturing method of the copper clad laminate comprises: growing copper grains on one surface of a laminate by electroplating to obtain a [111]-oriented nano-twinned copper film; and annealing the [111]-oriented nano-twinned copper film under a temperature of 200-500° C. to obtain a copper film with large grains.
To perform the heat treatment, heating equipment is necessary and time and temperature have to be controlled. The processes including electroplating and heat treatment are complex and increase the cost. In addition, the heat treatment may cause diffusion of impurity in the copper and thus reduce conductivity.
The manufacturing method of ultra-large copper grains according to the present invention is performed without heat treatment.
This method comprises steps of: A. providing an electrodeposit equipment; and B. performing an electrodeposition process using the electrodeposit equipment with a current density of 1-80 A/dm2.
In step A, the electrodeposit equipment primarily comprises an anode, a cathode, an electrolytic solution, a power unit, a temperature controller, and a mixer. The anode and the cathode respectively connect to the power unit and are immersed in the electrolytic solution. The temperature controller contacts the electrolytic solution to control the electrolytic solution at 25-55° C. The mixer is used to fast agitate the electrolytic solution. The electrolytic solution is obtained by mixing and dissolving chemical components such as chloride ions, wetting agent, sulfuric acid, copper sulfate and sulfur-containing compound having the formula (1) together in deionized water,
R1—S—CnH2n—R2 (1)
wherein R1═—H, —S—CnH2n—R2 or —CnH2n—R2;
In step B, ultra-large single crystal copper grains having an average size of at least 10 μm are deposited on a surface of the cathode to form a layer of copper grains. The sulfur-containing compound preferably is alkanesulfonate sulfide (R—S—CnH2n—SO3−).
Examples of the sulfur-containing compound include 3-Mercaptopropanesulfonate (MPS), Bis-(3-sulfopropyl)-disulfide (SPS), 3-(2-Benzthiazolylthio)-1-propanesulfonate (ZPS), 3-(N,N-Dimethyl-thiocarbamoyl)-thiopropanesulfonate (DPS), (O-Ethyldithiocarbonato) —S-(3-sulfopropyl)-ester (OPX), 3-[(Amino-iminomethyl)thio]-1-propanesulfonate (UPS) and 3,3-Thiobis(1-propanesulfonate (TBPS).
A copper film is manufactured by the method aforementioned. The copper film comprises a plurality of the ultra-large single crystal copper grains having an average size of at least 10 μm.
By performing an electrodeposition process in the electrolytic solution, the ultra-large single crystal copper grains having an average size of at least 10 μm are deposited on the cathode.
The sulfur-containing compound preferably is alkanesulfonate sulfide (R—S—CnH2n—SO3−).
The present invention further comprises a connecting structure of electric elements comprising the ultra-large copper grains produced by the aforementioned method. The connecting structure of electric elements comprises:
a copper pad comprising the ultra-large copper grains having an average size of at least 10 μm;
a solder unit soldered on a surface of the copper pad; and
an intermetallic compound (IMC) layer formed between the pad and the solder unit, and containing no void at the interface between the copper pad and IMC, and between the IMC and the solder unit.
Through the electrodeposition process without heat treatment, ultra-large copper grains having an average size of at least 10 μm, and copper films with less impurities, lower electrical resistance, shining appearance and anti-fingerprint property can be manufactured with lower costs.
The product of the present invention can be applied to circuit boards, substrates for IC packaging, copper traces and bumps of semiconductor chips, and decorative electroplating.
Through the heat treatment at 200° C. for 1000 hours, the connecting structure of electric elements having less impurity, lower electrical resistance and better reliability can be manufactured without Kirkendall void in the intermetallic compound layer.
In the following, the manufacturing method of ultra-large copper grains, the copper film and connecting structure of electric elements comprising the ultra-large copper grains are discussed in detail in conjunction with the accompanying figures.
In the present invention, the electrodeposition process for manufacturing the copper film of ultra-large single crystal grains can be the electroforming process or the electroplating process.
The temperature controller 6 contacts with the electrolytic solution 4 which is fast agitated with the mixer 5. The mixer 5 is a jet mixer located between the cathode 1 and the anode 2. The cathode 1 can be a rotary cylinder complimentary to the anode 2, as shown in
The electrolytic solution is obtained by mixing and dissolving chloride ions, wetting agent, sulfuric acid, copper sulfate pentahydrate (CuSO4.5H2O) and sulfur-containing compound having the formula (1) together in deionized water,
R1—S—CnH2n—R2 (1)
wherein R1═—H, —S—CnH2n—R2, or —CnH2n—R2;
The electrolytic solution is controlled at 25-55° C. The copper sulfate pentahydrate in the electrolytic solution has a concentration of 125-320 g/L. The low concentration of copper sulfate pentahydrate (125 g/L) is operated at low temperature (25 degree), vice versa. The sulfuric acid in the electrolytic solution has a concentration of 17.6-176 g/L. The chloride ions are supplied by sodium chloride or hydrochloric acid and have a concentration of 30-60 ppm in the electrolytic solution. The wetting agent is polyethylene glycol (PEG) with a molecular weight of 200-2000, and has a concentration of 10-200 ppm in the electrolytic solution. The sulfur-containing compound is alkanesulfonate sulfide (R—S—CnH2n—SO3−) and has a concentration of 0.1-5 ppm in the electrolytic solution. The alkanesulfonate sulfide includes but is not limited to 3-Mercaptopropanesulfonate (MPS), Bis-(3-sulfopropyl)-disulfide (SPS), 3-(2-Benz-thiazolylthio)-1-propanesulfonate (ZPS), 3-(N,N-Dimethyl-thiocarbamoyl)- thiopropanesulfonate (DPS), (O-Ethyl dithiocarbonato)-S-(3-sulfopropyl)-ester (OPX), 3-[(Amino-iminomethyl)thio]-1-propanesulfonate (UPS) and 3,3-Thiobis-(1-propanesulfonate (TBPS).
In a preferred embodiment, the DC power source with an output 100 A/10V is used for the power unit 7.
The current density of the current provided by the power unit 7 is 1-80 A/dm2, and the current efficiency is 94%.
By means of electrodeposition, ultra-large copper grains (ULG) having an average size of at least 10 μm are deposited on the cathode. The thickness is determined according to Faraday's law (δ=0.003445×j×t; wherein δ is thickness (μm), j is current density (A/dm2), and t is time for electrodeposition (second)). In a preferred embodiment, the deposit of ultra-large copper grains each have a size of 18 cm×21 cm×30 μm (thickness).
In
In the present invention, the ultra-large copper grains having an average size of at least 10 μm, less impurities and lower electrical resistance can be manufactured through the electrodeposition (electroforming or electroplating) process without any heat treatment.
Number | Date | Country | Kind |
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106118936 | Jun 2017 | TW | national |