JP2018165375A - Acidic copper plating liquid, acidic copper plated article, and method of producing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acidic copper plating liquid capable of controlling the heat expansion of a plated article, an acidic copper plated article obtained by using the plating liquid, and a method of producing a semiconductor device using the plating liquid.SOLUTION: The acidic copper plating liquid according to the present invention comprises a first additive comprised of a cationic polymer, at least one kind of a second additive selected from the group consisting of 2-mercapto-5-benzimidazole sulfonic acid, dihydrate sodium 2-mercapto-5-benzimidazole sulfonate, ethylene thiourea, and a partial 2-mercapto-5-benzimidazole sulfonic acid salt of poly(diallyldimethyl ammonium chloride), and a third additive comprised of an organic compound comprising a sulfur atom, with the copper concentration therein being 10 to 60 g/L, the sulfuric acid concentration therein being 10 to 200 g/L, and a chloride ion contained therein in an amount of 90 mg/L or less. The acidic copper plating liquid can produce an acidic copper plated article of low thermal expansion.SELECTED DRAWING: Figure 5

Description

  The present invention relates to an acidic copper plating solution, an acidic copper plating product, and a method for manufacturing a semiconductor device.

  As one technique that exceeds the limit of miniaturization of LSI chips, a three-dimensional mounting technique in which a large number of LSI chips are stacked to form one package has been studied. In the three-dimensional mounting technology, an upper transistor and a lower transistor are connected by a through silicon via (hereinafter abbreviated as TSV). The Viamide process, which is one of TSV manufacturing processes, is a process for forming a TSV before a wiring process. In the Viamide process, a non-through via is formed on a silicon substrate on which a transistor is formed, and the non-through via is filled with copper by electroplating using an acidic copper plating solution. Further, the silicon substrate is thinned by CMP to expose the bottom of the non-through via, and an insulating oxide film is formed when the wiring layer is formed.

  However, in the biamide process, when the insulating oxide film is formed, heating is performed at 400 to 600 ° C. However, since the linear expansion coefficient of copper is larger than that of silicon, TSV copper expands (hereinafter referred to as pumping). There is a problem that a defect occurs when the upper wiring layer is disconnected (for example, Non-Patent Documents 1, 2, and 3). Therefore, 3D mounting technology has not been put to practical use.

  In order to prevent the pumping of the TSV, for example, a method has been proposed in which heat is applied to the manufactured TSV, followed by cooling and flattening by CMP a plurality of times (for example, Non-Patent Documents 2 and 3). 4). However, this method has a problem that the manufacturing cost increases because the heating process and the expensive CMP process increase.

Che, F.X. et al., “Numerical and experimental study on Cu protrusion of Cu filled through-silicon vias (TSV)”, Proc. 3DIC, pp.1-6, 2011 Redolfi, A. et al., “Implementation of an industry compliant, 5 x 50 μm, via-middle TSV technology on 300mm wafers”, Proc. ECTC. Pp.1384-1388, 2011 Solid State TECHNOLOGY, December 15, 2010, “Cu protrusion, keep out zones highlight 3D talk at IEDM”, URL, http://www.electroiq.com/articles/ap/2010/12/cu-protrusion-keep-out .html De Messemaeker, J. et al., “Correlation between Cu microstructure and TSV Cu pumping”, Proc. ECTC IEEE64th, pp.613-619, 2014.

  Therefore, in view of the above-described conventional problems, the present invention provides an acidic copper plating solution capable of suppressing thermal expansion of a plated product, an acidic copper plated product obtained using the plating solution, and a plating solution thereof. An object of the present invention is to provide a method for manufacturing a semiconductor device to be used.

As a result of earnest research to solve the above-mentioned problems, the present inventor has developed an acidic copper plating solution capable of producing an acidic copper plating product having a smaller linear expansion coefficient than that of conventional plated copper. The present invention has been completed by finding that it is possible to suppress thermal expansion of an object.
That is, the acidic copper plating solution of the present invention comprises a first additive comprising a cationic polymer, 2-mercapto-5-benzimidazole sulfonic acid, 2-mercapto-5-benzimidazole sodium dihydrate, Ethylenethiourea and poly (diallyldimethylammonium chloride) partial 2-mercapto-5-benzimidazole sulfonate, at least one second additive selected from the group consisting of, and a sulfur atom-containing organic compound. 3 additives, the copper concentration is 10 to 60 g / L, the sulfuric acid concentration is 10 to 200 g / L, and contains chloride ions of 90 mg / L or less.

  In addition, the acidic copper plating product of the present invention is characterized in that the lattice constant at room temperature is larger than 3.6147 mm.

  Further, in the method of manufacturing a semiconductor device having a through silicon via of the present invention, the step of producing the through silicon via includes a non-through via on the one main surface of the silicon substrate on which a transistor is formed on one main surface. Forming a copper, electroplating at least the non-penetrating via by electroplating using the acidic copper plating solution, and polishing the other main surface of the silicon substrate to form the non-penetrating via. And forming the through silicon via by exposing the copper filled in the substrate.

  According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device having a through silicon via, wherein the step of producing the through silicon via includes a transistor and a wiring layer on the other main surface of the silicon substrate. And a step of copper plating by electroplating using the acidic copper plating solution of the present invention on the through via.

  The printed wiring board manufacturing method of the present invention includes a step of forming an opening reaching the copper foil on the upper surface of the substrate having a copper foil on the lower surface, and a conductive base layer on the upper surface of the substrate and the opening. And a step of forming a copper wiring layer by electroplating using the acidic copper plating solution according to claim 1 and a step of patterning the copper wiring layer. To do.

  Further, another method of manufacturing a printed wiring board according to the present invention includes a step of forming an opening reaching the copper foil on an upper surface of a substrate having a copper foil on a lower surface, and a conductive property on the upper surface of the substrate and the opening. The acidic copper plating solution according to claim 1 is used on the surface of the underlayer exposed from the resist layer, a step of forming a base layer, a step of forming a resist layer of a predetermined shape on the underlayer, and then the resist layer. The method includes a step of forming a copper wiring layer by electroplating, and then a step of removing the resist layer and the base layer.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the acidic copper plating solution which can suppress the thermal expansion of acidic copper plating thing. By using the acidic copper plating solution of the present invention, for example, pumping of TSV can be prevented without increasing the heating process and the CMP process, so that the three-dimensional mounting technology using TSV can be put into practical use. It becomes.

It is a graph which shows an example of the measurement result of the linear expansion coefficient of the acidic copper plating thing manufactured using the acidic copper plating solution of this invention. It is a scanning electron micrograph which shows an example of the cross-sectional structure of TSV manufactured using the acidic copper plating solution of this invention. It is a scanning electron micrograph which shows the surface state in room temperature (left side) and after heating (right side) of the comparative TSV sample. It is a scanning electron micrograph which shows the surface state of room temperature (left side) and after heating (right side) of the TSV sample of this invention. It is a scanning electron micrograph which shows the surface state of the TSV sample of this invention after 6 times heating. It is a scanning electron micrograph which shows the surface state of the comparative TSV sample after 6 times heating. It is a graph which shows another example of the measurement result of the linear expansion coefficient of the acidic copper plating thing manufactured using the acidic copper plating solution of this invention. It is a scanning electron micrograph which shows the change of the structure accompanying heating about the acidic copper plating thing manufactured using the acidic copper plating solution of this invention, a is 203 degreeC, b is 310 degreeC, c is 350 degreeC, d Indicates observation results when heated to 450 ° C. It is a scanning electron micrograph of the part used for the field emission type Auger electron spectroscopy (FEAES) analysis of the sample which heated the acidic copper plating thing manufactured using the acidic copper plating liquid of this invention at 450 degreeC. It is a figure which shows the result of the FEAES analysis of the black spot part in the photograph of FIG. It is a figure which shows the result of the FEAES analysis of the part shown with the code | symbol 2 as area | regions other than the black spot part in the photograph of FIG. It is a figure which shows an example of the result of the X-ray diffraction of the sample which heated the acidic copper plating thing manufactured using the acidic copper plating solution of this invention at 450 degreeC. It is a schematic diagram which shows the structure of the measurement cell used for the measurement of a linear expansion coefficient. It is a schematic diagram which shows the structure of the sample stage for high temperature used for observation of the pumping phenomenon of TSV.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

Embodiment 1
In the present embodiment, the acidic copper plating solution of the present invention will be described.
The acidic copper plating solution of the present invention comprises a first additive comprising a cationic polymer, 2-mercapto-5-benzimidazole sulfonic acid, 2-mercapto-5-benzimidazole sodium sulfonate dihydrate, ethylenethiourea , And at least one second additive selected from the group consisting of poly (diallyldimethylammonium chloride) moiety 2-mercapto-5-benzimidazole sulfonate and a third compound comprising a sulfur atom-containing organic compound An additive, a copper concentration of 10 to 60 g / L, a sulfuric acid concentration of 10 to 200 g / L, and a chloride ion of 90 mg / L or less.

  The cationic polymer used as the first additive is not particularly limited as long as it is a polymer having a cationic group in the molecule. Examples of the cationic group include a primary amine group, a secondary amine group, a tertiary amine group, and a quaternary ammonium group. Examples of the polymer containing a primary, secondary, or tertiary amine group in the molecule (also referred to as a primary, secondary, or tertiary amine salt polymer) include polydiallylamine salts, polyallylamine salts, and polyethyleneimine. . Examples of the polymer containing a quaternary ammonium group in the molecule (also referred to as a quaternary ammonium salt polymer) include poly (diallyldimethylammonium chloride) homopolymers and copolymers thereof. Can include a copolymer of diallyldimethylammonium chloride and sulfur dioxide. The composition of the copolymer is such that the molar ratio of diallyldimethylammonium chloride: sulfur dioxide is 0.5: 0.5 to 0.95: 0.05. Preferably, the molar ratio is 0.5: 0.5. A plurality of cationic polymers can also be used as the first additive. For example, a primary, secondary or tertiary amine salt polymer and a quaternary ammonium salt polymer may be used together. Further, a quaternary ammonium salt polymer homopolymer and a copolymer thereof may be used together.

  The concentration of the first additive is 1 to 50 mg / L, preferably 2 to 20 mg / L. This is because the linear expansion coefficient is unlikely to be small even if it is smaller than 1 mg / L or larger than 50 mg / L. The molecular weight of the quaternary ammonium salt polymer is preferably in the range of 1,000 to 100,000 as the number average molecular weight. Poly (diallyldimethylammonium chloride) and a copolymer of diallyldimethylammonium chloride and sulfur dioxide are commercially available. In the present invention, commercially available products can also be used. Examples of poly (diallyldimethylammonium chloride) include PAS-H-1L and PAS-5L (manufactured by Nitto Bo Medical). Examples of the copolymer of diallyldimethylammonium chloride and sulfur dioxide include PAS-A-1 and PAS-A-5 manufactured by Nitto Bo Medical Co., Ltd.

  The second additive includes 2-mercapto-5-benzimidazole sulfonic acid, 2-mercapto-5-benzimidazole sodium sulfonate dihydrate, ethylenethiourea, and poly (diallyldimethylammonium chloride) moiety 2- At least one compound selected from the group consisting of mercapto-5-benzimidazole sulfonate is used. Preferably, 2-mercapto-5-benzimidazole sulfonic acid, 2-mercapto-5-benzimidazole sodium sulfonate dihydrate, and poly (diallyldimethylammonium chloride) partial 2-mercapto-5-benzimidazole sulfonic acid A salt, more preferably a partial 2-mercapto-5-benzimidazole sulfonate of poly (diallyldimethylammonium chloride). The concentration of the second additive is 0.1 to 100 mg / L, preferably 1 to 50 mg / L. This is because the coefficient of linear expansion is unlikely to be small even if it is smaller than 0.1 mg / L or larger than 100 mg / L.

  Incidentally, the partial 2-mercapto-5-benzimidazole sulfonate of poly (diallyldimethylammonium chloride) means that a part of chloride ion which is a counter ion of poly (diallyldimethylammonium chloride) is 2-mercapto-5- It is substituted with benzimidazole sulfonate ion. The substitution ratio is preferably in the range of chloride body: 2-mercapto-5-benzimidazole sulfonate = 90: 10 to 50:50 in terms of molar ratio.

  As the third additive, a sulfur atom-containing organic compound is used. As the sulfur atom-containing organic compound, one or more known sulfur atom-containing organic compounds that are used as accelerators for increasing the plating deposition rate in acidic copper plating can be used. The sulfur atom-containing organic compound used in the present invention is an organic compound containing one or more sulfur atoms. For example, (di) alkanesulfonic acid and its salt, mercaptoalkanesulfonic acid and its salt, aromatic sulfonic acid and Mention may be made of one or more compounds selected from the group consisting of salts thereof, bis- (sulfoalkyl) disulfides and salts thereof, and dialkyldithiocarbamic acids and salts thereof. Examples of (di) alkanesulfonic acid include ethanesulfonic acid, propanesulfonic acid, dipropanesulfonic acid and the like. Examples of mercaptoalkanesulfonic acid include mercaptoethylsulfonic acid and mercaptopropanesulfonic acid. Moreover, as aromatic sulfonic acid, p-toluenesulfonic acid, m-xylenesulfonic acid, polystyrene sulfonic acid etc. can be mentioned, for example. Examples of bis- (sulfoalkyl) disulfide include bis- (sulfopropyl) disulfide. Examples of the dialkyldithiocarbamic acid include N, N-dimethyl-dithiocarbamylpropanesulfonic acid.

  The concentration of the third additive is 0.1 to 100 mg / L, preferably 0.5 to 50 mg / L. This is because the linear expansion coefficient is unlikely to be small even if it is smaller than 0.5 mg / L or larger than 50 mg / L.

  When a copolymer of poly (diallyldimethylammonium chloride) and / or diallyldimethylammonium chloride and sulfur dioxide is used as the first additive, the second additive is 2-mercapto-5-benzimidazolesulfonic acid. , Sodium 2-mercapto-5-benzimidazolesulfonate dihydrate, ethylenethiourea, or poly (diallyldimethylammonium chloride) partial 2-mercapto-5-benzimidazole sulfonate, A combination of poly (diallyldimethylammonium chloride) and poly (diallyldimethylammonium chloride) partial 2-mercapto-5-benzimidazole sulfonate. By combining poly (diallyldimethylammonium chloride) and poly (diallyldimethylammonium chloride) partial 2-mercapto-5-benzimidazole sulfonate, acidic copper plating that is less susceptible to thermal expansion, that is, has a smaller linear expansion coefficient Can be manufactured.

  As the copper ion source used in the acidic copper plating solution of the present invention, various inorganic copper salts and organic copper salts used in the acidic copper plating solution can be used, but copper sulfate pentahydrate is preferable. In order to reduce the linear expansion coefficient, the copper concentration in the plating solution is 10 to 60 g / L, preferably 15 to 55 g / L. The concentration of sulfuric acid used to dissolve the copper salt is 10 to 200 g. / L, preferably 25 to 180 g / L, and the concentration of chloride ions is 90 mg / L or less and is not zero, preferably 1 to 70 mg / L.

  By using the acidic copper plating solution of the present invention, it is possible to produce an acidic copper plating product having a low coefficient of linear expansion compared to conventional plated copper. The acidic copper plating solution of the present invention can be used as a copper material for electronic devices that require low thermal expansion. For example, TSV, the copper wiring of the glass substrate for circuits, the copper foil for copper clad laminated boards, the copper wiring for semiconductors, a copper heat sink, etc. can be mentioned.

Embodiment 2
In this embodiment, an acidic copper plating product obtained by electroplating using the acidic copper plating solution of the present invention will be described.

  The acidic copper plating product of the present invention is characterized in that the lattice constant at room temperature is larger than that of a conventional acidic copper plating product, for example, larger than 3.6147 mm. The lattice constant of the acidic copper plating product of the present invention is preferably 3.6147 to 3.62.

Furthermore, the acidic copper plating product of this invention has a small linear expansion coefficient compared with the conventional acidic copper plating product. Conventional plated copper has a linear expansion coefficient of 1.70 × 10 ⁻⁵ / K and takes a constant value independent of temperature. On the other hand, the acidic copper plating product of the present invention has a linear expansion coefficient smaller than that of conventional plated copper at a certain temperature or higher or in a certain temperature range. Hereinafter, the aspect of the acidic copper plating product of this invention is demonstrated using the minimum temperature and upper limit temperature of the heat processing temperature or use temperature of acidic copper plating product. The acidic copper plating product of a certain aspect always has a smaller linear expansion coefficient than the conventional plated copper within the range from the minimum temperature to the maximum temperature (Aspect 1). In addition, the acidic copper plating product of another aspect has a linear expansion coefficient smaller than that of the conventional plated copper up to a certain intermediate temperature between the lower limit temperature and the upper limit temperature. The coefficient is large (Aspect 2). Moreover, the acidic copper plating product of another aspect has a linear expansion coefficient smaller than the conventional plated copper only within a certain temperature range between the minimum temperature and the maximum temperature (Aspect 3). In addition, the acidic copper plating product of another aspect has a linear expansion coefficient smaller than that of conventional plated copper up to an intermediate temperature between the lower limit temperature and the upper limit temperature, and when the intermediate temperature is exceeded, the linear expansion coefficient is zero or negative. (Shrink) (Aspect 4). In another aspect, the linear expansion coefficient is larger than that of the conventional plated copper up to a certain intermediate temperature between the lower limit temperature and the upper limit temperature, and when the intermediate temperature is exceeded, the linear expansion coefficient decreases and becomes zero or minus (shrinks). (Aspect 5) Here, the lower limit temperature is 0 ° C to 100 ° C, and the upper limit temperature is 600 ° C to 800 ° C. The combination of the minimum temperature and the maximum temperature is 0 ° C to 800 ° C, preferably 100 ° C to 600 ° C. In addition, a certain temperature range in which the linear expansion coefficient is smaller than that of the conventional plated copper is not particularly limited as long as it is within an intermediate temperature range between the lower limit temperature and the upper limit temperature. For example, a combination of the lower limit temperature and the upper limit temperature is used. In the case of 100 ° C to 600 ° C, 100 ° C to less than 500 ° C, 100 ° C to less than 400 ° C, 100 ° C to less than 300 ° C, 100 ° C to less than 200 ° C, 200 ° C to less than 600 ° C, 200 ° C to less than 500 ° C, 200 ° C. to less than 400 ° C., 200 ° C. to less than 300 ° C., 300 ° C. to less than 600 ° C., 300 ° C. to less than 500 ° C., 300 ° C. to less than 400 ° C., 400 ° C. to less than 600 ° C., 400 ° C. to less than 500 ° C. It is 500 degreeC or more and less than 600 degreeC.

For example, the acidic copper plating product of the present invention includes one having a linear expansion coefficient at 200 ° C. of 1.58 × 10 ⁻⁵ / K or less. The acidic copper plating product of the present invention includes one having a linear expansion coefficient at 400 ° C. of 1.55 × 10 ⁻⁵ / K or less. The acidic copper plating product of the present invention has a linear expansion coefficient at 200 ° C. of 1.58 × 10 ⁻⁵ / K or less and a linear expansion coefficient at 400 ° C. of 1.55 × 10 ^{− What is 5} / K or less is included. Furthermore, the acidic copper plating product of the present invention includes those having a negative linear expansion coefficient at a certain temperature or higher and contracting conversely.

  In addition, the acidic copper plating product of the present invention preferably has a high carbon content after heat treatment. This is because the linear expansion coefficient tends to be small. For example, the carbon content after heat treatment at 450 ° C. is 0.005 wt% or more, preferably 0.01 wt% or more, more preferably 0.015 wt%. In addition, the value measured by the high frequency combustion infrared absorption method can be used for carbon content.

Here, a method for measuring the linear expansion coefficient used in the present invention will be described. For the measurement, a linear expansion measuring device (model TD5000 SA / 25/15) manufactured by NETZSCH JAPAN was used. As a measurement sample, a pipe-shaped sample prepared by the following procedure was used.
1. Production of cathode electrode for copper plating An Au film having a thickness of 15 nm was formed by sputtering on the surface of an aluminum pipe having an outer diameter of 4 mm, a thickness of 0.2 mm, and a length of 100 mm.
(Copper plating)
An aluminum pipe with an Au film whose upper part was masked with a fluororesin tape was immersed in the acidic copper plating solution of the present invention to form a cathode, and copper was deposited on the Au film at a constant current of 5 to 100 mA / cm ² . A DC power source PMX18-2A manufactured by Kikusui Electronics Co., Ltd. was used as the power source, and a magnet pump (Iwaki MD-15R-N) manufactured by Iwaki was used for stirring the plating solution. Moreover, the plating area on the surface of the aluminum pipe was adjusted with a masking tape, and was (1.5 × 0.4 × π) = 1.88 cm ² .
(Aluminum dissolution)
An aluminum pipe with copper deposited on the surface is immersed in a 100 g / L sodium hydroxide solution to dissolve aluminum, and is made of a copper plating product. The inner diameter is 4 mm, the thickness is about 20 μm, and the length. A 15 mm pipe (hereinafter abbreviated as a copper plated pipe) was obtained.
The linear expansion coefficient was measured by attaching the prepared copper plated pipe 12 in the measurement cell 10 shown in the plan view of FIG. 11 and using a quartz rod 11 as a standard sample in a temperature range from room temperature to 500 ° C. . With the thermal expansion of the sample (copper plating pipe) 12, the detection rod 14 in contact with the sample 12 is displaced, and the displacement is optically detected. The load of the detection rods 13 and 14 holding the standard sample 11 and the sample 12 was 1.0 g, and measurement was performed in an argon atmosphere. The measurement cell is mounted in an oven (not shown).

  The acidic copper plating product of the present invention can be used as a copper material for electronic devices that require low thermal expansion. For example, TSV, the copper wiring of the glass substrate for circuits, the copper foil for copper clad laminated boards, the copper wiring for semiconductors, a copper heat sink, etc. can be mentioned.

Embodiment 3
In the present embodiment, a method for manufacturing a semiconductor device having a through silicon via electrode using the acidic copper plating solution of the present invention will be described.
In the method of manufacturing a semiconductor device having a through silicon via of the present invention, the step of producing the through silicon via includes forming a non-through via on the one main surface of the silicon substrate on which a transistor is formed on one main surface. Forming at least the non-penetrating via, electroplating with an acidic copper plating solution according to claim 1, and polishing the other main surface of the silicon substrate to form the non-penetrating via. And exposing the filled copper to form the silicon through electrode.

  Moreover, in this manufacturing method, copper can be filled into a non-penetrating via in the step of copper plating.

  The semiconductor device manufactured by this manufacturing method is not particularly limited as long as it is an apparatus including TSV, and examples thereof include an LSI chip laminated with TSV, a glass substrate using TSV, and the like.

  The opening diameter of the non-through via is 0.5 to 100 μm, preferably 1 to 50 μm. The depth of the non-through via is 1 to 1000 μm, preferably 2 to 500 μm. The aspect ratio is 0.1 to 100, preferably 1 to 40.

As electroplating conditions in the step of filling copper by electroplating, the bath temperature is room temperature to 99 ° C, preferably 20 to 40 ° C. Further, as the energization method, direct current electrolysis or PR electrolysis (periodic current reversal electrolysis) can be used. The current density is 0.1 to 800 mA / cm ² , preferably 1 to 200 mA / cm ² . The plating time is preferably 20 to 300 minutes, although it depends on the diameter and depth of the via. The anode is not particularly limited as long as it is used for acidic copper plating, and a soluble electrode or an insoluble electrode can be used. The plating solution can be stirred by a general method such as aeration or jet.

  According to this manufacturing method, even when heated to 400 to 600 ° C. when forming the insulating oxide film, pumping can be prevented because the linear expansion coefficient of the acidic copper plating product forming the TSV is small. Thereby, pumping of TSV can be prevented without increasing the heating process and the CMP process.

Embodiment 4
In the third embodiment, the method of manufacturing a semiconductor device having a through silicon via using the biamide process has been described. However, the method of manufacturing a semiconductor device having a silicon through electrode using a via last process and a via last backside process is also described. The acidic copper plating solution of the present invention can be used.
That is, in the method of manufacturing a semiconductor device having a through silicon via according to another aspect of the present invention, the step of producing the through silicon via includes the step of producing the through silicon via on the other main surface of the silicon substrate on which the transistor and the wiring layer are formed. The method includes a step of forming a through via on a main surface, and a step of copper plating the electroconductive via plating using the acidic copper plating solution of the present invention on the through via.

  Further, in the present manufacturing method, the through via can be filled with copper in the copper plating step.

  In this manufacturing method, the opening via diameter, depth, and aspect ratio of the through via can use the same values as those of the non-through via of the third embodiment. The electroplating conditions are the same as in the third embodiment. The semiconductor device to be manufactured is the same as that in the third embodiment.

  According to the present manufacturing method, pumping of TSV can be prevented because the coefficient of linear expansion of the acidic copper plating product forming TSV is small even at the solder reflow temperature.

Embodiment 5
In the present embodiment, a method for manufacturing a printed wiring board using the acidic copper plating solution of the present invention will be described.

  The method for manufacturing a printed wiring board according to the present invention includes a step of forming an opening reaching the copper foil on an upper surface of a substrate having a copper foil on a lower surface, and a conductive underlayer is formed on the upper surface of the substrate and the opening. And a step of forming a copper wiring layer on the surface of the underlayer by electroplating using the acidic copper plating solution according to claim 1, and a step of patterning the copper wiring layer. Is.

  Moreover, in this manufacturing method, the step of forming the copper wiring layer may include filling the opening with copper.

As electroplating conditions, the bath temperature is room temperature to 99 ° C, preferably 20 to 40 ° C. Moreover, direct current electrolysis can be used for the energization method. The current density is 0.1 to 800 mA / cm ² , preferably 1 to 500 mA / cm ² . The plating time is preferably 20 to 300 minutes. The anode is not particularly limited as long as it is used for acidic copper plating, and a soluble electrode or an insoluble electrode can be used. The plating solution can be stirred by a general method such as aeration or jet.

  Due to recent demands for smaller and thinner electronic devices, there is an increasing demand for fine pitches in printed wiring boards. However, there is a possibility that the wiring board warps due to the thermal expansion of the copper wiring at the solder reflow temperature at the time of component mounting, and the connection failure occurs due to the contact between the solder bumps. On the other hand, by using the acidic copper plating solution of the present invention, it is also possible to suppress warping of the wiring board.

Embodiment 6
This Embodiment demonstrates the manufacturing method of another printed wiring board using the acidic copper plating solution of this invention.

  The method for manufacturing a printed wiring board according to the present invention includes a step of forming an opening reaching the copper foil on an upper surface of a substrate having a copper foil on a lower surface, and a conductive underlayer is formed on the upper surface of the substrate and the opening. 2. A copper wiring by electroplating using the acidic copper plating solution according to claim 1; a step of forming a resist layer having a predetermined shape on the underlayer; and then, the surface of the underlayer exposed from the resist layer. A step of forming a layer, and then a step of removing the resist layer and the underlayer.

  Moreover, in this manufacturing method, the step of forming the copper wiring layer may include filling the opening with copper.

  The electroplating conditions of this manufacturing method can be the same conditions as in the fifth embodiment.

  Also in this manufacturing method, as in the case of the fifth embodiment, by using the acidic copper plating solution of the present invention, the warpage of the wiring board due to the thermal expansion of the copper wiring at the solder reflow temperature during component mounting is suppressed. It becomes possible to do.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to a following example.

(Preparation of acidic copper plating solution)
Tables 1 to 10 show the compositions of the acidic copper plating solutions used in Examples and Comparative Examples. The abbreviations and sources of the additives used are as follows.
SPS: Bis- (sulfopropyl) disulfide (manufactured by Aldrich)
PD-1H: Polystyrene sulfonic acid PDSH: 1,3-propanedisulfonic acid SDDACC: Poly (diallyldimethylammonium chloride) (manufactured by Nittobo Medical)
NMDSC: Copolymer of diallyldimethylammonium chloride and sulfur dioxide (Nitto Bo Medical Co., Ltd.)
2M5S: 2-mercapto-5-benzimidazolesulfonic acid (Wako Pure Chemical Industries, Ltd.)
ETU: Ethylenethiourea (manufactured by Wako Pure Chemical Industries)
A2M5S: part of poly (diallyldimethylammonium chloride) 2-mercapto-5-benzimidazole sulfonate (manufactured by Nitto Bo Medical) (chloride body: 2-mercapto-5-benzimidazole sulfonate = 75: 25)
MB1: Sodium 2-mercapto-5-benzimidazolesulfonate dihydrate (Wako Pure Chemical Industries, Ltd.)

Test Example 1 (Measurement of linear expansion coefficient)
Using the cathode for copper plating described in the above method for measuring the linear expansion coefficient, plating is performed at a liquid temperature of 25 ° C. and a current density of 10 to 100 mA / cm ² to dissolve and remove the aluminum core material. A copper plated pipe having a thickness of about 20 μm and a length of 15 mm was obtained.

The linear expansion coefficient was measured in the range of room temperature to 500 ° C. using the above-described linear expansion measuring device made by NETZSCH JAPAN. The measurement results are shown in Tables 1 to 10. In addition, also about the commercially available copper pipe, when the linear expansion coefficient was measured in the range of room temperature to 500 degreeC, the linear expansion coefficient was (1.70 ± 0.01) * 10 < ^-5 > / K. .

The linear expansion coefficient of an Example is demonstrated. Comparative Example 1 is a plating solution that contains the first additive and the third additive but does not contain the second additive. In the case of Comparative Example 1, the elongation increases linearly with temperature as in the case of the conventional plated copper, and the linear expansion coefficient is 1.65 × 10 ⁻⁵ / K at 200 ° C. and 1.70 × at 400 ° C. 10 ⁻⁵ / K. In contrast, in Examples 1 to 13 including the first additive, the second additive, and the third additive, 1.03 × 10 ^{−5 /} K to 1.58 × 10 at 200 ° C. A low linear expansion coefficient of ^-5 / K was obtained. Further, when A2M5S was used as the second additive, in Example 3, a very low value of about 30% of pure copper was obtained, which was 0.535 × 10 ⁻⁵ / K at 400 ° C. Further, in Example 14, as shown in FIG. 1, the linear expansion coefficient tends to be negative from about 350 ° C. to a high temperature. For example, at 400 ° C., it is −7.5 × 10 ⁻⁵ / K.

  Examples 16 to 32 and Comparative Examples 2 to 4 are experimental examples using NMDSC as the first additive, 2M5S as the second additive, and SPS as the third additive. Examples 33 to 53 are experimental examples in which SDDACC is used as the first additive, A2M5S is used as the second additive, and SPS is used as the third additive. Examples 54 to 57 are experimental examples using ETU as the second additive. In Example 54, NMDSC was used as the first additive, and in Examples 55 to 57, the first additive was used. SDDAC was used. About copper concentration, if it was the range of 10-60 g / L, the low linear expansion coefficient was obtained (for example, Examples 16, 18, 36), but when it exceeded 60 g / L, the linear expansion coefficient became high ( Comparative Example 2). Further, when the sulfuric acid concentration was in the range of 10 to 200 g / L, a low linear expansion coefficient was obtained (for example, Examples 16, 19, 20, 37 to 39). Moreover, about the chloride ion density | concentration, the low linear expansion coefficient was obtained in the range below 90 mg / L except zero (Examples 21-24, 40-43, Comparative Examples 3 and 4). Moreover, even when the concentration of SPS was changed in a wide range, a low linear expansion coefficient was obtained (for example, Examples 25 to 28, 44 to 47). Moreover, even if it changed the density | concentration of A2M5S in the wide range, the low linear expansion coefficient was obtained (Examples 30-32, 51-53). Moreover, even when ETU was used, the low linear expansion coefficient was obtained (Examples 54-57). Further, a low linear expansion coefficient was obtained even when the concentration of SDDACC was changed in a wide range (for example, Examples 48 to 50). Moreover, about the influence of bath temperature, the low linear expansion coefficient was obtained in any case of room temperature (about 20 degreeC, Example 33), 40 degreeC (Example 34), and 50 degreeC (Example 35).

  Also, when MB1 was used as the second additive, a low linear expansion coefficient was obtained (Examples 58 and 59). Moreover, a low linear expansion coefficient was obtained even when PS-1H was used as the third additive (Example 60) or when PDSH was used (Example 61).

Test Example 2 (TSV pumping evaluation)
Next, TSV was produced using the acidic copper plating solution of the present invention, and the pumping of the produced TSV was evaluated.

  A silicon substrate having a non-through via having an opening diameter of 6 μm × depth of 25 μm (aspect ratio of 4) was used, and a base layer having a thickness of 200 nm was formed on the surface thereof by sputtering.

The silicon substrate on which the underlayer was formed was immersed in an acidic copper plating solution having the composition of Example 2, and copper plating was performed using a (phosphorus-containing copper) anode and plating time of 90 minutes under the following PR electrolysis conditions. It was. In addition, copper plating was performed under the same PR electrolysis conditions using the plating solution having the composition of Comparative Example 1.
Positive electrolysis current value (Ion) −3 mA / cm ²
Reverse electrolysis current value (Irev) 18 mA / cm ²
Positive electrolysis time (Ton) 200ms
Reverse electrolysis time (Trev) 10ms
Rest time (Toff) 200ms

  The state of the cross section of the non-through via filled with copper plating was observed with a scanning electron microscope (hereinafter also referred to as SEM) (S-4300 manufactured by Hitachi, Ltd.). FIG. 2 shows an SEM photograph of the section. It was confirmed that a TSV completely filled with no voids was obtained.

  Next, the produced TSV was fixed to a high temperature sample stage 20 for in situ observation shown in FIG. The sample stage 20 has a ceramic support 23 that supports a ceramic heater 21 having a carbon plate 22 disposed on the surface thereof. The sample 28 is fixed on the carbon plate 22 by a pair of clamps 24 and 25. The temperature of the ceramic heater 21 is controlled by the thermocouple 27, and the temperature of the sample 28 is detected by the thermocouple 26.

  FIG. 3A shows scanning electron micrographs of a TSV produced using the plating solution of Comparative Example 1 at room temperature (left side) and when heated to 450 ° C. (right side). It can be seen that TSV overflows on the surface of the silicon substrate and pumping occurs. On the other hand, FIG. 3B is a scanning electron micrograph of TSV produced using the plating solution of Example 14 when heated to room temperature (left side) and 450 ° C. (right side). The swelling of TSV from the silicon substrate surface was not recognized, and it was confirmed that pumping was suppressed.

  4A and 4B are scanning electron micrographs after heating at 450 ° C. six times, and no pumping is observed in the TSV produced using the plating solution of Example 14 (FIG. 4A). On the other hand, pumping was recognized in TSV (FIG. 4B) produced using the plating solution of Comparative Example 1. In addition, TSV produced using the plating solution of Comparative Example 1 was pumped from the surface of the silicon substrate to a height of 1.419 μm at the maximum.

Test Example 3 (TSV electrical resistance measurement)
Using a plating solution having the composition of Example 2, an electrode obtained by sputtering gold on the surface of a glass plate (size: 25 × 75 mm) was used as a cathode, and phosphorous copper was used as an anode, with a current density of 3 mA / cm ^2. Plating was performed. On the other hand, using a plating solution having the composition of Comparative Example 1 and performing copper plating under the same conditions was used as a comparative sample. The produced sample was subjected to the following heat treatment after measuring electrical resistance at room temperature.
Rate of temperature increase: 10 ° C./min. Degree of vacuum: 1.5 × 10 ⁻⁵ Torr
Holding temperature: 400 ° C
Retention time: 30 minutes

The electrical resistance was measured at room temperature using the four probe method. The volume resistance value of the comparative sample was 3.7 × 10 ⁻⁶ Ω · cm. On the other hand, the volume resistance value of the acidic copper plating product produced using the plating solution having the composition of Example 2 was 4.0 × 10 ⁻⁶ Ω · cm. The difference was about 9%, and it was confirmed that it had an electrical resistance equivalent to the conventional one.

Test Example 4 (Evaluation as printed wiring board wiring)
A copper plated pipe produced using the same method as in Test Example 1 was used as a sample, except that the plating solution having the composition of Example 15 was used and the current density was 3 mA / cm ² . The sample was heated at 200 ° C. for 60 minutes, and then the linear expansion coefficient was measured. Moreover, what performed the copper plating on the same conditions using the plating solution of the composition of the comparative example 1 was made into the comparative sample.

The results are shown in FIG. The sample using the plating solution having the composition of Example 15 had a linear expansion coefficient at 230 ° C. of 0.5 × 10 ⁻⁵ / K, and its elongation was about 34% smaller than that of the comparative sample. . From this, it was confirmed that copper-plated wiring capable of suppressing thermal expansion was possible at the solder reflow temperature.

In addition, a sample for measuring electrical resistance was prepared in the same manner as in Test Example 3 using the plating solution having the composition of Example 1. A comparative sample was prepared in the same manner as in Test Example 3 using the plating solution having the composition of Comparative Example 1. The produced sample was subjected to the following heat treatment.
Rate of temperature increase: 10 ° C./min. Degree of vacuum: 1.5 × 10 ⁻⁵ Torr
Holding temperature and holding time: 60 minutes at 200 ° C, 1 minute at 230 ° C

The electrical resistance was measured at room temperature using the four probe method. The volume resistance value of the comparative sample was 3.7 × 10 ⁻⁶ Ω · cm. On the other hand, the volume resistance value of the acidic copper plating product manufactured using the plating solution having the composition of Example 15 was 5.1 × 10 ⁻⁶ Ω · cm. The difference was about 39%, and it was confirmed that it had an electrical resistance equivalent to the conventional one.

(Analysis of acidic copper plating)
About the acidic copper plating thing produced using the acidic copper plating liquid of this invention, the FEAES analysis and the X-ray diffraction analysis were performed. FEAES analysis was performed using a field emission Auger electron spectrometer (model 686) manufactured by ULVAC-PHI. The acidic copper plating product of Example 14 was used for the analysis.

  The structure observation result of the acidic copper plating product of this invention accompanying heat processing in FIG. 6 is shown. It is a structure | tissue observation result with maintaining the heating temperature when a is heated at 203 degreeC, b is 310 degreeC, c is 350 degreeC, and d is 450 degreeC. In a, a copper crystal having a particle size of about 1.0 μm can be observed. In b, a black structure having a particle size of about 100 μm appeared. Many black structures were deposited near the triple point of the grain boundary of the copper crystal. Moreover, the number of the black structures increased in c and d.

  FIG. 7 is a SEM photograph of the acidic copper plating product of the present invention heated to 450 ° C., where the black spot 1 visible in the center of the photograph is a black structure and the other structure is copper. 8 and 9 are FEAES analysis results of the black tissue and the other tissues in the photograph of FIG. 7, respectively, the horizontal axis indicates kinetic energy (eV), and the vertical axis indicates intensity. The black spot 1 has almost no copper strength near 910 eV. However, the strength of carbon near 280 eV is strong. The black texture is a lump of carbon. On the other hand, in the structure other than the black structure, for example, in the portion indicated by reference numeral 2 in the photograph, the strength of copper is remarkably strong, and the strength of carbon is also strong at the same time. FEAES gives information on the outermost surface of the metal. Metals easily adsorb carbon in the atmosphere. Therefore, it is considered that the strength of carbon was strong in the portion of reference numeral 2.

  In addition, about the acidic copper plating material of this invention heated to 450 degreeC, when carbon content analysis was performed by the high frequency combustion infrared absorption method using carbon / sulfur analyzer CSLS600 made from LECO Japan, it was 0.018 weight % Values were obtained. On the other hand, when the carbon content was also analyzed for Comparative Example 1 not including the second additive, the carbon content was 0.004% by weight.

  FIG. 10 is a diagram showing the results of X-ray diffraction of an as-deposited acidic copper plating product and the acidic copper plating product after annealing at 450 ° C. for 30 minutes (hereinafter referred to as “annealing”). The Cu (222) αh and Cu (222) α2 on the high angle side where the change of the lattice constant can be detected remarkably are shown. Cu (222) αh is displaced to the high angle side by about 0.3 degrees after annealing. When this displacement of the lattice constant is expressed by the lattice constant, d = 3.6155Å in as-deposit and d = 3.6139Å after annealing, confirming that the lattice constant is reduced and the copper unit cell is contracted.

  The as-deposited copper is considered to have a solid solution of carbon in the copper unit cell. Therefore, this solid solution copper is in a non-equilibrium state. With heating, the non-equilibrium solid solution copper changes to an equilibrium copper that does not dissolve carbon. This carbon diffuses and precipitates at the triple point of the copper grain boundary (b, c, d in FIG. 6 and black structure in FIG. 7). It is considered that the contraction of the unit cell from the nonequilibrium copper to the equilibrium copper accompanying the heat treatment is a mechanism in which copper having a lower linear expansion coefficient than that of the conventional plated copper is developed.

  According to the present invention, it is possible to provide an acidic copper plating solution capable of suppressing the thermal expansion of a plated product. Thereby, it becomes possible to provide the copper material for electronic devices, such as wiring and a heat sink, in which low thermal expansion is required.

DESCRIPTION OF SYMBOLS 10 Measurement cell 11 Quartz rod 12 Copper plated pipe 13, 14 Detection rod 20 Sample stage 21 Ceramic heater 22 Carbon plate 23 Ceramic support 24, 25 Clamp 26, 27 Thermocouple 28 Sample

Claims (15)

A first additive comprising a cationic polymer;
2-mercapto-5-benzimidazolesulfonic acid, 2-mercapto-5-benzimidazole sodium sulfonate dihydrate, ethylenethiourea, and poly (diallyldimethylammonium chloride) moiety 2-mercapto-5-benzimidazolesulfonic acid At least one second additive selected from the group consisting of salts;
A third additive comprising a sulfur atom-containing organic compound,
An acidic copper plating solution having a copper concentration of 10 to 60 g / L, a sulfuric acid concentration of 10 to 200 g / L, and containing chloride ions of 90 mg / L or less.   The acidic copper plating solution according to claim 1, wherein the first additive is a quaternary ammonium salt polymer.   The acidic copper plating solution according to claim 2, wherein the first additive is poly (diallyldimethylammonium chloride) or a copolymer of diallyldimethylammonium chloride and sulfur dioxide.   The acidic copper plating solution according to any one of claims 1 to 3, wherein the second additive is poly (diallyldimethylammonium chloride) partial 2-mercapto-5-benzimidazole sulfonate.   Said third additive comprises (di) alkanesulfonic acid and its salt, mercaptoalkanesulfonic acid and its salt, aromatic sulfonic acid and its salt, bis- (sulfoalkyl) disulfide and its salt, and dialkyldithiocarbamic acid and The acidic copper plating solution according to any one of claims 1 to 4, which is one or more compounds selected from the group consisting of salts thereof.   An acidic copper plating product having a lattice constant at room temperature larger than 3.6147 mm and a carbon content after heat treatment at 450 ° C. of 0.005 wt% or more. The acidic copper plating product according to claim 6 whose linear expansion coefficient in 200 ° C is 1.58x10 < ^-5 > / K or less. The acidic copper plating product according to claim 6 or 7, wherein the linear expansion coefficient at 400 ° C is 1.55 × 10 ^-5 / K or less.   The acidic copper plating product according to any one of claims 6 to 8, wherein the acidic copper plating product is a through silicon via electrode. A method for manufacturing a semiconductor device having a through silicon via,
The step of producing the silicon through electrode comprises
Forming a non-through via in the one main surface of the silicon substrate having a transistor formed on one main surface;
The step of copper plating by electroplating using the acidic copper plating solution according to claim 1 at least on the non-through via,
Polishing the other main surface of the silicon substrate to expose the copper filled in the non-penetrating via to form the silicon through electrode, and a method for manufacturing the semiconductor device.   A method of manufacturing a semiconductor device having a through silicon via, wherein the step of forming the through silicon via forms a through via on the other main surface of the silicon substrate on which a transistor and a wiring layer are formed on one main surface. The manufacturing method of this semiconductor device including the process and the process of carrying out copper plating to the said penetration via by the electroplating using the acidic copper plating solution of Claim 1.   The method of manufacturing a semiconductor device according to claim 10, wherein in the copper plating step, the non-through via or the through via is filled with copper.   Forming an opening reaching the copper foil on the upper surface of the substrate having a copper foil on the lower surface, forming a conductive underlayer on the upper surface of the substrate and the opening, and then charging the surface of the underlayer A method for producing a printed wiring board, comprising: a step of forming a copper wiring layer by electroplating using the acidic copper plating solution according to Item 1; and a step of patterning the copper wiring layer.   Forming an opening reaching the copper foil on an upper surface of a substrate having a copper foil on a lower surface; forming a conductive underlayer on the upper surface of the substrate and the opening; and a predetermined layer on the underlayer A step of forming a resist layer having a shape; a step of forming a copper wiring layer by electroplating using the acidic copper plating solution according to claim 1; and a step of forming the resist layer on the surface of the underlayer exposed from the resist layer. And a step of removing the foundation layer.   The method for manufacturing a printed wiring board according to claim 13, wherein in the step of forming the copper wiring layer, the opening is filled with copper.

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