JP5105162B2 - Copper surface treatment method - Google Patents

Description

The present invention relates to a process how the copper surface.

  The development of the information society in recent years has been remarkable, and consumer devices have been reduced in size, weight, performance, and functionality, such as personal computers and mobile phones. Industrial equipment includes wireless base stations, optical communication devices, and servers. In addition, there is a demand for improvement in functions in the same way regardless of whether it is large or small, such as routers and other network-related devices. In addition, with the increase in the amount of information transmitted, the frequency of signals handled tends to increase year by year, and high-speed processing and high-speed transmission technology are being developed. With regard to mounting relations, the development of system-on-chip (SoC), system-in-package (SiP), etc., as new high-density mounting technologies, along with higher speed and higher functionality of LSIs such as CPUs, DSPs, and various memories Has been done. For this reason, on the semiconductor chip mounting substrate and the mother board, fine wiring with a wiring width / space (L / S) = 15 μm / 15 μm or less is formed in order to cope with high frequency, high density wiring, and high functionality. Build-up type multilayer wiring boards have come to be used.

  A build-up multilayer wiring board is manufactured by repeating an interlayer insulating layer forming step and a wiring forming step. In this manufacturing method, it is important to ensure the adhesive strength between the wiring and the insulating resin. In order to satisfy the characteristics shown above, conventionally, the following copper surface treatment method has been performed. That is, as shown in Patent Document 1, a roughened shape on the order of microns is imparted to the copper surface to make the copper surface non-glossy, and further, the adhesion between the copper surface and the resist or the copper surface and the insulating resin due to the anchor effect. Is the way to get. For example, the height of the copper surface is 2.0 to 3.0 μm using an aqueous solution containing a main agent composed of an inorganic acid and a copper oxidizing agent and an auxiliary composed of at least one azole and at least one etching inhibitor. There is a method of imparting a roughened shape.

  Moreover, it is the method of obtaining the adhesive force of a copper surface and insulating resin by an anchor effect by providing a fine copper oxide needle-like crystal on the copper surface and forming irregularities. For example, there is a method of imparting fine copper oxide needle crystals by immersing at about 80 ° C. using an alkaline aqueous solution containing an oxidizing agent such as sodium chlorite. In addition, after forming irregularities with fine copper oxide needle-like crystals on the copper surface as shown in Patent Document 2, by performing a reduction treatment, by giving fine metal copper needle-like crystals, by the anchor effect, This is a method for obtaining an adhesive force between the copper surface and the insulating resin. For example, by using an alkaline aqueous solution containing an oxidizing agent such as sodium chlorite and soaking at about 80 ° C., fine needle-like crystals of copper oxide are imparted, and then at least one of amine boranes and boron-based There is a method of giving fine metallic copper needle crystals by performing a reduction treatment with an acidic solution mixed with a chemical. Furthermore, as shown in Patent Document 3, after a metal that is nobler than copper is discretely formed on the copper surface, copper is oxidized, and after forming irregularities with crystals of copper oxide, a reduction treatment is performed, thereby reducing the metal. In this method, nano-level irregularities are formed by copper crystals, and an adhesive effect between the copper surface and the insulating resin is obtained by an anchor effect.

JP 2000-282265 A Japanese Patent No. 2656622 JP 2006-249519 A

  A first conventional technique for imparting a micron-order roughened shape to the above-described copper surface and improving the adhesive strength between the copper surface and the insulating resin is 2.0 on the copper surface with an Rz (10-point average surface roughness) of 2.0. An unevenness of ˜3.0 μm was formed, and the adhesive strength was secured by the anchor effect. However, since the unevenness of the wiring surface has a rough shape exceeding 1 μm, when a high-frequency electrical signal is passed through such wiring, the current flows in the vicinity of the wiring surface due to the skin effect, resulting in transmission loss. There is a problem that becomes larger. In addition, when the wiring has a fine wiring width / space (L / S) = less than 25 μm / 25 μm, there is a problem that the wiring is clearly thinner or the variation in the wiring width becomes larger than before processing.

  The second conventional technique for improving the adhesive strength between the copper surface and the insulating resin by imparting fine copper oxide needle-like crystals to the copper surface is that the surface roughness Rz of the wiring surface is 0.1 to 1.5 μm. By forming the projections and depressions, the adhesive strength was secured by the anchor effect as in the first prior art. However, there is a problem that the unevenness of the unevenness is large, and when Rz <0.5 μm, there is a problem that the adhesion reliability at the time of high temperature / high humidity test is lowered. There is a problem of growing. In addition, when this copper oxide needle crystal dissolves in the plating process for through-hole connection, a pink ring (pink ring) is generated around the through-hole. And the peeling between the copper surface and the insulating resin tends to occur.

  The third conventional technique for improving the adhesive strength between the copper surface and the insulating resin by applying fine metallic copper needle crystals to the copper surface is the dissolution of the metal copper needle crystals during the through-hole plating process. There is no occurrence of pink rings. However, as with the second prior art, when Rz <0.5 μm, there is a problem that the adhesion reliability at the time of the high temperature / high humidity test decreases, and when Rz> 1.0 μm, the transmission loss is similar to the first prior art. There is a problem that becomes larger.

In order to solve these problems of the prior art, the present inventors discretely form noble metals on the copper surface disclosed in Patent Document 3, and then oxidize with an alkaline solution containing an oxidizing agent to obtain copper oxide. Then, by carrying out an alkaline solution reduction treatment containing a reducing agent, a fine metal copper crystal having an Rz of 1 to 1,000 nm is imparted to improve the adhesive strength between the copper surface and the insulating resin. A fourth technique was proposed. However, it has been found that depending on the insulating resin used, there is a problem that the adhesive strength during the high temperature / high humidity test is lowered. The object of the present invention is to improve the above-mentioned problems of the prior art, and ensure the adhesive strength between the copper surface and the insulating resin without forming irregularities exceeding 1,000 nm on the copper surface. is to provide a process how the copper surface which can improve various reliability.

The present invention relates to the following.
1. A step of discretely forming a metal nobler than copper on the copper surface, a step of forming copper oxide on the copper surface by oxidizing with an alkaline solution containing an oxidizing agent, and then dissolving the copper oxide in an acidic solution A step of oxidizing the copper surface again with an alkaline solution containing an oxidizing agent to form copper oxide on the surface, and then reducing the copper oxide with an alkaline solution containing a reducing agent to form metallic copper. The processing method of the copper surface which has the process of forming.
2. Item 2. The copper surface treatment according to Item 1, wherein the oxidizing agent is one or more selected from the group consisting of chlorate, chlorite, hypochlorite, perchlorate, and peroxodisulfate. Method.
3. Item 3. The metal according to Item 1 or 2, wherein the metal nobler than copper is a metal selected from the group consisting of gold, silver, platinum, palladium, rhodium, rhenium, ruthenium, osmium, and iridium, or an alloy containing the metal. Copper surface treatment method.
4). Forming amount of noble metal, 0.001μmol / dm ² or more and is 5 [mu] mol / dm ² or less, the processing method of the copper surface as claimed in any one of claim 1 to 3.
5. Item 5. The copper surface treatment method according to any one of Items 1 to 4, wherein the roughness of the copper surface is 1 nm or more and 1000 nm or less in terms of Rz .

The present invention, without forming irregularities in excess of 1,000nm the copper surface, to ensure the adhesive strength between the copper surface and an insulating resin, to provide a process how the copper surface which can improve various reliability It became possible.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. Here, as an example of application of the copper surface treatment method of the present invention, surface treatment of copper wiring of a substrate for mounting a semiconductor chip will be described as an example, but other copper surface treatment methods can be similarly applied.
(Copper surface unevenness forming method)
By forming a noble metal (noble metal) discretely on the copper surface and then oxidizing the copper surface with an alkaline solution containing an oxidizing agent, fine irregularities due to dense and uniform copper oxide crystals are formed on the copper surface. Can be formed. Moreover, when it processes with an acidic solution after the said oxidation process, a hole-shaped fine unevenness | corrugation can be formed by selectively removing the crystal | crystallization of copper oxide. Furthermore, after that, oxidation treatment is performed again with an alkaline solution containing an oxidizing agent, whereby dense and uniform fine irregularities with a higher crystal density of copper oxide can be formed on the copper surface. Further, by performing a reduction treatment after the oxidation treatment, fine irregularities due to dense and uniform metal copper crystals can be formed. Further, after the oxidation treatment or after the reduction treatment, the copper surface roughness generated by the surface treatment of copper is preferably 1 nm or more and 1,000 nm or less in terms of Rz. Further, Rz is more preferably 1 nm or more and 100 nm or less, and further preferably 1 nm or more and 50 nm or less. If Rz is less than 1 nm, the adhesive strength with an insulating resin or the like tends to decrease, and if Rz exceeds 1,000 nm, a problem that transmission loss increases tends to occur. “Dense and uniform” means that the shape of the copper surface is processed with a scanning electron microscope (SEM) or with a focused ion beam processing observation device (FIB) and observed with a scanning ion microscope (SIM) image. Meaning that the size and height of the crystal in which the plating film is formed on copper oxide, metal copper or metal copper is 1 nm or more and 1,000 nm or less, and the formed crystals are densely packed. It is.

Below, each process mentioned above is demonstrated in detail. In addition, in this invention, it is preferable to perform as a pre-processing of each process the degreasing process which cleans the copper surface, a pickling process, or combining these suitably.
(Method of forming noble metal on copper surface)
The method for discretely forming a noble metal (noble metal) on the copper surface is not particularly limited, but without completely covering the underlying copper surface by electroless plating, electroplating, displacement plating, sputtering, vapor deposition, or the like. It is preferably formed so as to be uniformly dispersed on the copper surface. More preferably, it is a method of discretely forming on the copper surface by displacement plating. Displacement plating uses the difference in ionization tendency between copper and noble metals, and according to this, noble metals can be formed discretely on the copper surface easily and inexpensively. The noble metal is not particularly limited, but it is preferable to use a metal selected from the group consisting of gold, silver, platinum, palladium, rhodium, rhenium, ruthenium, osmium, iridium, or an alloy containing these metals. Is preferred. Palladium is preferred because, during the displacement plating is because can be easily be formed of palladium on copper surface discretely 0.001μmol / dm ² or more and 5 [mu] mol / dm ² or less.

The formation amount of noble metal formed discretely on the copper surface is not particularly limited, it is preferably 0.001μmol / dm ² or more and is 5 [mu] mol / dm ² or less. The formation amount is more preferably at 0.01μmol / dm ² or more and 5 [mu] mol / dm ² or less, more preferably 0.1 [mu] mol / dm ² or more and is 4μmol / dm ² or less. When the formation amount is less than 0.001 μmol / dm ² , it tends to be difficult to form dense and uniform fine irregularities. Further, it tends to be difficult to form a plating film during the electroless plating process described later. If it exceeds 5 μmol / dm ² , the adhesive strength with the insulating resin tends to decrease. The amount of the noble metal formed discretely on the copper surface can be determined by dissolving the noble metal on the copper surface with aqua regia and quantitatively analyzing the dissolved solution with an atomic absorption photometer. The term “discrete” means that the noble metal formed in an amount of 0.001 μmol / dm ² or more and 40 μmol / dm ² or less is dispersed on the copper surface without completely covering the copper surface with the noble metal. Meaning.

(Copper surface oxidation method)
In the present invention, after the noble metal is discretely formed on the copper surface as described above, the copper surface is oxidized with an alkaline solution containing an oxidizing agent.
The alkaline solution containing the oxidizing agent is not particularly limited. For example, an alkaline solution containing an alkali metal or an alkaline earth metal may be added to chlorate, chlorite, hypochlorite, perchlorate. The alkaline solution further contains an oxidizing agent such as peroxodisulfate. The alkaline solution containing the alkali metal or alkaline earth metal is, for example, an alkali metal compound such as sodium hydroxide, potassium hydroxide, or sodium carbonate or water obtained by treating an alkaline earth metal compound with water or an ion exchange resin. What is obtained by adding to a solvent is preferable. More specifically, the oxidizing agent is, for example, sodium hypochlorite, sodium chlorite, sodium chlorate, sodium perchlorate, potassium hypochlorite, potassium chlorite, potassium chlorate, It is preferable to use potassium perchlorate, ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate, etc., and sodium chlorite is particularly preferred from the viewpoints of handleability such as storage stability and safety and price. . Moreover, it is more preferable to add a phosphate to the alkaline solution. Although it does not specifically limit as a phosphate which can be used, For example, it is preferable to use trisodium phosphate, tripotassium phosphate, trilithium phosphate, etc. Furthermore, it is more preferable to add a known organic acid or chelating agent to the alkaline solution.

  Although the oxidizing agent density | concentration of the alkaline solution containing the said oxidizing agent is not specifically limited, It is preferable that it is 1-100 g / L. Moreover, when adding a phosphate to the said solution, it is preferable to add so that the density | concentration may be 1-40 g / L. Moreover, the pH of the said solution should just be a value which shows alkalinity, Although it does not specifically limit, It is preferable that it is 11-13. The pH can be adjusted appropriately using an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, potassium hydroxide, or the like.

The crystal amount of copper oxide generated on the copper surface is preferably 0.001 mg / cm ² or more and 0.3 mg / cm ² or less, 0.01 mg / cm ² or more and 0.2 mg / cm ² or less. It is more preferable that it is 0.03 mg / cm ² or more and 0.1 mg / cm ² or less. If the amount of copper oxide crystals is less than 0.001 mg / cm ² , the adhesive strength with insulating resin or the like tends to decrease, and if it exceeds 0.3 mg / cm ² , the problem of increased transmission loss tends to occur. It is in. The amount of copper oxide crystals formed on the copper surface can be examined by measuring the amount of electrolytic reduction. For example, using oxidized copper as a working electrode (cathode), a constant amount of electricity of 0.5 mA / cm ² is passed, and the surface potential of copper completely changes from the potential of copper oxide to the potential of metallic copper. The amount of copper oxide crystals can be determined from the amount of electrolytic reduction by measuring the time until a stable potential of −1.0 V or less is obtained.

  Further, the temperature of the solution at the time of performing the oxidation treatment with the alkaline solution containing the oxidizing agent is not particularly limited, but in consideration of sufficient oxidation treatment and damage to the base material given by the alkaline solution, the temperature is 20 to 95 ° C. It is preferable that the temperature is 30 to 80 ° C, and 40 to 60 ° C is particularly preferable. In addition, the oxidation treatment time may be appropriately determined so that a desired amount of copper oxide crystals is formed in consideration of the concentration of the oxidation treatment liquid, the liquid temperature, and the like. In addition, in the oxidation treatment of the copper surface with the above-described oxidation treatment liquid, the copper surface is covered with copper oxide needle crystals in a short time, and the oxidation reaction is stopped, so that the treatment time can be shortened compared to the prior art. is there.

(Treatment method with acidic solution after oxidation treatment)
After forming the fine unevenness | corrugation by the crystal | crystallization of the copper oxide formed in the copper surface by the said oxidation process, it processes with an acidic solution. Although it does not specifically limit as said acidic solution, For example, you may process with the acidic solution containing a sulfuric acid, hydrochloric acid, and nitric acid as an inorganic acid. It is particularly preferable to treat with an acidic solution containing sulfuric acid. Although the density | concentration of the inorganic acid of the said acidic solution is not specifically limited, It is preferable that it is 0.1-100 g / L. Moreover, the pH of the said solution should just be a value which shows acidity, Although it does not specifically limit, It is preferable that it is pH2 or less. The pH can be adjusted appropriately using an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, potassium hydroxide, or the like. Moreover, the temperature of the said solution at the time of processing with the said acidic solution is although it does not specifically limit, It is 10-40 degreeC in order to consider the safety | security in use and to selectively remove a crystal of copper oxide. It is preferably 15 to 35 ° C, more preferably 20 to 30 ° C. The treatment time with the acidic solution may be appropriately determined so that the copper oxide crystals can be selectively removed in consideration of the concentration of the acidic solution, the liquid temperature, and the like.

(Re-oxidation method after treatment with acidic solution)
In the present invention, after the copper oxide crystals are selectively removed by treatment with an acidic solution as described above, the copper surface is again oxidized with an alkaline solution containing an oxidizing agent. The details are the same as the method for oxidizing the copper surface.

(Reduction treatment method)
It is preferable that the fine unevenness due to the copper oxide crystals formed on the copper surface by the oxidation treatment is made into a fine unevenness of metallic copper by the reduction treatment. In this reduction treatment, an aqueous solution in which formaldehyde, paraformaldehyde, an aromatic aldehyde compound or the like is added to an alkaline solution adjusted to pH 9.0 to 13.5, or an aqueous solution in which hypophosphorous acid or hypophosphite is added. It is preferable to use an aqueous solution to which dimethylamine borane or a compound containing it is added, an aqueous solution to which a borohydride salt or a compound containing it is added, or the like. More specifically, for example, HIST-100 (manufactured by Hitachi Chemical Co., Ltd., trade names, including HIST-100B and HIST-100D) and the like are more preferably used as the solution for the reduction treatment. In addition, the alkaline solution shown here is not particularly limited, but for example, an alkaline solution containing an alkali metal or an alkaline earth metal is preferable. More specifically, for example, those obtained by adding an alkali metal compound such as sodium hydroxide, potassium hydroxide or sodium carbonate or an alkaline earth metal compound to a solvent such as water or water treated with an ion exchange resin are more preferable.

(Coupling process)
After the reduction treatment, a coupling treatment may be performed in order to further improve the adhesive strength between the copper surface and the insulating layer (build-up layer or the like). Examples of the coupling agent used in the coupling treatment include silane coupling agents, aluminum coupling agents, titanium coupling agents, and zirconium coupling agents, and these include one or more types. You may use together. Of these, silane coupling agents are preferable, and the silane coupling agent has a functional group such as an epoxy group, amino group, mercapto group, imidazole group, vinyl group, or methacryl group in the molecule. Is preferred. The coupling agent can be used as a solution containing the same, and the solvent used for the preparation of the coupling agent solution is not particularly limited, but water, alcohol, ketones, and the like can be used. It is. A small amount of acid such as acetic acid or hydrochloric acid can be added to promote hydrolysis of the coupling agent. In addition, the content of the coupling agent is preferably 0.01% by mass to 5% by mass and more preferably 0.1% by mass to 1.0% by mass with respect to the entire coupling agent solution. preferable. The treatment with the coupling agent can be performed by a method of immersing copper to be treated in the coupling agent solution adjusted as described above, or spraying or applying the coupling agent solution to copper. The copper treated with the silane coupling agent is dried by natural drying, heat drying, or vacuum drying. Depending on the type of coupling agent used, it may be washed with water or ultrasonically before drying. Is possible.

(Corrosion suppression treatment)
After the reduction treatment, a corrosion inhibition treatment is preferably performed in order to further inhibit copper corrosion. Although it does not specifically limit as a corrosion inhibitor used for a corrosion inhibition process, For example, what contains at least 1 or more types of a sulfur containing organic compound or a nitrogen containing organic compound is preferable, such as a mercapto group, a sulfide group, or a disulfide group. More preferred is a sulfur atom-containing organic compound or a compound containing at least one nitrogen-containing organic compound containing —N═, N═N, or —NH ₂ in the molecule.

More specifically, examples of the sulfur-containing organic compound include, for example, a general formula HS- (CH ₂ ) nR (wherein n is an integer from 1 to 23, R is a monovalent organic group, hydrogen Or a halogen atom, preferably R is a substituted or unsubstituted amino group, an amide group, a carboxyl group, a carbonyl group, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An acyloxy group, a haloalkyl group, a halogen atom, a hydrogen group, a thioalkyl group, a thiol group, an optionally substituted phenyl group, a biphenyl group, a naphthyl group, a heterocyclic ring, etc., and n is an integer from 4 to 15 More preferably, R is an amino group, an amide group, a carboxyl group, a carbonyl group, or a hydroxyl group, and n is an integer of 6 to 12. Aliphatic thiols, thiazoles or derivatives thereof (2-aminothiazole, 2-aminothiazole-4-carboxylic acid, aminothiophene, benzothiazole, 2-mercaptobenzothiazole, 2-aminobenzothiazole, 2-amino-4-methyl Benzothiazole, 2-benzothiazolol, 2,3-dihydroimidazo [2,1-b] benzothiazol-6-amine, ethyl 2- (2-aminothiazol-4-yl) -2-hydroxyiminoacetate, 2-methylbenzothiazole, 2-phenylbenzothiazole, 2-amino-4-methylthiazole, etc.), thiadiazole derivatives (1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 2-amino-5-ethyl-1 , 3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-mercapto-1,3,4-thiadiazole, 3-methylmercapto-5-mercapto-1,2, 4-thiadiazole, 2-amino-1,3,4-thiadiazole, 2- (ethylamino) -1,3,4-thiadiazole, 2-amino-5-ethylthio-1,3,4-thiadiazole, etc.), mercapto Benzoic acid, mercaptonaphthol, mercaptophenol, 4-mercaptobiphenyl, mercaptoacetic acid, mercaptosuccinic acid, 3-mercaptopropionic acid, thiouracil, 3-thiourazol, 2-thiouramil, 4-thiouramil, 2-mercaptoquinoline, thioformic acid, 1 -Thiocoumarin, Thiocumothiazone, Thiocresol, Thiosarici Acid, thiothianuric acid, thionaphthol, thiotolene, thionaphthene, thionaphthenecarboxylic acid, thionaphthenequinone, thiobarbituric acid, thiohydroquinone, thiophenol, thiophene, thiophthalide, thiobutene, thiolthione carbonate, thiolutidone, thiol histidine, 3-carboxypropyl disulfide 2-hydroxyethyl disulfide, 2-aminopropionic acid, dithiodiglycolic acid, D-cysteine, di-t-butyl disulfide, thiocyan, thiocyanic acid and the like are preferable.

  More specifically, examples of the nitrogen-containing organic compound include triazole derivatives (1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole, benzotriazole, 1-aminobenzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 3-amino-1H-1,2,4-triazole, 3 , 5-diamino-1,2,4-triazole, 3-oxy-1,2,4-triazole, aminourazole, etc.), tetrazole derivatives (tetrazolyl, tetrazolylhydrazine, 1H-1,2,3,4) -Tetrazole, 2H-1,2,3,4-tetrazole, 5-amino-1H-tetrazole, 1-ethyl-1,4-dihydroxy-5H-tetra -5-one, 5-mercapto-1-methyltetrazole, tetrazole mercaptan, etc.), oxazole derivatives (oxazole, oxazolyl, oxazoline, benzoxazole, 3-amino-5-methylisoxazole, 2-mercaptobenzoxazole, 2 -Aminooxazoline, 2-aminobenzoxazole, etc.), oxadiazole derivatives (1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3 , 4-oxadiazole, 1,2,4-oxadiazolone-5, 1,3,4-oxadiazolone-5, etc.), oxatriazole derivatives (1,2,3,4-oxatriazole, 1, 2,3,5-oxatriazole, etc.), purine derivatives (purine, 2-amino-6-hydroxy) -8-mercaptopurine, 2-amino-6-methylmercaptopurine, 2-mercaptoadenine, mercaptopoxanthine, mercaptopurine, uric acid, guanine, adenine, xanthine, theophylline, theobromine, caffeine, etc.), imidazole derivatives (imidazole, Benzimidazole, 2-mercaptobenzimidazole, 4-amino-5-imidazolecarboxylic acid amide, histidine, etc.), indazole derivatives (indazole, 3-indazolone, indazolol, etc.), pyridine derivatives (2-mercaptopyridine, aminopyridine, etc.), Pyrimidine derivatives (2-mercaptopyrimidine, 2-aminopyrimidine, 4-aminopyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-6-hydroxy-2-merca Putopyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine, 4-amino-6-hydroxy-2-methylpyrimidine, 4-amino-6-hydroxypyrazolo [3,4-d] pyrimidine, 4-amino- 6-mercaptopyrazolo [3,4-d] pyrimidine, 2-hydroxypyrimidine, 4-mercapto-1H-pyrazolo [3,4-d] pyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4- Diamino-6-hydroxypyrimidine, 2,4,6-triaminopyrimidine, etc.), thiourea derivatives (thiourea, ethylenethiourea, 2-thiobarbituric acid, etc.), amino acids (glycine, alanine, tryptophan, proline, oxyproline) Etc.), 1,3,4-thiooxadiazolone-5, thiocoumazone, 2-thiocoumarin, thio Caffeine, thiohydantoin, thiopyrine, γ-thiopyringanazine, guanazole, guanamine, oxazine, oxadiazine, melamine, 2,4,6-triaminophenol, triaminobenzene, aminoindole, aminoquinoline, aminothiophenol, aminopyrazole Etc.

  Moreover, water and an organic solvent can be used for adjustment of the solution containing the said corrosion inhibitor. The type of the organic solvent is not particularly limited, but alcohols such as methanol, ethanol, n-propyl alcohol and n-butyl alcohol, ethers such as di-n-propyl ether, di-n-butyl ether and diallyl ether. Aliphatic hydrocarbons such as hexane, heptane, octane and nonane, and aromatic hydrocarbons such as benzene, toluene and phenol can be used, and these solvents can be used alone or in combination of two or more. It is also possible to add the corrosion inhibitor to an alkaline solution or a coupling agent solution containing the oxidizing agent.

  The concentration of the solution containing the corrosion inhibitor is preferably 0.1 to 5000 ppm, more preferably 0.5 to 3000 ppm, and particularly preferably 1 to 1000 ppm. When the concentration of the corrosion inhibitor is less than 0.1 ppm, the ion migration suppressing effect and the adhesive strength between the copper surface and the insulating layer tend to decrease. On the other hand, when the concentration of the corrosion inhibitor exceeds 5000 ppm, an ion migration suppressing effect can be obtained, but the adhesive strength between the copper surface and the insulating layer tends to decrease. The treatment time with the solution containing the corrosion inhibitor is not particularly limited, but it is preferable to appropriately change the treatment time according to the type and concentration of the corrosion inhibitor. It is also possible to perform ultrasonic cleaning after the treatment.

(Wiring board and semiconductor package)
The wiring board of the present invention has wiring formed by applying the copper surface treatment method of the present invention. Hereinafter, as an embodiment of the wiring substrate of the present invention, a semiconductor chip mounting substrate is taken as an example, and its general structure, a method of manufacturing a semiconductor chip mounting substrate by applying the copper surface treatment method of the present invention Although a semiconductor package using the substrate will be described with reference to the drawings, the present invention is not limited to these descriptions.

(Semiconductor chip mounting board)
FIG. 1 is a schematic cross-sectional view of an embodiment of a semiconductor chip mounting substrate of the present invention. Here, an embodiment in which two build-up layers (interlayer insulating layers) are formed on one side will be described, but the build-up layer may be formed on both sides as required (see FIG. 8).

  In the semiconductor chip mounting substrate shown in FIG. 1, the first wiring 106a including the semiconductor chip connection terminal and the first interlayer connection terminal 101 is formed on the side on which the semiconductor chip is mounted on the core substrate 100 which is an insulating layer. The second wiring 106 b including the second interlayer connection terminal 103 is formed on the other side of the core substrate 100, and the second interlayer connection terminal 103 is formed on the core substrate 100. It is electrically connected to the first interlayer connection terminal 101 via an interlayer connection IVH (interstitial via hole) 102. Also, a buildup layer 104 is formed on the second wiring 106b, and a third wiring 106c including a third interlayer connection terminal is formed on the buildup layer 104, and the third interlayer The connection terminal is electrically connected to the second interlayer connection terminal 103 via the second interlayer connection IVH 108. Further, an external connection terminal 107 connected to the motherboard is formed on the outermost buildup layer, and the external connection terminal 107 and the third interlayer connection terminal are electrically connected via the third interlayer connection IVH 105. It is connected. Note that the shape of the wiring and the arrangement of the connection terminals are not particularly limited, and can be appropriately designed in order to manufacture a semiconductor chip to be mounted and a target semiconductor package. Further, the semiconductor chip connection terminal and the first interlayer connection terminal can be shared. Furthermore, an insulating coating 109 such as a solder resist can be provided on the outermost buildup layer as necessary.

(Core substrate)
The material of the core substrate is not particularly limited as long as it has a certain level of strength and insulation, but an organic substrate, a ceramic substrate, a silicon substrate, a glass substrate, or the like is preferably used. In consideration of the thermal expansion coefficient and insulation, it is preferable to use a ceramic substrate or a glass substrate. As the glass substrate, a non-photosensitive glass substrate or a photosensitive glass substrate can be used. As the non-photosensitive glass substrate, for example, soda lime glass (component example: SiO ₂ 65 to 75 wt%, Al ₂ O ₃ 0.5-4 wt%, CaO 5-15 wt%, MgO 0.5-4 wt%, Na ₂ O 10-20 wt%), borosilicate glass (component example: SiO ₂ 65-80 wt%, B ₂ O _{3 5~25wt%, Al 2 O 3} 1~5wt%, CaO 5~8wt%, MgO 0.5~2wt%, Na 2 O 6~14wt%, K 2 O 1~6wt%) and the like are preferable. As the photosensitive glass, for example, those containing gold ions and silver ions as a photosensitive agent into Li _{2 O-SiO} 2 based crystallized glass is preferable.

  As the organic substrate, it is preferable to use a substrate or a resin film obtained by laminating a material (prepreg) obtained by impregnating a glass cloth with a resin. As the resin to be used, a thermosetting resin, a thermoplastic resin, or a mixed resin thereof is preferable, and a thermosetting organic insulating material is more preferable. Thermosetting resins include phenolic resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, polybenzimidazole resin, polyamide resin, polyamideimide resin, silicon resin, cyclohexane Resin synthesized from pentadiene, resin containing tris (2-hydroxyethyl) isocyanurate, resin synthesized from aromatic nitrile, trimerized aromatic dicyanamide resin, resin containing triallyl trimetallate, furan resin, ketone resin, Xylene resins, thermosetting resins containing condensed polycyclic aromatics, benzocyclobutene resins, and the like are preferred. As the thermoplastic resin, polyimide resin, polyphenylene oxide resin, polyphenylene sulfide resin, aramid resin, liquid crystal polymer, and the like are preferable. Moreover, it is more preferable to add a filler to these resins. Examples of the filler include silica, talc, aluminum hydroxide, aluminum borate, aluminum nitride, and alumina.

  Further, the thickness of the core substrate is not particularly limited, but is preferably 100 to 800 μm from the viewpoint of IVH formation, and more preferably 150 to 500 μm. If the thickness is less than 100 μm, it is difficult to obtain the rigidity of the substrate, and warping and twisting tend to occur. If the thickness exceeds 800 μm, the entire substrate tends to be thick and hole processing tends to be difficult.

(Build-up layer)
The interlayer insulating layer (build-up layer) 104 may be a layer made of an insulating material, and the material is not particularly limited. As the insulating material, a thermosetting resin, a thermoplastic resin, or a mixed resin thereof is preferable, and a material mainly composed of a thermosetting organic insulating material is more preferable. Thermosetting resins include phenolic resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, polybenzimidazole resin, polyamide resin, polyamideimide resin, silicon resin, cyclohexane Resin synthesized from pentadiene, resin containing tris (2-hydroxyethyl) isocyanurate, resin synthesized from aromatic nitrile, trimerized aromatic dicyanamide resin, resin containing triallyl trimetallate, furan resin, ketone resin, It is preferable to use a xylene resin, a thermosetting resin containing a condensed polycyclic aromatic, a benzocyclobutene resin, or the like. As the thermoplastic resin, polyimide resin, polyphenylene oxide resin, polyphenylene sulfide resin, aramid resin, liquid crystal polymer, and the like are preferable. In addition, it is preferable to add a filler to the insulating material. Examples of the filler include silica, talc, aluminum hydroxide, aluminum borate, aluminum nitride, and alumina.

(Coefficient of thermal expansion)
The thermal expansion coefficient of the core substrate 100 is not particularly limited, but is preferably approximated to the thermal expansion coefficient of the semiconductor chip and approximate to the thermal expansion coefficient of the buildup layer. The semiconductor chip, the core substrate, It is more preferable that α1 ≦ α2 ≦ α3, where α1, α2, and α3 (ppm / ° C.) are the thermal expansion coefficients of the buildup layers. Specifically, the thermal expansion coefficient α2 of the core substrate is preferably 7 to 13 ppm / ° C, and more preferably 9 to 11 ppm / ° C. Further, the thermal expansion coefficient α3 of the buildup layer is preferably 10 to 40 ppm / ° C, more preferably 10 to 20 ppm / ° C, and particularly preferably 11 to 17 ppm / ° C.

(Young's modulus)
The Young's modulus of the buildup layer is preferably 1 to 5 GPa in terms of stress relaxation against thermal stress. The Young's modulus and thermal expansion coefficient of the buildup layer can be controlled by the amount of filler added, and preferably the thermal expansion coefficient of the buildup layer is 10 to 40 ppm / ° C. and the Young's modulus is 1 to 5 GPa. Adjust to.

(Wiring layout and terminal shape)
The arrangement of the wiring is not particularly limited, but as shown in FIG. 5 and FIG. 6 (inner layer wiring, interlayer connection terminals, etc. are omitted), at least on the side where the semiconductor chip is mounted, the semiconductor chip connection terminal 16 (wire bond Terminals, etc.) are arranged, and on the opposite side, external connection terminals (locations where solder balls or the like are mounted) electrically connected to the mother board, development wirings connecting them, interlayer connection terminals, etc. are arranged. 5 shows a fan-in type semiconductor chip mounting board in which the external connection terminals 19 are formed inside the semiconductor chip connection terminals 16. FIG. 6 shows the external connection terminals 19 outside the semiconductor chip connection terminals 16. The fan-out type semiconductor chip mounting board formed with the above-mentioned structure may be used. 5 and 6, reference numeral 13 denotes a semiconductor package area, 14 denotes a die bond film adhesion area (flip chip type), 15 denotes a semiconductor chip mounting area (flip chip type), and 17 denotes a die bond film adhesion area (wire bond type). , 18 is a semiconductor chip mounting area (wire bond type), and 20 is a developed wiring.

  The shape of the semiconductor chip connection terminal 16 is not particularly limited as long as wire bond connection or flip chip connection is possible. Also, any type of fan-out, fan-in, and fan-in / out can be wire-bonded or flip-chip connected. Further, if necessary, a dummy pattern 21 (see FIG. 6) that is not electrically connected to the semiconductor chip may be formed. The shape and arrangement of the dummy pattern are not particularly limited, but it is preferable to arrange the dummy pattern uniformly in the semiconductor chip mounting region. As a result, voids are less likely to occur when a semiconductor chip is mounted with a die bond adhesive, and reliability can be improved.

(Shape of semiconductor chip mounting substrate)
The shape of the semiconductor chip mounting substrate is not particularly limited, but is preferably a frame shape as shown in FIG. By making the shape of the semiconductor chip mounting substrate into a frame shape, the semiconductor package can be assembled efficiently. Hereinafter, a preferred embodiment of the frame-shaped semiconductor chip mounting substrate will be described in detail with reference to FIG.

  The frame-shaped semiconductor chip mounting substrate shown in FIG. 7 has a plurality of semiconductor package regions 13 (parts to be a single semiconductor package) arranged in rows and columns in a grid at equal intervals. In addition, a plurality of such blocks are arranged in rows and columns at regular intervals in a grid pattern. In FIG. 7, the minimum two blocks necessary for explanation are shown, and the other blocks are omitted. Here, the width of the space between the semiconductor package regions is preferably 50 to 500 μm, and more preferably 100 to 300 μm. Furthermore, it is most preferable that the blade width of the dicer used when the semiconductor package is cut later is made the same.

  By disposing the semiconductor package region as described above, the semiconductor chip mounting substrate can be effectively used. Further, a positioning mark 11 or the like is preferably formed on the end portion of the semiconductor chip mounting substrate, and more preferably a pin hole by a through hole. The shape and arrangement of the pin holes may be selected so as to match the forming method and the semiconductor package assembly apparatus.

  Furthermore, it is preferable that a reinforcing pattern 24 is formed outside the space between the semiconductor package regions and the block. The reinforcing pattern may be prepared separately and bonded to the semiconductor chip mounting substrate, but is preferably a metal pattern formed at the same time as the wiring formed in the semiconductor package region. It is more preferable that the same plating such as nickel or gold is applied or an insulating coating is applied. When the reinforcing pattern is such a metal, it can also be used as a plating lead for electrolytic plating. Further, it is preferable that a cutting position alignment mark 25 for cutting with a dicer is formed outside the block.

(Manufacturing method of semiconductor chip mounting substrate)
Hereinafter, an embodiment of a method for manufacturing a semiconductor chip mounting substrate that is preferable for obtaining a highly reliable semiconductor package will be described step by step with reference to schematic cross-sectional views of FIGS. However, the order of the manufacturing process is not particularly limited as long as it does not depart from the object of the present invention.

(Process a)
(Step a) is a step of forming the first wiring 106a on the core substrate 100 as shown in FIG. Examples of the wiring formation method include a subtractive method, an additive method, a semi-additive method, and the like, and it is preferable to select according to the purpose. Note that since the first wiring 106a includes the first interlayer connection terminal 101 and the semiconductor chip connection terminal (portion electrically connected to the semiconductor chip), a semi-additive method advantageous for forming fine wiring is used. It is preferable to use it.
(

Subtractive method)
In the subtractive method, a copper layer is formed on the core substrate surface or the build-up layer, an etching resist is formed in a portion to be a wiring on the copper layer, and the copper foil exposed from the etching resist is removed by etching, and wiring is performed. It is a method of forming. This copper layer can be formed, for example, by forming a thin film copper by sputtering, vapor deposition, plating or the like and then performing a method of performing electrolytic copper plating or a method of attaching a copper foil until a desired thickness is obtained. The etching resist pattern is, for example, a photomask that screen-prints resist ink, or laminates a negative photosensitive dry film for etching resist on copper foil, and transmits light in the shape of wiring on it. Can be formed by removing the portions that have not been exposed with a developing solution. Also, as an etchant used for etching, a chemical etchant used for a normal wiring board such as a solution of cupric chloride and hydrochloric acid, a ferric chloride solution, a solution of sulfuric acid and hydrogen peroxide, an ammonium persulfate solution, or the like should be used. Can do. Moreover, it is preferable to use the etching resist material which can be used for a normal wiring board as an etching resist.

(Additive method)
The additive method is a method of forming a wiring by plating only a necessary portion on a core substrate or a buildup layer. More specifically, for example, after depositing an electroless plating catalyst on the core substrate, a plating resist is formed on a surface portion where plating is not performed, and immersed in an electroless copper plating solution. Electroless plating is performed only on uncovered portions to form wiring.

(Semi-additive method)
In the semi-additive method, a thin copper layer (seed layer) is formed on the core substrate surface or build-up layer, then the necessary wiring is formed by electrolytic copper plating, and then the unnecessary thin copper layer is removed by etching. This method is optimal as a process for forming fine wiring with L / S = 35 μm / 35 μm or less. More specifically, for example, after forming a seed layer (thin film copper) on the core substrate surface by a method such as vapor deposition, plating, sputtering or bonding a copper foil, a plating resist is formed on the seed layer, After forming necessary wiring by electrolytic copper plating and removing the plating resist, an unnecessary thin copper layer is removed by an etching method to form wiring.

  When the core layer or build-up layer has an adhesive function, it is desirable to form the seed layer by bonding copper foil by pressing or laminating, but it is very difficult to directly bond thin copper foil. Therefore, the seed layer is usually formed by laminating a thick metal foil and then thinning it by etching or the like, or peeling the carrier layer after laminating the copper foil with carrier. Specifically, for example, a method of using a three-layer copper foil of carrier copper / nickel / thin film copper, removing carrier copper with an alkaline etching solution, removing nickel with a nickel etching solution, and using thin film copper as a seed layer and a thickness of 9 to 9 An example is a method in which an 18 μm copper foil is pasted and uniformly thinned to a thickness of 5 μm or less by etching to form a seed layer. Moreover, as a copper foil with a carrier used for the latter formation method, for example, a peelable copper foil using aluminum, copper, an insulating material or the like as a carrier can be exemplified, which is preferable when a seed layer having a thickness of 5 μm or less is formed. .

  In addition, the seed layer is preferably formed by sputtering, for example, by forming a base metal and a copper layer having a thickness of 200 to 500 nm by sputtering on the surface of the core substrate or the buildup layer. As the sputtering apparatus used for forming the copper layer, dipolar sputtering, tripolar sputtering, quadrupolar sputtering, magnetron sputtering, mirrortron sputtering, or the like can be used. In order to ensure adhesion, the base metal is formed by sputtering a metal such as Cr, Ni, Co, Pd, Zr, an alloy of Ni and Cr, or an alloy of Ni and Cu so as to have a thickness of 5 to 50 nm. Is preferably formed. Moreover, the formation of the seed layer by the above plating includes, for example, a method of forming plated copper having a thickness of 0.5 to 3 μm by electroless copper plating on the surface of the core substrate or the buildup layer.

(Process b)
In step (b), as shown in FIG. 2B, a first interlayer connection IVH 102 (via hole) for connecting the first interlayer connection terminal 101 and a second wiring to be described later. Is a step of forming. Via holes are provided with holes for connection in the core substrate or build-up layer, and then subjected to desmear treatment as necessary to electrically connect the layers, and then the holes are formed with conductive paste, plating, etc. And can be formed by filling and conducting. As the hole processing method, mechanical processing such as punching and drilling, laser processing such as CO ₂ laser, YAG laser, and excimer laser, chemical etching processing using a chemical solution, dry etching method using plasma, and the like can be applied. In the case where the core substrate 100 is a non-photosensitive base material, it is preferably formed by irradiating a laser beam such as a CO ₂ laser, a YAG laser, or an excimer laser to a portion that becomes a via hole. From the viewpoint of productivity and hole quality, it is preferable to use a CO ₂ laser. When the IVH diameter is less than 30 μm, a YAG laser capable of focusing the laser beam is suitable.

  When the core substrate 100 is a photosensitive base material, a region other than a portion that becomes a via hole is masked, irradiated with ultraviolet light, and then a hole that becomes a via hole is formed by heat treatment and etching. In addition, when the core substrate 100 is a base material that can be chemically etched by a chemical solution such as an organic solvent, it is preferable to form a hole that becomes a via hole by chemical etching. As described above, a hole to be a via hole is formed, and the hole is made conductive by a conductive paste or plating to form a via hole.

  Further, as a method for forming a via hole in the buildup layer, a method in which a conductive layer is previously formed on the buildup layer with a conductive paste or plating, and this is laminated on the core substrate by pressing or the like is also preferable.

(Process c)
(Step c) is a step of forming the second wiring 106b on the surface of the core substrate 100 opposite to the surface on which the first wiring 106a is formed, as shown in FIG. 2 (c). The second wiring 106b can be formed in the same manner as the first wiring in the above (step a). Note that the second wiring 106b includes the second interlayer connection terminal 103, and a semi-additive method is preferably used as a method for forming the fine wiring.

(Process d)
(Step d) is a step of forming a buildup layer (interlayer insulating layer) 104 on the surface on which the second wiring 106b is formed as shown in FIG. 2 (d). Here, first, it is preferable that the surface of the second wiring 106b is degreased and washed with hydrochloric acid or sulfuric acid. Next, noble metal is discretely formed on the surface of the copper wiring (on the second wiring 106b), and is oxidized by immersing it in an alkaline solution containing an oxidizing agent. Then, oxidation treatment is performed again, and then reduction treatment is performed. It is preferable that the roughness Rz of the copper wiring surface be 1 nm or more and 1,000 nm or less.

  Next, the buildup layer 104 is formed on the surface of the core substrate 100 and the surface of the second wiring 106b. As the insulating material for the build-up layer 104, a thermosetting resin, a thermoplastic resin, or a mixed resin thereof can be used as described above, but it is preferable to use a thermosetting material as a main component. The build-up layer 104 is preferably formed by printing or spin coating when the insulating material is varnished, or by lamination or pressing when the insulating material is film-like. When the insulating material includes a thermosetting material, it is preferable that the insulating material is further heat-cured.

(Process e)
(Step e) is a step of forming a second interlayer connection IVH (via hole) 108 in the build-up layer 104 as shown in FIG. 2 (e). This is preferably performed in the same manner as the first interlayer connection IVH 102 in (Step b).

(Process f)
(Step f) is a step of forming the third wiring 106c on the buildup layer on which the second IVH 108 is formed, as shown in FIG. 2 (f). The third wiring 106c can be formed in the same manner as the first wiring 106a in the above (step a). Further, by repeating steps (d) to (f), two or more buildup layers 104 may be formed as shown in FIG. In this case, the wiring including the third interlayer connection IVH 105 formed in the outermost buildup layer becomes the external connection terminal 107 for electrical connection with the mother board or another semiconductor package. The external connection terminals can be sequentially subjected to nickel and gold plating, and may be nickel, palladium and gold plating as necessary. For the plating, either electroless plating or electrolytic plating may be used, but electroless plating is preferable particularly for a substrate having fine wiring or high-density wiring.

(Process g)
(Step g) is a step of forming an insulating coating 109 for protecting wirings other than the external connection terminals as shown in FIG. 2 (g). As the insulating coating material, a thermosetting or ultraviolet curable solder resist can be used, but an ultraviolet curable material capable of finishing the resist shape with high accuracy is preferable. The insulating coating pattern can be formed by printing as long as it is a varnish-like material, but it is preferable to use a photosensitive solder resist, a coverlay film, or a film-like resist in order to ensure more accuracy. . As a material, an epoxy-based material, a polyimide-based material, an epoxy acrylate-based material, or a fluorene-based material can be used. In addition, since such insulation coating has shrinkage | contraction at the time of hardening, if it forms only on one side, it will be easy to produce a big curvature on a board | substrate. Therefore, an insulating coating can be formed on both surfaces of the semiconductor chip mounting substrate as necessary. Furthermore, since the warpage varies depending on the thickness of the insulating coating, it is more preferable to adjust the thicknesses so that no warpage occurs when the insulating coating is formed on both surfaces. In this case, it is preferable to conduct preliminary examination and determine the thickness of the insulating coating on both sides. In order to obtain a thin semiconductor package, the thickness of the insulating coating is preferably 50 μm or less, and more preferably 30 μm or less.

(Semiconductor package)
The semiconductor package of the present invention is obtained by mounting a semiconductor chip on the wiring substrate (substrate for mounting a semiconductor chip) of the present invention. FIG. 3 shows a schematic cross-sectional view of one embodiment (flip chip type semiconductor package) of the semiconductor package of the present invention. In this semiconductor package, the semiconductor chip 111 is mounted at a predetermined position of the semiconductor chip mounting substrate of FIG. 2G, and solder balls 114 for electrical connection with the mother board are formed on the external connection terminals 107. The semiconductor chip and the semiconductor chip connection terminal are flip-chip connected by connection bumps 112. The space between the semiconductor chip and the semiconductor chip mounting substrate is sealed with an underfill material 113. The thermal expansion coefficient of the underfill material is preferably close to the thermal expansion coefficient of the semiconductor chip and the core substrate 100, but is not limited thereto. More preferably, (thermal expansion coefficient of the semiconductor chip) ≦ (thermal expansion coefficient of the underfill material) ≦ (thermal expansion coefficient of the core substrate). In addition, the mounting of the semiconductor chip can be performed using an anisotropic conductive film (ACF) or an adhesive film (NCF) that does not contain conductive particles. In this case, there is no need to seal with an underfill material. ,preferable. Furthermore, if ultrasonic waves are used together when mounting a semiconductor chip, electrical connection can be made at a low temperature and in a short time. The solder balls may be eutectic solder or Pb free solder. As a method for fixing the solder ball to the external connection terminal 107, for example, an N ₂ reflow apparatus or the like can be used. However, the method is not limited to this.

  FIG. 4 shows a cross-sectional view of an embodiment of a wire bond type semiconductor package. Although a general die bond paste can be used for mounting the semiconductor chip, it is more preferable to use a die bond film 117. Electrical connection between the semiconductor chip and the semiconductor chip connection terminal is performed by wire bonding using a gold wire 115. Further, the semiconductor chip can be sealed by transfer molding using a semiconductor sealing resin 116. In this case, the sealing region may seal only a necessary portion, for example, only the face surface of the semiconductor chip, but it is desirable to seal the entire semiconductor package region as shown in FIG. This is a particularly effective method for obtaining individual semiconductor packages in a semiconductor chip mounting substrate in which a plurality of semiconductor package regions are arranged in rows and columns by simultaneously cutting the substrate and the sealing resin with a dicer or the like.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.
Example 1
In order to evaluate the reliability of the semiconductor package produced by applying the copper surface treatment of the present invention, a semiconductor package sample was produced as follows.
(Process a)
A 0.4 mm thick soda glass substrate (thermal expansion coefficient: 11 ppm / ° C.) was prepared as the core substrate 100, a 200 nm copper thin film was formed on one side by sputtering, and then plated to a thickness of 10 μm by electrolytic copper plating. In addition, sputtering was performed on condition 1 shown below using the apparatus model number MLH-6315 by Nippon Vacuum Technology Co., Ltd.
Condition 1
Current: 3.5A
Voltage: 500V
Argon flow rate: 35 SCCM (0.059 Pa · m ³ / s)
Pressure: 5 × 10 ⁻³ Torr (6.6 × 10 ⁻¹ Pa)
Deposition rate: 5 nm / second Thereafter, an etching resist is formed in a portion to be the first wiring 106a, etched using a ferric chloride etchant, and the etching resist is removed, whereby the first wiring 106a ( 1st interlayer connection terminal 101 and a semiconductor chip connection terminal) were formed.

(Process b)
A hole having a hole diameter of 50 μm was formed with a laser until reaching the first interlayer connection terminal 101 from the surface opposite to the first wiring 106a of the glass substrate on which the first wiring 106a was formed. A YAG laser LAVIA-UV2000 (manufactured by Sumitomo Heavy Industries, Ltd., trade name) was used as the laser, and a hole having IVH was formed under the conditions of a frequency of 4 kHz, a shot number of 50, and a mask diameter of 0.4 mm. Then, desmear treatment in the hole was performed. Thereafter, the hole is filled with conductive paste MP-200V (trade name, manufactured by Hitachi Chemical Co., Ltd.), cured at 160 ° C. for 30 minutes, and electrically connected to the first interlayer connection terminal 101 on the glass substrate. The first interlayer connection IVH102 (via hole) was formed.

(Process c)
In order to electrically connect to the first interlayer connection IVH 102 (first via hole) formed in (Step b), a surface of the glass substrate opposite to the first wiring 106a is sputtered to 200 nm. After forming the copper thin film, plating was performed to a thickness of 10 μm by electrolytic copper plating. Sputtering was performed in the same manner as in (Step a). Thereafter, as in (Step a), an etching resist is formed in the shape of the second wiring 106b, etched using a ferric chloride etchant, and the etching resist is removed, whereby the second wiring 106b ( A second interlayer connection terminal 103 is formed.

(Process d)
(Step d-1)
The wiring surface on the second wiring 106b side formed in (Step c) was immersed in an acidic degreasing solution Z-200 (trade name, manufactured by World Metal Co., Ltd.) adjusted to 200 ml / L for 2 minutes at a liquid temperature of 50 ° C. Then, it was washed with hot water by immersing it in water having a liquid temperature of 50 ° C. for 2 minutes, and further washed with water for 1 minute. Subsequently, it was immersed in a 3.6 N sulfuric acid aqueous solution for 1 minute and washed with water for 1 minute.

(Step d-2)
The second wiring 106b having undergone the pretreatment step is immersed in a substituted palladium plating solution SA-100 (Hitachi Chemical Industry Co., Ltd., product name) at 30 ° C. for 3 minutes, and palladium plating, which is a noble metal than copper, is performed. the 1.0 [mu] mol / dm ² applied, washed with water for 1 minute, further, 50 to the oxidation treatment solution was added sodium chlorite 15 g / L alkaline solution containing sodium phosphate tribasic 10 g / L and potassium hydroxide 25 g / L By immersing at 3 ° C. for 3 minutes, a 0.08 mg / cm ² copper oxide crystal was formed on the surface of the second wiring 106b. Then, after washing with water for 1 minute, the formed copper oxide crystals were selectively removed by immersing in an acidic solution containing 2 g / L of sulfuric acid at 25 ° C. for 30 seconds. After that, the second wiring is again immersed in an oxidizing solution containing 15 g / L of sodium chlorite in an alkaline solution containing 10 g / L of trisodium phosphate and 25 g / L of potassium hydroxide at 50 ° C. for 1 minute. A 0.10 mg / cm ² copper oxide crystal was formed on the surface of 106b. Thereafter, it was washed with water for 1 minute, and immersed in a reduction treatment solution HIST-100D (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 3 minutes at 40 ° C. to form a metal copper crystal on the surface of the second wiring 106b. Thereafter, it was washed with water for 5 minutes and dried at 85 ° C. for 30 minutes.

(Step d-3)
Next, an interlayer insulating layer (build-up layer) 104 was formed on the surface on the second wiring 106b side as follows. That is, the build-up material AS-ZII (Hitachi Chemical Industry Co., Ltd., product name) is applied to the surface on the second wiring 106b side by vacuum lamination under the conditions of evacuation time 30 seconds, pressurization 40 seconds, and 0.5 MPa. After the buildup layer was laminated to form a resin layer having a thickness of 45 μm, the resin was thermally cured by being held at 180 ° C. for 120 minutes in an oven dryer to form the buildup layer 104.

(Process e)
A hole to be an IVH with a hole diameter of 50 μm was formed by a laser until reaching the second interlayer connection terminal 103 from the surface of the buildup layer 104 formed in the above (step d-3). A YAG laser LAVIA-UV2000 (manufactured by Sumitomo Heavy Industries, Ltd., trade name) was used as the laser, and a hole to be IVH was formed under the conditions of a frequency of 4 kHz, a shot number of 20 and a mask diameter of 0.4 mm. Thereafter, desmear treatment was performed. As a desmear treatment method, it was immersed in a swelling liquid circular positive hole 4125 (Rohm and Haas Electronic Materials Co., Ltd., product name) at 80 ° C. for 3 minutes and then washed with water for 3 minutes. Then, it was immersed in desmear liquid circulation MLB promoter 213 (Rohm and Haas Electronic Materials Co., Ltd., product name) at 80 ° C. for 5 minutes and then washed with water for 3 minutes. Subsequently, it was immersed in a reducing liquid circuposit MLB216-4 (Rohm and Haas Electronic Materials Co., Ltd., product name) at 40 ° C. for 3 minutes, washed with water for 3 minutes, and dried at 85 ° C. for 30 minutes.

(Process f)
In order to form the third wiring 106c and the second IVH 108 on the buildup layer 104 formed in the above (step d-3), a Ni layer (underlying metal) having a thickness of 20 nm is formed on the buildup layer 104 by sputtering. ) And a thin film copper layer having a thickness of 200 nm is formed on the Ni layer to form a seed layer. Sputtering was performed under the condition 2 shown below using MLH-6315 manufactured by Nippon Vacuum Technology Co., Ltd.
Condition 2
(Ni layer)
Current: 5.0A
Current: 350V
Voltage argon flow rate: 35 SCCM (0.059 Pa · m ³ / s)
Pressure: 5 × 10 ⁻³ Torr (6.6 × 10 ⁻¹ Pa)
Deposition rate: 0.3 nm / second (thin copper layer)
Current: 3.5A
Voltage: 500V
Argon flow rate: 35 SCCM (0.059 Pa · m ³ / s)
Pressure: 5 × 10 ⁻³ Torr (6.6 × 10 ⁻¹ Pa)
Deposition rate: 5 nm / second

Next, a plating resist PMER P-LA900PM (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name) was applied onto the seed layer (on the thin film copper layer) by a spin coating method to form a plating resist layer having a thickness of 10 μm. Next, the plating resist layer was exposed under the condition of 1000 mJ / cm ² and then immersed in PMER developer P-7G at 23 ° C. for 6 minutes to form a resist pattern of L / S = 10 μm / 10 μm. Thereafter, electrolytic copper plating was performed using a copper sulfate plating solution to form a third wiring 106c having a thickness of about 5 μm. The plating resist was peeled off by immersion for 1 minute at room temperature (25 ° C.) using methyl ethyl ketone. In addition, for quick etching of the seed layer, a 5-fold diluted solution of CPE-700 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name) is used for etching removal by immersing and shaking at 30 ° C. for 30 seconds. A wiring pattern was formed.

(Process g)
Thereafter, the steps (d) to (step f) were repeated again to form a further outermost layer wiring including the buildup layer and the external connection terminal 107. Finally, a solder resist 109 is formed, and then the external connection terminal 107 and the semiconductor chip connection terminal are subjected to gold plating, and FIG. 1 (sectional view for one package), FIG. 5 (plan view for one package), A fan-in type BGA semiconductor chip mounting substrate as shown in FIG. 7 (overall view of the semiconductor chip mounting substrate) was produced.

(Process h)
While applying an ultrasonic wave to the semiconductor chip 111 on which the connection bumps 112 are formed in the semiconductor chip mounting region of the semiconductor chip mounting substrate manufactured by the above-described (step a) to (step g), using a flip chip bonder. Installed as many as needed. Furthermore, an underfill material 113 is injected from the end of the semiconductor chip into the gap between the semiconductor chip mounting substrate and the semiconductor chip, and primary curing is performed at 80 ° C. for 1 hour and secondary curing at 150 ° C. for 4 hours using an oven. Went. Next, a lead / tin eutectic solder ball 114 having a diameter of 0.45 mm was fused to the external connection terminal 107 using an N ₂ reflow apparatus. Finally, the semiconductor chip mounting substrate was cut with a dicer equipped with a blade having a width of 200 μm to produce the semiconductor package shown in FIG.

(Example 2)
The fan-in type was carried out in the same manner as in Example 1 except that the treatment in (Step d-2) of (Example 1) was performed with an acidic solution containing 2 g / L of hydrochloric acid instead of the acidic solution containing 2 g / L of sulfuric acid. A semiconductor chip mounting substrate and a semiconductor package for BGA were produced.

(Example 3)
The fan-in type was carried out in the same manner as in Example 1 except that the treatment in (Step d-2) of (Example 1) was performed with an acidic solution containing 2 g / L of nitric acid instead of the acidic solution containing 2 g / L of sulfuric acid. A semiconductor chip mounting substrate and a semiconductor package for BGA were produced.

(Comparative Example 1)
After performing the pretreatment in (Step d-1) in (Step d), the surface of the second wiring 106b is subjected to an oxidation treatment solution at 85 ° C. for 3 minutes without performing substitution palladium plating in (Step d-2). Immersion was performed to form a 0.50 mg / cm ² copper oxide crystal on the wiring surface. Thereafter, a semiconductor chip mounting substrate and a semiconductor package for fan-in type BGA were produced in the same manner as in Example 1 except that the substrate was washed with water for 5 minutes and dried at 85 ° C. for 30 minutes.

(Comparative Example 2)
After performing the pretreatment in (Step d-1) in (Step d), the surface of the second wiring 106b is subjected to an oxidation treatment solution at 85 ° C. for 3 minutes without performing substitution palladium plating in (Step d-2). Immersion is performed to form a 0.50 mg / cm ² copper oxide crystal on the surface of the wiring 106b, and then the substrate is washed with water for 5 minutes, and the reduction treatment liquid HIST-100D (trade name, manufactured by Hitachi Chemical Co., Ltd.) A reduction treatment step was performed by immersion at 40 ° C. for 3 minutes. Thereafter, a semiconductor chip mounting substrate and a semiconductor package for fan-in type BGA were produced in the same manner as in Example 1 except that the substrate was washed with water for 5 minutes and dried at 85 ° C. for 30 minutes.

(Comparative Example 3)
After performing the pretreatment in (Step d-1) in (Step d), the surface of the second wiring 106b is made of a microetching agent without performing substitution palladium plating and oxidation treatment in (Step d-2). The film was immersed in etch bond CZ8100 (trade name, manufactured by MEC Co., Ltd.) at 40 ° C. for 1 minute and 30 seconds. Then, the board | substrate for semiconductor chip mounting and semiconductor package for fan-in type BGAs were produced like Example 1 except having washed with water for 1 minute and making it dry at 85 degreeC for 30 minutes.

(Comparative Example 4)
After performing the pretreatment in (Step d-1) in (Step d), in (Step d-2), the second wiring 106b is replaced with a substituted palladium plating solution SA-100 (Hitachi Chemical Industry Co., Ltd., product name). ) At 30 ° C. for 3 minutes, palladium plating which is a noble metal than copper is applied at 1.0 μmol / dm ² , washed with water for 1 minute, and further, trisodium phosphate 10 g / L and potassium hydroxide 25 g A copper oxide crystal of 0.07 mg / cm ² is formed on the surface of the second wiring 106b by immersing in an oxidizing solution containing 15 g / L of sodium chlorite in an alkaline solution containing / L for 3 minutes at 50 ° C. did. Further, after this, the substrate was washed with water for 5 minutes, and a reduction treatment step was performed in which it was immersed in a reduction treatment solution HIST-100D (trade name, manufactured by Hitachi Chemical Co., Ltd.) at 40 ° C. for 3 minutes. Thereafter, a semiconductor chip mounting substrate and a semiconductor package for fan-in type BGA were produced in the same manner as in Example 1 except that the step of washing with water for 5 minutes and drying at 85 ° C. for 30 minutes was performed.

(Comparative Example 5)
After the pretreatment in (Step d-1) in (Step d), the step (Step d-2) was not performed. That is, the unevenness forming process was not performed. Other than that was carried out similarly to Example 1, and produced the semiconductor chip mounting substrate and semiconductor package for fan-in type BGA.

(Comparative Example 6)
After performing the pretreatment in (Step d-1) in (Step d), the surface of the second wiring 106b is subjected to an oxidation treatment solution at 85 ° C. for 3 minutes without performing substitution palladium plating in (Step d-2). Immersion was performed to form a 0.50 mg / cm ² copper oxide crystal on the wiring surface. Then, after washing with water for 1 minute, the formed copper oxide crystals were selectively removed by immersing in an acidic solution containing 2 g / L of sulfuric acid at 25 ° C. for 30 seconds. Thereafter, it was again immersed in an oxidation treatment solution at 85 ° C. for 3 minutes to form a 0.90 mg / cm ² copper oxide crystal on the surface of the second wiring 106b. Thereafter, it was washed with water for 1 minute, and immersed in a reduction treatment solution HIST-100D (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 3 minutes at 40 ° C. to form a metal copper crystal on the surface of the second wiring 106b. Thereafter, a semiconductor chip mounting substrate and a semiconductor package for fan-in type BGA were produced in the same manner as in Example 1 except that the substrate was washed with water for 5 minutes and dried at 85 ° C. for 30 minutes.

Example 4
In order to evaluate the adhesion and smoothness of the copper surface after the copper surface treatment of the present invention, an 18 μm electrolytic copper foil GTS-18 (trade name, manufactured by Furukawa Circuit Foil Co., Ltd.) is 5 cm × 8 cm (for adhesion test, Cut out to copper surface smoothness evaluation), each of the electrolytic copper foil on one surface (S surface: shiny surface) each of the wiring surface described in (step d-1) and (step d-2) of Example 1 The surface treatment was performed and the test piece of the electrolytic copper foil was produced.

(Example 5)
As a surface treatment for the electrolytic copper foil, a test piece of an electrolytic copper foil was prepared in the same manner as in Example 4 except that the same surface treatment as each surface treatment for the wiring surface described in Example 2 was performed.

(Example 6)
As a surface treatment for the electrolytic copper foil, a test piece of an electrolytic copper foil was prepared in the same manner as in Example 4 except that the same surface treatment as each surface treatment for the wiring surface described in Example 3 was performed.

(Comparative Example 7)
As a surface treatment for the electrolytic copper foil, a test piece of the electrolytic copper foil was prepared in the same manner as in Example 4 except that the same surface treatment as the surface treatment for the wiring surface described in Comparative Example 1 was performed.

(Comparative Example 8)
As a surface treatment for the electrolytic copper foil, a test piece of an electrolytic copper foil was prepared in the same manner as in Example 4 except that the same surface treatment as the surface treatment for the wiring surface described in Comparative Example 2 was performed.

(Comparative Example 9)
As a surface treatment for the electrolytic copper foil, a test piece of an electrolytic copper foil was prepared in the same manner as in Example 4 except that the same surface treatment as the surface treatment for the wiring surface described in Comparative Example 3 was performed.

(Comparative Example 10)
As a surface treatment for the electrolytic copper foil, a test piece of an electrolytic copper foil was prepared in the same manner as in Example 4 except that the same surface treatment as the surface treatment for the wiring surface described in Comparative Example 4 was performed.

(Comparative Example 11)
As a surface treatment for the electrolytic copper foil, a test piece of an electrolytic copper foil was prepared in the same manner as in Example 4 except that the same surface treatment as each surface treatment for the wiring surface described in Comparative Example 5 was performed.

(Comparative Example 12)
As a surface treatment for the electrolytic copper foil, a test piece of an electrolytic copper foil was prepared in the same manner as in Example 4 except that the same surface treatment as the surface treatment for the wiring surface described in Comparative Example 6 was performed.

(Example 7)
In order to evaluate the insulation resistance value between wirings by the treatment of the copper surface of the present invention in (Step d), the following evaluation substrate was prepared.
(Process a ')
A 0.4 mm thick soda glass substrate (thermal expansion coefficient 11 ppm / ° C.) was prepared as the core substrate 100 shown in FIGS. 9 and 10, and the interlayer insulating layer 104 was formed on one side as follows. That is, an insulating varnish of a cyanate ester resin composition was applied onto a glass substrate by spin coating at 1500 rpm to form a resin layer having a thickness of 20 μm, and then increased from room temperature (25 ° C.) to 6 ° C./min. Heating to 230 ° C. at a temperature rate and thermosetting by maintaining at 230 ° C. for 80 minutes, an interlayer insulating layer 104 was formed. Thereafter, a Ni layer having a thickness of 20 nm was formed by sputtering in the same manner as in (Step f) of Example 1, and only a copper thin film 118 having a thickness of 200 nm was formed on the Ni layer.

Next, a plating resist PMER P-LA900PM (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name) was applied onto the copper thin film by a spin coating method to form a plating resist layer having a thickness of 10 μm. Next, the plating resist layer was exposed under the condition of 1000 mJ / cm ² and then immersed in PMER developer P-7G for 6 minutes at 23 ° C. to form a resist pattern 119. Thereafter, electrolytic copper plating was performed using a copper sulfate plating solution to form a wiring 106 having a thickness of about 5 μm. The plating resist was peeled off by immersion for 1 minute at room temperature (25 ° C.) using methyl ethyl ketone. In addition, for quick etching of the seed layer, a 5-fold diluted solution of CPE-700 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name) is used for etching removal by immersing and shaking at 30 ° C. for 30 seconds. The wiring 106 was formed.

(Process d ')
The surface treatment (pretreatment, palladium) described in (Step d-1), (Step d-2), and (Step d-3) of Example 1 is performed on the wiring 106 formed in the above (Step a ′). After the formation, oxidation treatment, reduction treatment, and electroless nickel-P plating treatment, an interlayer insulating layer (build-up layer) 104 shown in FIG. 9 and a solder resist 109 shown in FIG. 10 are formed, respectively. An evaluation substrate having L / S = 5 μm / 5 μm and L / S = 10 μm / 10 μm shown in FIG. 12 was produced.

(Example 8)
A substrate for evaluation was produced in the same manner as in Example 7 except that the same surface treatment as the surface treatment described in Example 2 was performed as each surface treatment in the above (Step d ′).

Example 9
A substrate for evaluation was produced in the same manner as in Example 7 except that the same surface treatment as that for each surface treatment described in Example 3 was performed as each surface treatment in (Step d ′) above.

(Comparative Example 13)
A substrate for evaluation was produced in the same manner as in Example 7 except that the same surface treatment as the surface treatment described in Comparative Example 1 was performed as each surface treatment in the above (Step d ′).

(Comparative Example 14)
A substrate for evaluation was produced in the same manner as in Example 7 except that the same surface treatment as the surface treatment described in Comparative Example 2 was performed as each surface treatment in (Step d ′) above.

(Comparative Example 15)
A substrate for evaluation was produced in the same manner as in Example 7 except that the same surface treatment as that for each surface treatment described in Comparative Example 3 was performed as each surface treatment in the above (Step d ′).

(Comparative Example 16)
A substrate for evaluation was produced in the same manner as in Example 7 except that the same surface treatment as that for each surface treatment described in Comparative Example 4 was performed as each surface treatment in (Step d ′) above.

(Comparative Example 17)
A substrate for evaluation was produced in the same manner as in Example 7 except that the same surface treatment as that for each surface treatment described in Comparative Example 5 was performed as each surface treatment in the above (Step d ′).

(Comparative Example 18)
A substrate for evaluation was produced in the same manner as in Example 7 except that the same surface treatment as that for each surface treatment described in Comparative Example 6 was performed as each surface treatment in the above (Step d ′).

The various test samples prepared as described above were subjected to each evaluation test as follows.
(Semiconductor package reliability test)
After performing a moisture absorption process on each of the semiconductor package samples described in Examples 1 to 3 and Comparative Examples 1 to 6, the reflow furnace having an ultimate temperature of 240 ° C. and a length of 2 m was subjected to a condition of 0.5 m / min. Each sample was run and reflowed. Then, the presence or absence of crack generation was examined for each sample, and the case where it occurred was determined as NG. The results are shown in Table 1.
Also, each semiconductor package sample is mounted on a 0.8 mm thick motherboard, and a temperature cycle test is performed under the conditions of -55 ° C, 30 minutes to 125 ° C, 30 minutes, and the 500th cycle, 1000th cycle, 1500th cycle. The electrical resistance of the wiring was measured using a multimeter 3457A manufactured by Hewlett-Packard (HP). NG was determined when the measured resistance value changed by 10% or more from the initial resistance value. The results are shown in Table 1. However, in Comparative Example 3, the wiring accuracy could not be maintained and a test substrate could not be manufactured.

(Adhesion test 1)
2. A prepreg E-679 (Hitachi Chemical Industry Co., Ltd., trade name) in which a glass cloth is impregnated with the electrolytic copper foils prepared in Examples 4 to 6 and Comparative Examples 7 to 12 is laminated. The substrate 1 for adhesion test was prepared by heating from normal temperature (25 ° C.) at a pressure of 0 MPa to 190 ° C. at a rate of temperature increase of 5 ° C./min and holding at 190 ° C. for 2 hours to laminate and bond. In addition, the said electrolytic copper foil is adhere | attached with the insulating layer (prepreg) in the surface side which gave various surface treatments. Next, each of the adhesion test substrates 1 obtained above was initially (0 hour), left at a high temperature of 120 ° C. for 120 hours, left at a high temperature of 150 ° C. for 240 hours, and PCT for 48 hours at 121 ° C. and 0.2 MPa. The mixture was left to stand for 96 hours at 121 ° C. and 0.2 MPa.

  Thereafter, an epoxy resin composition was applied to the copper surface of one side of a 0.8 mm thick copper-clad laminate using a chemical etching roughening solution HIST-7300 (manufactured by Hitachi Chemical Co., Ltd.). A prepreg impregnated with glass cloth is laminated on the outermost layer so that the resin side of the above-mentioned initial and high-temperature and PCT-adhesive test substrate 1 is combined with the above-mentioned prepreg. The substrate was heated to 220 ° C. at a temperature increase rate of 6 ° C./min from (25 ° C.) and held at 220 ° C. for 2 hours to laminate and bond, thereby producing an adhesion test substrate 2. Next, for each of the adhesive test substrates 2 obtained above, after sticking a 5 mm wide adhesive tape on the adhesive test substrate 1, it was immersed in an etching solution of a 200 g / L ammonium persulfate solution and pasted. After all the copper was etched, the adhesion at the interface between the 5 mm wide electrolytic copper foil and the insulating resin was measured. In addition, the measurement of the peel strength (N / m) used as the said parameter | index of adhesiveness uses rheometer NRM-3002D-H (Fudo Kogyo Co., Ltd. make, brand name), and makes an electrolytic copper foil perpendicular | vertical with respect to a board | substrate. The peeling was performed at a speed of 50 mm / min. The case where the peel strength value showed a value of 400 N / m or more was marked with ◯, and the case where the peel strength value was less than 400 N / m was marked with x. The results are shown in Table 2.

(Adhesion test 2)
Prepreg I-671 (Hitachi Chemical Industry Co., Ltd., trade name) in which a glass cloth was impregnated with the electrolytic copper foil, epoxy resin composition, and polyimide resin composition prepared in Examples 4 to 6 and Comparative Examples 7 to 12 Is laminated at a pressure of 3.0 MPa from room temperature (25 ° C.) to 190 ° C. at a rate of temperature increase of 5 ° C./min, and held at 190 ° C. for 3 hours to laminate and adhere to the substrate 1 for adhesion test. Was made. In addition, the said electrolytic copper foil is adhere | attached with the insulating layer (prepreg) in the surface side which gave various surface treatments. Next, each of the adhesion test substrates 1 obtained above was initially (0 hour), left at a high temperature of 120 ° C. for 120 hours, left at a high temperature of 150 ° C. for 240 hours, and PCT for 48 hours at 121 ° C. and 0.2 MPa. The mixture was left to stand for 96 hours at 121 ° C. and 0.2 MPa.

  Thereafter, an epoxy resin composition was applied to the copper surface of one side of a 0.8 mm thick copper-clad laminate using a chemical etching roughening solution HIST-7300 (manufactured by Hitachi Chemical Co., Ltd.). A prepreg impregnated with glass cloth is laminated on the outermost layer so that the resin side of the above-mentioned initial and high-temperature and PCT-adhesive test substrate 1 is combined with the above-mentioned prepreg. The substrate was heated to 220 ° C. at a temperature increase rate of 6 ° C./min from (25 ° C.) and held at 220 ° C. for 2 hours to laminate and bond, thereby producing an adhesion test substrate 2. Next, for each of the adhesive test substrates 2 obtained above, after sticking a 5 mm wide adhesive tape on the adhesive test substrate 1, it was immersed in an etching solution of a 200 g / L ammonium persulfate solution and pasted. After all the copper was etched, the adhesion at the interface between the 5 mm wide electrolytic copper foil and the insulating resin was measured. In addition, the measurement of the peel strength (N / m) used as the said parameter | index of adhesiveness uses rheometer NRM-3002D-H (Fudo Kogyo Co., Ltd. make, brand name), and makes an electrolytic copper foil perpendicular | vertical with respect to a board | substrate. The peeling was performed at a speed of 50 mm / min. The case where the peel strength value showed a value of 400 N / m or more was marked with ◯, and the case where the peel strength value was less than 400 N / m was marked with x. The results are shown in Table 3.

(Copper surface smoothness evaluation test)
The surface roughness (Rz) of the surface side subjected to the surface treatment of the electrolytic copper foils prepared in Examples 4 to 6 and Comparative Examples 7 to 12 is shown below using a simple atomic force microscope (AFM) Nanopics 2100. The measurement was performed under the condition 3.
Condition 3
Measurement length: 1 μm
SCAN SPEED: 1.35 μm / sec
FORCE REFERENCE: 160
When Rz is 1 nm or more and 100 nm or less, ◎, when Rz exceeds 100 nm and 1000 nm or less, ○, and when Rz is less than 1 nm or more than 1000 nm, Δ. The results are shown in Table 4.

(Insulation between wiring by copper surface treatment to wiring)
About each board | substrate for evaluation described in Examples 7-9 and Comparative Examples 13-18, the short circuit between wiring of L / S = 5micrometer / 5micrometer and L / S = 10micrometer / 10micrometer, and wiring were performed as follows. An evaluation board without disconnection was selected, and the insulation resistance value between the wirings was measured. However, the evaluation board of Comparative Example 15 was not measured because the wiring accuracy could not be maintained. First, using an R-8340A type digital ultra-high resistance microammeter manufactured by Advantest Corporation, a voltage of DC 5 V was applied between the wires at room temperature for 30 seconds, and the insulation resistance value between the wires was measured. Note that a digital multimeter 3457A manufactured by Hewlett-Packard Co., Ltd. was used for measuring the insulation resistance of 1 GΩ or less. Next, in a constant temperature and humidity chamber maintained at 85 ° C. and a relative humidity of 85%, a DC5V voltage is continuously applied between the wirings, and the same as above after 24 h, 48 h, 96 h, 200 h, 500 h, and 1,000 h. The insulation resistance value between the wires was measured. The constant temperature and humidity chamber was an EC-10HHPS type constant temperature and humidity chamber manufactured by Hitachi, Ltd., and was measured up to 1000 hours after being charged.
With respect to the evaluation board measured as described above, the minimum value of the insulation resistance value was x when it was less than 1 GΩ, and it was marked when it was 1 GΩ or more. The results are shown in Tables 5 and 6.

  As shown in Table 1, the semiconductor packages manufactured in Examples 1 to 3 showed extremely good reliability. Further, as shown in Tables 2 and 3, the electrolytic copper foils produced in Examples 4 to 6 have dense and uniform tens of nano level irregularities on the surface, so that the copper surface, the insulating layer, The adhesive strength (peel strength) after leaving at 150 ° C. for 240 hours and after standing at 1211 ° C. for 2 atm for 96 hours was 400 N / m or more, and was good. Further, as shown in Table 4 and Table 5, the inter-wiring insulation reliability in the evaluation boards manufactured in Examples 7 to 9 is extremely high in both L / S = 5 μm / 5 μm and L / S = 10 μm / 10 μm. It was good. On the other hand, in the case where the conventional technology and the copper surface treatment were not performed, as shown in the comparative example, the reliability, smoothness, adhesion, and inter-wiring insulation reliability test of the semiconductor package are all satisfied. could not. Therefore, by performing the copper surface treatment according to the present invention, the adhesion between the copper surface and the insulating layer, the inter-wiring insulation reliability, the wiring board and the semiconductor chip mounting substrate excellent in fine wiring formation, and the reflow resistance, It becomes possible to manufacture a semiconductor package having excellent temperature cycle characteristics.

It is sectional drawing of the board | substrate for semiconductor chip mounting to which one Embodiment of this invention is applied. (A)-(g) is process drawing which shows one Embodiment of the manufacturing method of the board | substrate for semiconductor chip mounting of this invention. 1 is a cross-sectional view of a flip chip type semiconductor package to which an embodiment of the present invention is applied. 1 is a cross-sectional view of a wire bond type semiconductor package to which an embodiment of the present invention is applied. It is a top view of the board | substrate for fan-in type semiconductor chips mounting of this invention. It is a top view of the board | substrate for fan-out type semiconductor chips mounting of this invention. It is a top view showing the frame shape of the board | substrate for semiconductor chip mounting of this invention. It is sectional drawing of the board | substrate for semiconductor chip mounting to which one Embodiment of this invention is applied. (A ')-(d') is process drawing which shows one Embodiment of the evaluation board | substrate manufacturing method for a test of this invention. (A ')-(d') is process drawing which shows one Embodiment of the evaluation board | substrate manufacturing method for a test of this invention. It is a top view of the evaluation board for electric corrosion tests to which one embodiment of the present invention is applied. It is a top view of the evaluation board for electric corrosion tests to which one embodiment of the present invention is applied.

Explanation of symbols

11. Positioning mark (guide hole for alignment)
13. Semiconductor package region 14. Die bond film bonding area (flip chip type)
15. Semiconductor chip mounting area (flip chip type)
16. Semiconductor chip connection terminal 17. Die bond film bonding area (wire bond type)
18. Semiconductor chip mounting area (wire bond type)
19. External connection terminal 20. Expanded wiring 21. Dummy pattern 22. Semiconductor chip mounting substrate 23. Block 24. Reinforcing pattern 25. Cutting alignment mark 100 Core substrate 101 First interlayer connection terminal 102 IVH (via hole) for first interlayer connection
103 Second interlayer connection terminal 104 Interlayer insulating layer (build-up layer)
105 Third layer connection IVH (via hole)
106 wiring 106a first wiring 106b second wiring 106c third wiring 107 external connection terminal 108 IVH (via hole) for second interlayer connection
109 Insulation coating (solder resist)
DESCRIPTION OF SYMBOLS 111 Semiconductor chip 112 Connection bump 113 Underfill material 114 Solder ball 115 Gold wire 116 Semiconductor sealing resin 117 Die-bonding film 118 Copper thin film 119 Resist pattern

Claims (5)

  A step of discretely forming a metal nobler than copper on the copper surface, a step of forming copper oxide on the copper surface by oxidizing with an alkaline solution containing an oxidizing agent, and then dissolving the copper oxide in an acidic solution A step of oxidizing the copper surface again with an alkaline solution containing an oxidizing agent to form copper oxide on the surface, and then reducing the copper oxide with an alkaline solution containing a reducing agent to form metallic copper. The processing method of the copper surface which has the process of forming.   The copper surface according to claim 1, wherein the oxidizing agent is at least one selected from the group consisting of chlorate, chlorite, hypochlorite, perchlorate, and peroxodisulfate. Processing method.   The metal nobler than copper is a metal selected from the group consisting of gold, silver, platinum, palladium, rhodium, rhenium, ruthenium, osmium, iridium, or an alloy containing the metal. Copper surface treatment method. Forming amount of noble metal is 0.001μmol / dm ² or more and 5 [mu] mol / dm ² or less, the processing method of the copper surface as claimed in any one of claims 1 to 3.   The processing method of the copper surface in any one of Claims 1-4 whose roughness of a copper surface is 1 nm or more and 1000 nm or less by Rz.

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