JP2013030504A - Adhesive sheet for manufacturing semiconductor device, and semiconductor device containing adhesive sheet for manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet capable of preventing product characteristics from being deteriorated and improving product reliability.
An adhesive sheet for manufacturing a semiconductor device containing an ion scavenger for manufacturing a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours in 50 ml of an aqueous solution containing 10 ppm of copper ions. The copper ion concentration in the aqueous solution after immersing the adhesive sheet and leaving it at 120 ° C. for 20 hours is 0 to 9.9 ppm, and the weight is 2.5 g heated at 175 ° C. for 5 hours in 50 ml of ion-exchanged water. An adhesive sheet for manufacturing a semiconductor device, in which the chloride ion concentration in an aqueous solution after immersing the adhesive sheet for manufacturing a semiconductor device and allowing it to stand at 120 ° C. for 20 hours is 0.1 ppm or less.
[Selection figure] None

Description

  The present invention relates to an adhesive sheet for manufacturing a semiconductor device and a semiconductor device having an adhesive sheet for manufacturing a semiconductor device.

  In recent years, a stacked MCP (Multi Chip Package) in which memory package chips for mobile phones and portable audio devices are stacked in multiple stages has become widespread. In addition, with the increasing functionality of image processing technology and mobile phones, etc., higher density, higher integration, and thinner packages are being promoted.

  On the other hand, when cations (for example, copper ions or iron ions) are mixed into the crystal substrate of the wafer from the outside during the semiconductor manufacturing process, and these cations reach the circuit formation surface formed on the wafer, the electrical characteristics There has been a problem of lowering. In addition, there is a problem that cations are generated from circuits and wires during use of the product, resulting in deterioration of electrical characteristics.

  In order to solve the above-described problems, conventionally, an extrinsic gettering (hereinafter also referred to as “EG”) in which a back surface of a wafer is processed to form a crushed layer (strain) and a cation is captured and removed by the crushed layer. Intrinsic gettering (hereinafter also referred to as “IG”) in which oxygen precipitation defects are formed in the crystal substrate of the wafer and cations are captured and removed by the oxygen precipitation defects has been attempted.

  However, with the recent thinning of the wafer, the IG effect is reduced, and the backside distortion that causes the wafer to crack and warp is removed, so that the EG effect cannot be obtained and the gettering effect is improved. There was a problem that it could not be obtained sufficiently.

  Patent Document 1 describes a film adhesive provided with a copper ion adsorption layer containing a resin having a skeleton capable of complexing with copper ions. In addition, it is described that copper ions can be chemically adsorbed inside the resin of the copper ion adsorption layer, and the influence of copper ions generated from a member made of copper can be significantly reduced as compared with the conventional case. ing. Patent Documents 2 and 3 describe an adhesive composition containing an ion scavenger, and it is disclosed that this ion scavenger has an effect of capturing chlorine ions and the like. Patent Document 4 describes a film adhesive containing an ion trapping agent, and describes that the ion trapping agent captures a halogen element. Patent Document 5 describes an adhesive sheet containing an anion exchanger. Patent Document 6 describes an adhesive sheet containing a metal impurity ion scavenger.

JP 2011-52109 A JP 2009-203337 A JP 2009-203338 A JP 2010-116453 A JP 2009-256630 A JP 2011-71216 A

  According to the film-like adhesive of Patent Document 1 and the adhesive sheet of Patent Document 6, copper ions can be captured. However, it does not disclose capturing chloride ions. Therefore, when a large amount of chloride ions are contained, generation of copper ions is promoted, and copper ions may not be sufficiently removed. In addition, the film adhesives of Patent Documents 2 to 5 do not disclose capturing copper ions. Therefore, it is difficult to prevent the deterioration of electrical characteristics based on copper ions only by capturing chloride ions.

  The present invention has been made in view of the above-described problems, and an object of the present invention is to provide an adhesive sheet that can prevent deterioration in electrical characteristics of a semiconductor device to be manufactured and improve product reliability, and manufacture of the semiconductor device. An object of the present invention is to provide a semiconductor device having an adhesive sheet.

  The inventors of the present application have studied an adhesive sheet for manufacturing a semiconductor device in order to solve the conventional problems. As a result, it was found that by suppressing both the influence of copper ions and the influence of chlorine ions, it was possible to prevent the deterioration of the electrical characteristics of the manufactured semiconductor device and improve the product reliability. It came to complete.

  That is, the adhesive sheet for manufacturing a semiconductor device according to the present invention is an adhesive sheet for manufacturing a semiconductor device containing an ion scavenger and heated at 175 ° C. for 5 hours in 50 ml of an aqueous solution containing 10 ppm of copper ions. A copper ion concentration in the aqueous solution after immersing an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g and leaving it at 120 ° C. for 20 hours is 0 to 9.9 ppm, and in 50 ml of ion-exchanged water, The chloride ion concentration in the aqueous solution after immersion of an adhesive sheet for manufacturing a semiconductor device weighing 2.5 g heated at 175 ° C. for 5 hours and left at 120 ° C. for 20 hours is 0.1 ppm or less. It is characterized by.

  According to the above configuration, an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours is immersed in 50 ml of an aqueous solution containing 10 ppm of copper ions and left at 120 ° C. for 20 hours. The copper ion concentration in the aqueous solution is 0 to 9.9 ppm. Therefore, copper ions mixed from the outside are captured during various processes in manufacturing the semiconductor device. As a result, it becomes difficult for copper ions mixed from the outside to reach the circuit formation surface formed on the wafer. Also, a chloride ion concentration in the aqueous solution after immersing an adhesive sheet for manufacturing a semiconductor device weighing 2.5 g heated at 175 ° C. for 5 hours in 50 ml of ion-exchanged water and leaving at 120 ° C. for 20 hours. However, it is 0.1 ppm or less. Therefore, promotion of copper ion generation is suppressed. That is, according to the above-described configuration, since copper ions are captured and the promotion of the generation is suppressed, a decrease in electrical characteristics of the semiconductor device manufactured using the adhesive sheet for manufacturing the semiconductor device is suppressed. Product reliability can be improved.

  The said structure WHEREIN: It is preferable that the said ion trapping agent is a both ion trapping agent. When the ion scavenger is a both ion scavenger, copper ions can be captured and chloride ions can be captured.

  The said structure WHEREIN: It is preferable that the addition amount of the said both ion scavenger is 0.1-20 weight part with respect to 100 weight part of resin components which comprise the said adhesive sheet. By making the addition amount of the both ion scavengers 0.1 parts by weight or more, copper ions and chloride ions can be effectively captured. Moreover, the fall of adhesive force can be suppressed by making the addition amount of the said both ion capture | acquisition agent into 20 weight part or less.

  In the above configuration, the ion scavenger is preferably a mixture of a copper ion scavenger and a chloride ion scavenger. When the ion scavenger is a mixture of a copper ion scavenger and a chloride ion scavenger, copper ions can be captured and chloride ions can be captured.

  The said structure WHEREIN: The addition amount of the mixture of the said copper ion scavenger and the said chloride ion scavenger is 0.2-40 weight part with respect to 100 weight part of resin components which comprise the said adhesive sheet. preferable. By making the addition amount of the mixture 0.2 parts by weight or more, copper ions and chloride ions can be effectively captured. Moreover, the fall of adhesive force can be suppressed by making the addition amount of the said mixture into 40 weight part or less.

  In the above configuration, when the addition amount of the copper ion scavenger is A parts by weight and the addition amount of the chloride ion scavenger is B parts by weight, the mixing ratio of the copper ion scavenger and the chloride ion scavenger is A / (A + B) is preferably 0.13 to 0.99. When the mixing ratio A / (A + B) is within the above range, a synergistic effect of the copper ion scavenger and the anion scavenger is obtained. That is, since the anion released as a counter ion when the chloride ion scavenger captures chloride ions is neutralized by the cation released as a counter ion when the copper ion scavenger captures copper ions, The ion trapping efficiency of each of the copper ion trapping agent and the chloride ion trapping agent is improved. Since ion trapping is performed by an equilibrium reaction (ion exchange), ion exchange of target ions is promoted by reducing the concentration of counter ions.

  The said structure WHEREIN: It is preferable to contain an epoxy resin. When an epoxy resin is contained as a curing agent, a high adhesive force between the adhesive sheet and the wafer can be obtained at a high temperature. As a result, it is difficult for water to enter the adhesive interface between the adhesive sheet and the wafer, making it difficult for ions to move. Thereby, reliability is improved.

  A semiconductor device according to the present invention includes the adhesive sheet for manufacturing a semiconductor device described above. According to the said structure, since it has the adhesive sheet for semiconductor device manufacture as described above, it can be set as the semiconductor device which product reliability improved.

The adhesive sheet for manufacturing a semiconductor device of the present invention is obtained by immersing an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours in 50 ml of an aqueous solution containing 10 ppm of copper ions at 120 ° C. The copper ion concentration in the aqueous solution after standing for 20 hours is 0 to 9.9 ppm, preferably 0 to 9.5 ppm, and more preferably 0 to 9.0 ppm. The adhesive sheet for manufacturing a semiconductor device is obtained by immersing an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours in 50 ml of an aqueous solution containing 10 ppm of copper ions, and at 120 ° C. for 20 hours. Since the copper ion concentration in the aqueous solution after being left is 0 to 9.9 ppm, copper ions mixed from the outside are captured during various processes in manufacturing the semiconductor device. As a result, it becomes difficult for copper ions mixed from the outside to reach the circuit formation surface formed on the wafer.
Moreover, the adhesive sheet for manufacturing a semiconductor device of the present invention is obtained by immersing an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours in 50 ml of ion-exchanged water, and at 120 ° C. for 20 hours. The chloride ion concentration in the aqueous solution after being left is 0.1 ppm or less. The adhesive sheet for manufacturing a semiconductor device was prepared by immersing an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours in 50 ml of ion-exchanged water and leaving it at 120 ° C. for 20 hours. Since the chloride ion concentration in the aqueous solution is 0.1 ppm or less, the promotion of copper ion generation is suppressed.
That is, according to the adhesive sheet for manufacturing a semiconductor device of the present invention, since copper ions are captured and the promotion of the generation is suppressed, the semiconductor device manufactured using the adhesive sheet for manufacturing the semiconductor device Deterioration of electrical characteristics can be suppressed and product reliability can be improved.

  The adhesive sheet for manufacturing a semiconductor device of the present invention is not particularly limited, but the film thickness is preferably 3 to 150 μm, more preferably 5 to 120 μm, and further preferably 5 to 60 μm. By setting the film thickness of the adhesive sheet for manufacturing the semiconductor device to 3 μm or more, copper ions can be captured better. On the other hand, when the film thickness of the adhesive sheet for manufacturing the semiconductor device is 150 μm or less, the film thickness can be easily controlled.

  The adhesive sheet for manufacturing a semiconductor device of the present invention (hereinafter also simply referred to as “adhesive sheet”) contains an ion scavenger. The ion scavenger is preferably a both ion scavenger. When the ion scavenger is a both ion scavenger, copper ions can be captured and chloride ions can be captured. The ion scavenger is preferably a mixture of a copper ion scavenger and a chloride ion scavenger. When the ion scavenger is a mixture of a copper ion scavenger and a chloride ion scavenger, copper ions can be captured and chloride ions can be captured.

(Both ion scavenger)
In the present invention, the amphoteric scavenger refers to those capable of trapping both a certain amount of both copper ions and chloride ions, and includes conventionally known inorganic amphoteric exchangers. Specifically, the inorganic both ion exchangers have a copper (II) ion distribution coefficient (Kd) of 10 or more determined according to the following copper (II) ion distribution coefficient measurement method, and the following ion exchange capacity: The ion exchange capacity (meq / g) calculated | required according to this measuring method can mention 0.5 or more.
<Measurement method of copper (II) ion partition coefficient>
Into a 100 ml plastic container, 5.0 g of an inorganic amphoteric ion exchanger and 50 ml of a test solution containing 0.01 N of copper (II) ions are put, sealed, and shaken at 25 ° C. for 24 hours. After shaking, the mixture is filtered with a 0.1 μm membrane filter, and the copper (II) ion concentration in the filtrate is measured with ICP-AES (SPS-1700HVR, manufactured by SII Nanotechnology Co., Ltd.). II) Obtain the ion distribution coefficient Kd. Kd (ml / g) is represented by (C ₀ -C) × V / (C × m), where C ₀ is the initial ion concentration, C is the test solution ion concentration, V is the test solution volume (ml), and m is inorganic. It is the weight (g) of both ion exchangers.
<Measurement method of ion exchange capacity>
1.0 g of inorganic both ion exchangers are immersed in 50 ml of saturated NaCl aqueous solution and left at room temperature for 20 hours. The amount of hydroxide ions generated by the inorganic amphoteric ion exchanger is quantified by titration with a 0.1N aqueous HCl solution to determine the ion exchange capacity (meq./g).

(Inorganic amphoteric ion exchanger)
Examples of the inorganic both ion exchangers include hydrotalcite compounds having a specific structure, and specific products include IXE-700F manufactured by Toa Gosei Co., Ltd. (ion distribution coefficient: 100,000 or more). , Ion exchange capacity: 4.5 (meq / g)), IXE-770 (ion distribution coefficient: 21000 or more, ion exchange capacity: 2.9 (meq / g)), IXE-770D (ion distribution coefficient: 100,000 or more) , Ion exchange capacity: 1.1 (meq / g)) and the like.

(Copper ion scavenger)
In the present invention, the copper ion scavenger refers to those capable of capturing a certain amount or more of copper ions and capturing only a certain amount or less of chloride ions, such as conventionally known inorganic copper ion exchangers, complex forming compounds, etc. Can be mentioned. Specifically, the inorganic copper ion exchanger has a copper (II) ion distribution coefficient (Kd) of 10 or more determined according to the following copper (II) ion distribution coefficient measurement method, and the following ion exchange capacity: The ion exchange capacity (meq / g) calculated | required according to this measuring method can be mentioned below.
<Measurement method of copper (II) ion partition coefficient>
Into a 100 ml polycontainer, 5.0 g of an inorganic copper ion exchanger and 50 ml of a test solution containing 0.01 N of copper (II) ions are put, sealed, and shaken at 25 ° C. for 24 hours. After shaking, the mixture is filtered with a 0.1 μm membrane filter, and the copper (II) ion concentration in the filtrate is measured with ICP-AES (SPS-1700HVR, manufactured by SII Nanotechnology Co., Ltd.). II) Obtain the ion distribution coefficient Kd. Kd (ml / g) is represented by (C ₀ -C) × V / (C × m), where C ₀ is the initial ion concentration, C is the test solution ion concentration, V is the test solution volume (ml), and m is inorganic. It is the weight (g) of the copper ion exchanger.
<Measurement method of ion exchange capacity>
1.0 g of inorganic copper ion exchanger is immersed in 50 ml of saturated NaCl aqueous solution and left at room temperature for 20 hours. The amount of hydroxide ions generated by the inorganic copper ion exchanger is quantified by titration with a 0.1N HCl aqueous solution to determine the ion exchange capacity (meq./g).

(Inorganic copper ion exchanger)
Examples of the inorganic copper ion exchanger include zirconium phosphate having a specific structure (for example, manufactured by Toa Gosei Co., Ltd., IXE-100, ion partition coefficient: 320), hydrous antimony (for example, Toa Gosei Co., Ltd.) IXE-300, ion distribution coefficient: 11000) Magnesium silicate (for example, Kyowa Chemical Industry Co., Ltd., Kyoward 600), aluminum silicate (for example, Kyowa Chemical Industry Co., Ltd., Kyoward) 700).

(Complex-forming compound)
The complex-forming compound is not particularly limited as long as it forms a complex with copper ions, but is preferably an organic complex-forming compound, from the viewpoint that copper ions can be suitably captured, It is preferably at least one selected from the group consisting of a nitrogen-containing compound, a hydroxyl group-containing compound, and a carboxylic acid group-containing compound.

(Nitrogen-containing compounds)
The nitrogen-containing compound is preferably in the form of fine powder, easily dissolved in an organic solvent, or liquid. Examples of such nitrogen-containing compounds include triazole compounds, tetrazole compounds, or bipyridyl compounds from the viewpoint of more suitably capturing copper ions, but the stability of complexes formed with copper ions. In view of the above, a triazole compound is more preferable. These can be used alone or in combination of two or more.

  The triazole compound is not particularly limited, but 1,2,3-benzotriazole, 1- {N, N-bis (2-ethylhexyl) aminomethyl} benzotriazole, carboxybenzotriazole, 2- {2′-hydroxy -5'-methylphenyl} benzotriazole, 2- {2'-hydroxy-3 ', 5'-di-t-butylphenyl} -5-chlorobenzotriazole, 2- {2'-hydroxy-3'-t -Butyl-5'-methylphenyl} -5-chlorobenzotriazole, 2- {2'-hydroxy-3 ', 5'-di-t-amylphenyl} benzotriazole, 2- {2'-hydroxy-5' -T-octylphenyl} benzotriazole, 6- (2-benzotriazolyl) -4-t-octyl-6'-t-butyl-4 ' Methyl-2,2′-methylenebisphenol, 1- (2 ′, 3′-hydroxypropyl) benzotriazole, 1- (1 ′, 2′-dicarboxydiethyl) benzotriazole, 1- (2-ethylhexamino) Methyl) benzotriazole, 2,4-di-t-benzyl-6-{(H-benzotriazol-1-yl) methyl} phenol, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzo Triazole, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, octyl-3- [3-t-butyl-4-hydroxy-5- (5- Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5 Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3 3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4-t-butylphenol, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′- Hydroxy-5'-t-octylphenyl) -benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chloro -Benzotriazole, 2- [2'-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2'-methylenebis [6- (2H-benzotriazole-2- Yl) -4- (1,1,3,3-metramethylbutyl) phenol], (2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, And methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate.

  Although it does not restrict | limit especially as a commercial item of the said triazole compound, The brand name made from Johoku Chemical Co., Ltd .: BT-120, BT-LX, CBT-1, JF-77, JF-78, JF-79, JF- Product names of 80, JF83, JAST-500, BT-GL, BT-M, BT-260, BT-365, BASF: TINUVIN PS, TINUVIN P, TINUVIN P FL, TINUVIN 99-2, TINUVIN 109, TINUVIN 900 , TINUVIN 928, TINUVIN 234, TINUVIN 329, TINUVIN 329 FL, TINUVIN 326, TINUVIN 326 FL, TINUVIN 571, TINUVIN 213, Taiwan Yongkou Chemical Co., Ltd. Product names: EVESORB 81, EVES RB109, EVESORB 70, EVESORB 71, EVESORB 72, EVESORB 73, EVESORB 74, EVESORB 75, can be cited EVESORB 76, EVESORB 78, EVESORB 80 or the like. Triazole compounds are also used as rust inhibitors.

  Although it does not specifically limit as said tetrazole compound, 5-amino-1H-tetrazole etc. are mentioned.

  Although it does not specifically limit as said bipyridyl compound, 2,2'-bipyridyl, 1, 10-phenanthroline etc. are mentioned.

(Hydroxyl-containing compound)
Although it does not restrict | limit especially as said hydroxyl-containing compound, The thing of a fine powder form, the thing easy to melt | dissolve in an organic solvent, or a liquid thing is preferable. As such a hydroxyl group-containing compound, a quinol compound, a hydroxyanthraquinone compound, or a polyphenol compound can be exemplified from the viewpoint of more suitably capturing a copper ion, but the stability of a complex formed with the copper ion can be mentioned. From the viewpoint of properties, a polyphenol compound is more preferable. These can be used alone or in combination of two or more.

  Although it does not specifically limit as said quinol compound, 1, 2- benzenediol etc. are mentioned.

  Although it does not specifically limit as said hydroxyanthraquinone compound, Alizarin, anthralfin, etc. are mentioned.

  Although it does not specifically limit as said polyphenol compound, A tannin, a tannin derivative (gallic acid, methyl gallate, pyrogallol) etc. are mentioned.

(Carboxylic acid group-containing compound)
Although it does not specifically limit as said carboxylic acid group containing compound, A carboxyl group containing aromatic compound, a carboxyl group containing fatty acid compound, etc. are mentioned.

  The carboxyl group-containing aromatic compound is not particularly limited, and examples thereof include phthalic acid, picolinic acid, and pyrrole-2-carboxylic acid.

  The carboxyl group-containing fatty acid compound is not particularly limited, and examples thereof include higher fatty acids and carboxylic acid chelating reagents.

  Although it does not restrict | limit especially as a commercial item of the said carboxylic acid type | system | group chelating reagent, The product name made from Kyrest Co., Ltd .: Kyrest A, Kyrest 110, Kyrest B, Kyrest 200, Kyrest C, Kyrest D, Kyrest 400, Kyrest 40, Examples include Kirest 0D, Kirest NTA, Kirest 700, Kirest PA, Kirest HA, Kirest MZ-2, Kirest MZ-4A, and Kirest MZ-8.

(Chloride ion scavenger)
In the present invention, the chloride ion scavenger refers to one that can capture a certain amount or more of chloride ions and can capture only a certain amount or less of copper ions, and is a conventionally known chloride ion exchanger such as a specific one. Aluminosilicates such as natural zeolite and synthetic zeolite having structures; metal oxides such as aluminum oxide and magnesium oxide; hydrous titanium oxide, hydrous bismuth oxide, hydrous antimony, hydrous aluminum oxide, hydrous magnesium oxide, hydrous zirconium oxide, etc. Hydroxides or hydrous oxides; acidic metal salts such as zirconium phosphate and titanium phosphate; basic salts and complex hydrous oxides such as hydrotalcite compounds; heteropolyphosphoric acids such as ammonium molybdophosphate; hexacyanoiron (III ) Salt and hexacyanozinc. Examples of the bismuth hydroxide as a chloride ion scavenger include trade names IXE-500 (ion exchange capacity: 3.9 (meq / g)) and IXE-530 (ion exchange capacity: manufactured by Toa Gosei Co., Ltd.). 3.7 (meq / g)), IXE-550 (ion exchange capacity: 4.1 (meq / g)), and the like. Examples of the hydrotalcite compound as a chloride ion scavenger include KW2200, KW2100, DHT-4A, DHT-4B, DHT-4C, and the like manufactured by Kyowa Chemical Industry Co., Ltd. Specifically, the chloride ion exchanger has a copper (II) ion distribution coefficient (Kd) of less than 10 determined according to the following copper (II) ion distribution coefficient measurement method, and the following ion exchange capacity: The ion exchange capacity (meq / g) calculated | required according to this measuring method can mention 0.5 or more.
<Measurement method of copper (II) ion partition coefficient>
In a 100 ml plastic container, 5.0 g of a chloride ion exchanger and 50 ml of a test solution containing 0.01N of copper (II) ions are put, sealed, and shaken at 25 ° C. for 24 hours. After shaking, the mixture is filtered with a 0.1 μm membrane filter, and the copper (II) ion concentration in the filtrate is measured with ICP-AES (SPS-1700HVR, manufactured by SII Nanotechnology Co., Ltd.). II) Obtain the ion distribution coefficient Kd. Kd (ml / g) is represented by (C ₀ -C) × V / (C × m), where C ₀ is the initial ion concentration, C is the test solution ion concentration, V is the test solution volume (ml), and m is the chloride. It is the weight (g) of the product ion exchanger.
<Measurement method of ion exchange capacity>
1.0 g of chloride ion exchanger is immersed in 50 ml of saturated NaCl solution and left at room temperature for 20 hours. The amount of hydroxide ions generated by the chloride ion exchanger is quantified by titration with a 0.1N HCl aqueous solution to determine the ion exchange capacity (meq./g).

  Examples of commercially available mixtures of copper ion scavenger and chloride ion scavenger include IXE-600, IXE-633, etc. manufactured by Toagosei Co., Ltd., which are a mixture of hydrous bismuth oxide and hydrous antimony. it can. In addition, examples include IXE-6107 and IXE-6136 manufactured by Toa Gosei Co., Ltd., which are a mixture of hydrous bismuth oxide and hydrous zirconium oxide.

  The ion-trapping agent (a) immerses an adhesive sheet for manufacturing a semiconductor device weighing 2.5 g heated at 175 ° C. for 5 hours in 50 ml of an aqueous solution containing 10 ppm of copper ions and left at 120 ° C. for 20 hours. The copper ion concentration in the aqueous solution after the heating is 0 to 9.9 ppm, and (b) for manufacturing a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours in 50 ml of ion-exchanged water. If the adhesive sheet satisfies that the chloride ion concentration in the aqueous solution after immersing the adhesive sheet and leaving it at 120 ° C. for 20 hours is 0.1 ppm or less, it is a copper ion scavenger. Also good. In this case, a resin having a low chloride ion concentration may be employed as the resin constituting the adhesive sheet.

  Moreover, you may use the said ion trapping agent in mixture of 2 or more types.

  When the ion scavenger is a both ion scavenger, the addition amount of the both ion scavengers is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the resin component constituting the adhesive sheet, More preferably, it is 3 to 20 parts by weight. By making the addition amount of the both ion scavengers 1 part by weight or more, copper ions and chloride ions can be effectively captured. Moreover, the fall of adhesive force can be suppressed by making the addition amount of the said both ion capture | acquisition agent into 20 weight part or less.

Further, when the ion scavenger is a mixture of a copper ion scavenger and a chloride ion scavenger, the addition amount of the mixture of the copper ion scavenger and the chloride ion scavenger constitutes the adhesive sheet It is preferable that it is 0.2-40 weight part with respect to 100 weight part of resin components to perform, and it is more preferable that it is 2-35 weight part. By making the addition amount of the mixture 0.2 parts by weight or more, copper ions and chloride ions can be effectively captured. Moreover, the fall of adhesive force can be suppressed by making the addition amount of the said mixture into 40 weight part or less.
In this case, when the addition amount of the copper ion scavenger is A parts by weight and the addition amount of the chloride ion scavenger is B parts by weight, the mixing ratio A / of the copper ion scavenger and the chloride ion scavenger is A /. (A + B) is preferably 0.13 to 0.99, more preferably 0.05 to 0.95, still more preferably 0.23 to 0.93, and 0.10 to 0.99. More preferably, it is 0.90. When the mixing ratio A / (A + B) is within the above range, a synergistic effect of the copper ion scavenger and the anion scavenger is obtained. That is, since the anion released as a counter ion when the chloride ion scavenger captures chloride ions is neutralized by the cation released as a counter ion when the copper ion scavenger captures copper ions, The ion trapping efficiency of each of the copper ion trapping agent and the chloride ion trapping agent is improved. Since ion trapping is performed by an equilibrium reaction (ion exchange), ion exchange of target ions is promoted by reducing the concentration of counter ions.

  The average particle size of the ion scavenger is preferably 0.05 to 20 μm, and more preferably 0.1 to 10 μm. By setting the average particle size of the ion scavenger to 20 μm or less, it is possible to suppress a decrease in adhesive force, and by setting it to 0.05 μm or more, dispersibility can be improved.

  The adhesive sheet preferably contains a thermoplastic resin. Moreover, it is preferable that the said adhesive sheet contains a thermoplastic resin and a thermosetting resin. Examples of the thermosetting resin include phenol resin, amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicone resin, and thermosetting polyimide resin. These resins can be used alone or in combination of two or more, and it is particularly preferable to use at least one of an epoxy resin and a phenol resin. Among these, it is preferable to use an epoxy resin. When an epoxy resin is contained as a curing agent, a high adhesive force between the adhesive sheet and the wafer can be obtained at a high temperature. As a result, it is difficult for water to enter the adhesive interface between the adhesive sheet and the wafer, making it difficult for ions to move. Thereby, reliability is improved.

  The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition, for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type. Biphenyl type, naphthalene type, fluorene type, phenol novolak type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type, etc., bifunctional epoxy resin or polyfunctional epoxy resin, or hydantoin type, trisglycidyl isocyanurate Type or glycidylamine type epoxy resin is used. These can be used alone or in combination of two or more. Of these epoxy resins, novolac type epoxy resins, biphenyl type epoxy resins, trishydroxyphenylmethane type resins or tetraphenylolethane type epoxy resins are particularly preferred. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent and are excellent in heat resistance and the like. Moreover, it is preferable to employ | adopt the thing (for example, Nippon Steel Chemical Co., Ltd. product name: KI-3000) with little content of chloride ion as an epoxy resin. If such an epoxy resin is adopted, both the ion scavenger and the chloride ion scavenger are not used, and only by adding the copper ion scavenger, (a) in an aqueous solution having 10 ppm of copper ions at 175 ° C. The copper ion concentration in the aqueous solution after immersing the adhesive sheet for manufacturing a semiconductor device weighing 2.5 g heated for 5 hours at 120 ° C. for 20 hours is 0 to 9.9 ppm, and (B) Chloride in the aqueous solution after immersing an adhesive sheet for manufacturing a semiconductor device weighing 2.5 g heated at 175 ° C. for 5 hours in 50 ml of ion-exchanged water and leaving at 120 ° C. for 20 hours It becomes possible to obtain an adhesive sheet satisfying that the ion concentration is 0.1 ppm or less.

  Further, the phenol resin acts as a curing agent for the epoxy resin, for example, a novolac type phenol resin such as a phenol novolac resin, a phenol aralkyl resin, a cresol novolac resin, a tert-butylphenol novolac resin, a nonylphenol novolac resin, Examples include resol-type phenolic resins and polyoxystyrenes such as polyparaoxystyrene. These can be used alone or in combination of two or more. Of these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.

  The mixing ratio of the epoxy resin and the phenol resin is preferably such that, for example, the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per 1 equivalent of the epoxy group in the epoxy resin component. . More preferred is 0.8 to 1.2 equivalents. That is, if the blending ratio of both is out of the above range, sufficient curing reaction does not proceed and the properties of the cured epoxy resin are likely to deteriorate.

  Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, heat Examples thereof include plastic polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, acrylic resins, saturated polyester resins such as PET and PBT, polyamideimide resins, and fluorine resins. These thermoplastic resins can be used alone or in combination of two or more. Of these thermoplastic resins, an acrylic resin that has few ionic impurities and high heat resistance and can ensure the reliability of the semiconductor element is particularly preferable.

  The acrylic resin is not particularly limited, and includes one or two or more esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms. Examples thereof include a polymer (acrylic copolymer) as a component. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, cyclohexyl, 2- Examples include an ethylhexyl group, an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a lauryl group, a tridecyl group, a tetradecyl group, a stearyl group, an octadecyl group, and a dodecyl group.

  In addition, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Carboxyl group-containing monomers such as acid anhydride monomers such as maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- (meth) acrylic acid 4- Hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) -Methyla Hydroxyl group-containing monomers such as relate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate or (meth) Examples thereof include sulfonic acid group-containing monomers such as acryloyloxynaphthalene sulfonic acid, and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate. These can be used alone or in combination of two or more.

  The blending ratio of the thermosetting resin is not particularly limited as long as the adhesive sheet exhibits a function as a thermosetting mold when heated under predetermined conditions, but is in the range of 5 to 60% by weight. It is preferable that it is in the range of 10 to 50% by weight.

  Among the adhesive sheets, an epoxy resin, a phenol resin, and an acrylic resin are contained, and the total amount of the epoxy resin and the phenol resin with respect to 100 parts by weight of the acrylic resin is preferably 10 to 2000 parts by weight. It is more preferably ˜1500 parts by weight, and further preferably 10 to 1000 parts by weight. By making the total amount of the epoxy resin and the phenol resin with respect to 100 parts by weight of the acrylic resin 10 parts by weight or more, an adhesive effect due to curing can be obtained, and peeling can be suppressed. It is possible to suppress the workability from being deteriorated due to the weakening of the film.

  When the adhesive sheet is previously crosslinked to some extent, it is preferable to add a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer as a crosslinking agent. Thereby, the adhesive property under high temperature can be improved and heat resistance can be improved.

  A conventionally well-known thing can be employ | adopted as said crosslinking agent. In particular, polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, adducts of polyhydric alcohol and diisocyanate are more preferable. The addition amount of the crosslinking agent is usually preferably 0.05 to 7 parts by weight with respect to 100 parts by weight of the polymer. By setting the amount of the crosslinking agent to 7 parts by weight or less, it is possible to suppress a decrease in adhesive force. On the other hand, when the content is 0.05 parts by weight or more, a lack of cohesive force can be reduced. Moreover, you may make it include other polyfunctional compounds, such as an epoxy resin, together with such a polyisocyanate compound as needed.

  Moreover, a filler can be appropriately blended in the adhesive sheet according to its use. The blending of the filler enables imparting electrical conductivity to the adhesive sheet, improving thermal conductivity, adjusting the elastic modulus, and the like. Examples of the filler include inorganic fillers and organic fillers, and inorganic fillers are preferable from the viewpoints of characteristics such as improvement in handleability, improvement in thermal conductivity, adjustment of melt viscosity, and imparting thixotropic properties. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and aluminum borate whisker. , Boron nitride, crystalline silica, amorphous silica and the like. These can be used alone or in combination of two or more. From the viewpoint of improving thermal conductivity, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, and amorphous silica are preferable. Further, from the viewpoint that the above properties are well balanced, crystalline silica or amorphous silica is preferable. In addition, a conductive substance (conductive filler) may be used as the inorganic filler for the purpose of imparting conductivity and improving thermal conductivity. Examples of the conductive filler include metal powder in which silver, aluminum, gold, cylinder, nickel, conductive alloy and the like are made into a spherical shape, needle shape and flake shape, metal oxide such as alumina, amorphous carbon black, graphite and the like.

  The filler may have an average particle size of 0.01 to 10 μm. By setting the average particle size of the filler to 0.01 μm or more, the wettability to the adherend and the adhesiveness can be improved. Moreover, by setting it as 10 micrometers or less, while being able to make the effect of the filler added for provision of said each characteristic sufficient, heat resistance can be ensured. In addition, the average particle diameter of a filler is the value calculated | required, for example with the photometric type particle size distribution analyzer (The product made from HORIBA, apparatus name; LA-910).

  In addition to the ion scavenger, other additives can be appropriately blended in the adhesive sheet as necessary. Examples of other additives include a dispersant, an antioxidant, a silane coupling agent, and a curing accelerator. These can be used alone or in combination of two or more.

  The method for producing the adhesive composition for forming the adhesive sheet is not particularly limited. For example, an ion scavenger and, if necessary, a thermosetting resin, a thermoplastic resin, and other additives in a container. , And dissolved in an organic solvent, and stirred uniformly to obtain an adhesive composition solution.

  The organic solvent is not particularly limited as long as it can uniformly dissolve, knead or disperse the components constituting the adhesive sheet, and a conventionally known one can be used. Examples of such a solvent include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like. Methyl ethyl ketone, cyclohexanone, and the like are preferably used because they have a high drying rate and can be obtained at low cost.

  The adhesive sheet according to the present embodiment is produced, for example, as follows. First, the adhesive composition solution is prepared. Next, the adhesive composition solution is applied on the base separator so as to have a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions. As the base material separator, polyethylene terephthalate (PET), polyethylene, polypropylene, or a plastic film or paper surface-coated with a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate-type release agent can be used. Moreover, it does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. As drying conditions, for example, the drying temperature is 70 to 160 ° C. and the drying time is 1 to 5 minutes. Thereby, the adhesive sheet which concerns on this embodiment is obtained.

  Since the adhesive sheet obtained in this way contains an ion scavenger, it can capture copper ions mixed from outside during various processes in the manufacture of semiconductor devices. In addition, when the ion scavenger contains both ion scavengers or chloride ion scavengers, chloride ions can be captured. As a result, copper ions are captured and the promotion of the generation is suppressed, so that the deterioration of the electrical characteristics of the semiconductor device manufactured using the adhesive sheet for manufacturing the semiconductor device is suppressed and the product reliability is improved. Can be made.

  In the above-described embodiment, the case where a thermosetting resin or a thermoplastic resin is used as the adhesive main component to be contained in the adhesive composition has been described. However, in the present invention, the adhesive mainly contained in the adhesive composition is used. Instead of the thermosetting resin and thermoplastic resin as described above, inorganic components such as ceramics, cements, and solders may be included as components.

  The adhesive sheet for manufacturing a semiconductor device is not particularly limited as long as it is used for manufacturing a semiconductor device. For example, a die bond film for fixing a semiconductor chip to an adherend such as a lead frame or a flip chip type Examples thereof include a protective film for protecting the back surface of the semiconductor chip of the semiconductor device and a sealing sheet for sealing the semiconductor chip.

  Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in this example are not intended to limit the gist of the present invention only to those unless otherwise limited. In the following, “parts” means parts by weight.

Example 1
The following (a) to (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) (Made by Co., Ltd., MEH-7851H) 5 parts (d) Silica filler (manufactured by Admatechs, SC-2050, average particle size 0.5 μm)
50 parts (e) amphoteric ion scavenger (manufactured by Toa Gosei Co., Ltd., IXE-770) 10 parts

(Example 2)
The following (a) to (f) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) 5 parts (d) silica filler (manufactured by Admatechs, SC-2050) 40 parts (e) chloride ion scavenger (manufactured by Toagosei Co., Ltd., IXE-550) ) 10 parts (f) Copper ion scavenger (manufactured by Toagosei Co., Ltd., IXE-100) 10 parts

(Example 3)
The following (a) to (f) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 29 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) 5 parts (d) silica filler (manufactured by Admatechs, SC-2050) 48 parts (e) chloride ion scavenger (manufactured by Toagosei Co., Ltd., IXE-550) ) 10 parts (f) Copper ion scavenger (Tokyo Chemical Industry Co., Ltd., dodecyl gallate) 3 parts

Example 4
The following (a) to (f) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) 5 parts (d) silica filler (manufactured by Admatechs, SC-2050) 39 parts (e) chloride ion scavenger (manufactured by Toagosei Co., Ltd., IXE-550) ) 1 part (f) Copper ion scavenger (Toa Gosei Co., Ltd., IXE-100) 20 parts

(Example 5)
The following (a) to (f) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) MEH-7851H) 5 parts (d) Silica filler (manufactured by Admatechs, SC-2050) 38 parts (e) Chloride ion scavenger (Toa Gosei Co., Ltd., IXE-550) ) 2 parts (f) Copper ion scavenger (Toa Gosei Co., Ltd., IXE-100) 20 parts

(Example 6)
The following (a) to (f) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) 5 parts (d) silica filler (manufactured by Admatechs, SC-2050) 49.5 parts (e) chloride ion scavenger (manufactured by Toa Gosei Co., Ltd., IXE) -550) 10 parts (f) Copper ion scavenger (Tokyo Chemical Industry Co., Ltd., dodecyl gallate) 0.5 parts

(Example 7)
The following (a) to (f) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) MEH-7851H) 5 parts (d) Silica filler (manufactured by Admatechs, SC-2050) 38 parts (e) Chloride ion scavenger (Toa Gosei Co., Ltd., IXE-550) ) 20 parts (f) Copper ion scavenger (Tokyo Chemical Industry Co., Ltd., dodecyl gallate) 2 parts

(Example 8)
The following (a) to (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., KI-3000) 5 parts (c) Phenol resin (Maywa Kasei) 5 parts (d) silica filler (manufactured by Admatechs, SC-2050) 50 parts (e) copper ion scavenger (manufactured by Toagosei Co., Ltd., IXE-100) 10 copies

(Comparative Example 1)
The following (a) to (d) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) 5 parts (d) Silica filler (manufactured by Admatechs, SC-2050) 60 parts

(Comparative Example 2)
The following (a) to (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) 5 parts (d) silica filler (manufactured by Admatechs, SC-2050) 50 parts (e) chloride ion scavenger (manufactured by Toagosei Co., Ltd., IXE-550) ) 10 copies

(Comparative Example 3)
The following (a) to (e) were dissolved in methyl ethyl ketone to obtain an adhesive composition solution having a concentration of 20% by weight.
(A) Acrylic resin (manufactured by Nagase ChemteX Corporation, SG-708-6) 30 parts (b) Epoxy resin (manufactured by Toto Kasei Co., Ltd., YDF-8170C) 5 parts (c) Phenolic resin (Maywa Kasei) 5 parts (d) silica filler (manufactured by Admatechs, SC-2050) 50 parts (e) copper ion scavenger (manufactured by Toagosei Co., Ltd., IXE-100) 10 copies

(Evaluation of copper ion scavenging properties)
The adhesive composition solution according to Example 1 was applied on a release treatment film made of a polyethylene terephthalate film having a thickness of 50 μm after the silicone release treatment, and then dried at 130 ° C. for 2 minutes. Thereby, an adhesive sheet having a thickness of 20 μm was produced. In addition, the adhesive composition solutions according to Examples 2 to 8 and Comparative Examples 1 to 3 were coated on the release treatment film in the same manner as described above, and then dried at 130 ° C. for 2 minutes to obtain a thickness. An adhesive sheet having a thickness of 20 μm was produced. Each adhesive sheet (thickness 20 μm) was cut into a size of about 240 mm × 300 mm (about 2.5 g) and heated at 175 ° C. for 5 hours. After that, it was folded in half and made into a size of 37.5 mm × 60 mm in a cylindrical sealed Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm, and a 10 ppm copper (II) ion aqueous solution. 50 ml was added. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (Espec Co., Ltd. product, PV-231). After taking out the film, the concentration of copper ions in the aqueous solution was measured using ICP-AES (manufactured by SII Nanotechnology, Inc., SPS-1700HVR). The case where the concentration of the copper ion in the aqueous solution was 0 to 9.8 ppm was evaluated as ◯, and the case where it was higher than 9.8 ppm was evaluated as x. The results are shown in Table 1.

(Evaluation of chloride ion scavenging properties)
The adhesive composition solution according to Example 1 was applied on a release treatment film made of a polyethylene terephthalate film having a thickness of 50 μm after the silicone release treatment, and then dried at 130 ° C. for 2 minutes. Thereby, an adhesive sheet having a thickness of 20 μm was produced. In addition, the adhesive composition solutions according to Examples 2 to 8 and Comparative Examples 1 to 3 were coated on the release treatment film in the same manner as described above, and then dried at 130 ° C. for 2 minutes to obtain a thickness. An adhesive sheet having a thickness of 20 μm was produced. Each adhesive sheet (thickness 20 μm) was cut into a size of about 240 mm × 300 mm (about 2.5 g) and heated at 175 ° C. for 5 hours. Thereafter, the sample was folded in half and made into a size of 37.5 mm × 60 mm in a cylindrical sealed Teflon (registered trademark) container having a diameter of 58 mm and a height of 37 mm, and 50 ml of ion-exchanged water was added. Then, it was left to stand at 120 degreeC for 20 hours in the constant temperature dryer (Espec Co., Ltd. product, PV-231). After removing the film, the concentration of chloride ions in the aqueous solution was measured using ion chromatography (product name ICS-2000, manufactured by Tokyo Dionex). The case where the concentration of the chloride ion in the aqueous solution was 0.1 ppm or less was rated as ◯, and the case where it was larger than 0.1 ppm was rated as x. The results are shown in Table 1.

(result)
In the adhesive sheets of Examples 1 to 8, since the chloride ion concentration is low and copper ions can be captured, the semiconductor device manufactured using the adhesive sheet, that is, the semiconductor device having the adhesive sheet, Connection reliability can be improved as compared with the case where the adhesive sheet of the comparative example is used.

Claims (8)

An adhesive sheet for manufacturing a semiconductor device containing an ion scavenger,
The copper ion in the aqueous solution after immersing an adhesive sheet for manufacturing a semiconductor device having a weight of 2.5 g heated at 175 ° C. for 5 hours in 50 ml of an aqueous solution containing 10 ppm of copper ions and leaving at 120 ° C. for 20 hours. The concentration is from 0 to 9.9 ppm,
After immersing an adhesive sheet for manufacturing a semiconductor device weighing 2.5 g heated at 175 ° C. for 5 hours in 50 ml of ion-exchanged water and leaving it at 120 ° C. for 20 hours, the chloride ion concentration in the aqueous solution was: An adhesive sheet for manufacturing a semiconductor device, wherein the adhesive sheet is 0.1 ppm or less.   The adhesive sheet for manufacturing a semiconductor device according to claim 1, wherein the ion scavenger is a both ion scavenger.   3. The semiconductor device manufacture according to claim 1, wherein the addition amount of the both ion scavengers is 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin component constituting the adhesive sheet. Adhesive sheet.   The adhesive sheet for manufacturing a semiconductor device according to claim 1, wherein the ion scavenger is a mixture of a copper ion scavenger and a chloride ion scavenger.   The addition amount of the mixture of the copper ion scavenger and the chloride ion scavenger is 0.2 to 40 parts by weight with respect to 100 parts by weight of the resin component constituting the adhesive sheet. Item 5. An adhesive sheet for manufacturing a semiconductor device according to Item 4.   When the addition amount of the copper ion scavenger is A parts by weight and the addition amount of the chloride ion scavenger is B parts by weight, the mixing ratio of the copper ion scavenger and the chloride ion scavenger A / (A + B ) Is 0.13 to 0.99, The adhesive sheet for manufacturing a semiconductor device according to claim 4 or 5.   The adhesive sheet for manufacturing a semiconductor device according to claim 1, comprising an epoxy resin. A semiconductor device comprising the adhesive sheet for manufacturing a semiconductor device according to claim 1.