TW201510215A - Surface treatment method for substrate for semiconductor, production method for semiconductor package and water-soluble preflux used thereby - Google Patents
Surface treatment method for substrate for semiconductor, production method for semiconductor package and water-soluble preflux used thereby Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
- H01L2224/92—Specific sequence of method steps
- H01L2224/921—Connecting a surface with connectors of different types
- H01L2224/9212—Sequential connecting processes
- H01L2224/92122—Sequential connecting processes the first connecting process involving a bump connector
- H01L2224/92125—Sequential connecting processes the first connecting process involving a bump connector the second connecting process involving a layer connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/153—Connection portion
- H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
- H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
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Abstract
Description
本發明係關於一種半導體用基板之表面處理方法、半導體封裝之製造方法、及用於該等方法之水溶性預焊劑。 The present invention relates to a surface treatment method for a substrate for a semiconductor, a method for producing a semiconductor package, and a water-soluble preflux for use in the methods.
於半導體封裝用途之***式基板(根據情況,亦稱作半導體用基板)之電極墊,通常為防止電極墊之表面之氧化,而對電極墊之表面實施鍍金處理。然而,存在由於鍍金處理中使用貴金屬,故成本變高之問題。因此,於通常之印刷配線基板中,代替鍍金處理,採用藉由水溶性預焊劑於配線之表面形成保護覆膜之方法(例如文獻1:日本專利特開平6-322551號公報)。 In the electrode pad of the interposer substrate (also referred to as a substrate for a semiconductor) used for semiconductor packaging, the surface of the electrode pad is usually subjected to gold plating treatment to prevent oxidation of the surface of the electrode pad. However, there is a problem that the cost becomes high due to the use of precious metals in the gold plating process. Therefore, in the conventional printed wiring board, a method of forming a protective film on the surface of the wiring by a water-soluble pre-flux is used instead of the gold plating treatment (for example, Japanese Laid-Open Patent Publication No. Hei 6-322551).
於***式基板中,於如文獻1所記載之藉由水溶性預焊劑於電極墊之表面形成保護覆膜代替鍍金處理之情形時,存在如下所述之問題。即,於製作半導體封裝之情形時,將晶片接著於***式基板,然後進行密封。於此情形時,於***式基板之一面形成焊料凸塊,藉由該焊料凸塊而接著晶片。於接著晶片後,藉由焊劑清洗劑去除形成焊料凸塊時所產生之焊劑殘渣。此時,形成於***式基板之另一面(欲抑制電極墊之表面之氧化之面)之保護覆膜亦因焊劑清洗劑而被去除。其結果存在如下問題:即便藉由水溶性預焊劑於電極墊之表面形成保護覆膜,亦無法充分地抑制***式基板之電極墊之表面之氧化,電極墊之焊料潤濕性及接合強度降低。 In the case of the interposer substrate, when a protective film is formed on the surface of the electrode pad by a water-soluble pre-flux as described in Document 1, instead of the gold plating treatment, there is a problem as described below. That is, in the case of fabricating a semiconductor package, the wafer is attached to the interposer substrate and then sealed. In this case, a solder bump is formed on one surface of the interposer substrate, and the wafer is followed by the solder bump. After the wafer is subsequently removed, the flux residue generated when the solder bumps are formed is removed by the flux cleaning agent. At this time, the protective film formed on the other surface of the interposer substrate (the surface on which the surface of the electrode pad is to be oxidized) is also removed by the flux cleaning agent. As a result, there is a problem that even if a protective film is formed on the surface of the electrode pad by the water-soluble preflux, the oxidation of the surface of the electrode pad of the interposer substrate cannot be sufficiently suppressed, and the solder wettability and bonding strength of the electrode pad are lowered. .
因此,本發明之目的在於提供一種即便於形成保護覆膜後藉由焊劑清洗劑清洗半導體用基板之情形時,亦可充分地抑制電極墊之表面之氧化的半導體用基板之表面處理方法、半導體封裝之製造方法、及用於該等方法之水溶性預焊劑。 Therefore, an object of the present invention is to provide a surface treatment method for a semiconductor substrate and a semiconductor which can sufficiently suppress oxidation of the surface of the electrode pad even when the semiconductor substrate is cleaned by a flux cleaning agent after the protective film is formed. A method of making a package, and a water soluble preflux for use in such methods.
本發明者等人為達成上述目的而反覆努力研究,結果發現如下見解。即,發現:作為水溶性預焊劑之構成成分之咪唑系化合物眾多,但於如此多之咪唑系化合物中,使用含有具有特定之化學結構且具有鹵素原子之咪唑系化合物的水溶性預焊劑之情形時,令人驚訝的是,即便於形成保護覆膜後藉由焊劑清洗劑清洗半導體用基板之情形時,亦可充分地抑制電極墊之表面之氧化,從而完成本發明。 The present inventors have repeatedly tried their best to achieve the above object, and as a result, found the following findings. In other words, it has been found that a large amount of the imidazole-based compound which is a constituent component of the water-soluble preflux is used, and in the case of such an imidazole-based compound, a water-soluble preflux containing an imidazole compound having a specific chemical structure and having a halogen atom is used. In the case where the semiconductor substrate is cleaned by the flux cleaning agent after the protective film is formed, the oxidation of the surface of the electrode pad can be sufficiently suppressed, and the present invention has been completed.
即,本發明之半導體用基板之表面處理方法之特徵在於包括:水溶性預焊劑處理步驟,其係使用含有下述通式(1)所表示之化合物之水溶性預焊劑,而於半導體用基板之電極墊上形成保護覆膜;及焊劑清洗步驟,其係利用焊劑清洗劑清洗上述基板。 That is, the surface treatment method for a semiconductor substrate of the present invention includes a water-soluble preflux treatment step of using a water-soluble preflux containing a compound represented by the following formula (1) for a semiconductor substrate. A protective film is formed on the electrode pad; and a flux cleaning step is performed by cleaning the substrate with a flux cleaning agent.
(通式(1)中,X及Y分別可相同亦可不同,表示選自由碳數1~7之直鏈或支鏈烷基、鹵素原子、胺基、二低級烷胺基、羥基、低級烷氧基、氰基、乙醯基、苯甲醯基、胺甲醯基、甲醯基、羧基、低級烷氧基羰基及硝基所組成之群中之至少一種,n表示0~4之整數,m表示0~10之整數,p表示0~4之整數,且X及Y中之至少1個為鹵素原子, 該鹵素原子為氯原子、溴原子或碘原子) (In the formula (1), X and Y may be the same or different, and each represents a linear or branched alkyl group selected from a carbon number of 1 to 7, a halogen atom, an amine group, a di-lower alkylamino group, a hydroxyl group, and a lower stage. At least one of a group consisting of an alkoxy group, a cyano group, an ethyl fluorenyl group, a benzamyl group, an amine carbaryl group, a decyl group, a carboxyl group, a lower alkoxycarbonyl group, and a nitro group, and n represents a group of 0 to 4 An integer, m represents an integer from 0 to 10, p represents an integer from 0 to 4, and at least one of X and Y is a halogen atom. The halogen atom is a chlorine atom, a bromine atom or an iodine atom)
於本發明之半導體用基板之表面處理方法中,較佳為上述通式(1)中之X及Y中之1個或2個為鹵素原子。 In the surface treatment method of the substrate for a semiconductor of the present invention, it is preferred that one or two of X and Y in the above formula (1) are halogen atoms.
於本發明之半導體用基板之表面處理方法中,較佳為上述通式(1)中之Y中之至少1個為鹵素原子。 In the surface treatment method of the substrate for a semiconductor of the present invention, at least one of Y in the above formula (1) is preferably a halogen atom.
於本發明之半導體用基板之表面處理方法中,較佳為上述通式(1)中之X及Y之鹵素原子為氯原子。 In the surface treatment method of the substrate for a semiconductor of the present invention, it is preferred that the halogen atom of X and Y in the above formula (1) is a chlorine atom.
本發明之半導體封裝之製造方法之特徵在於包括:水溶性預焊劑處理步驟,其係使用含有上述通式(1)所表示之化合物之水溶性預焊劑,而於半導體用基板之電極墊上形成保護覆膜;焊料凸塊形成步驟,其係將焊膏塗佈於上述基板之一面之電極墊上,進行回焊處理而形成焊料凸塊;晶片接著步驟,其係於焊料凸塊上配置晶片,進行回焊處理而將上述晶片接著於上述基板;及焊劑清洗步驟,其係利用焊劑清洗劑清洗上述基板。 The method for producing a semiconductor package of the present invention includes a water-soluble preflux treatment step of forming a protective layer on a semiconductor pad of a semiconductor substrate by using a water-soluble preflux containing a compound represented by the above formula (1). a solder bump forming step of applying a solder paste on an electrode pad on one surface of the substrate to perform a solder reflow process to form a solder bump; the wafer is followed by a step of arranging a wafer on the solder bump The wafer is subsequently soldered to the substrate; and a flux cleaning step is performed by cleaning the substrate with a flux cleaning agent.
本發明之水溶性預焊劑之特徵在於:其係用於半導體用基板之表面處理方法或半導體封裝之製造方法者,且含有上述通式(1)所表示之化合物。 The water-soluble preflux of the present invention is characterized in that it is used for a surface treatment method for a semiconductor substrate or a method for producing a semiconductor package, and contains a compound represented by the above formula (1).
根據本發明,可提供一種即便於形成保護覆膜後藉由焊劑清洗劑清洗半導體用基板之情形時,亦可充分地抑制電極墊之表面之氧化的半導體用基板之表面處理方法、半導體封裝之製造方法、及用於該等方法之水溶性預焊劑。 According to the present invention, it is possible to provide a surface treatment method for a semiconductor substrate and a semiconductor package which can sufficiently suppress oxidation of the surface of the electrode pad even when the semiconductor substrate is cleaned by a flux cleaning agent after forming the protective film. Manufacturing methods, and water soluble prefluxes for use in such methods.
1‧‧‧半導體用基板 1‧‧‧Semiconductor substrate
2‧‧‧焊料凸塊 2‧‧‧ solder bumps
3‧‧‧晶片 3‧‧‧ wafer
4‧‧‧底膠填充劑 4‧‧‧Bottom adhesive
5‧‧‧模塑劑 5‧‧‧ molding agent
6‧‧‧焊料球 6‧‧‧ solder balls
11A‧‧‧電極墊 11A‧‧‧electrode pad
11B‧‧‧電極墊 11B‧‧‧electrode pad
圖1A係用於說明本發明之半導體封裝之製造方法之說明圖。 Fig. 1A is an explanatory view for explaining a method of manufacturing a semiconductor package of the present invention.
圖1B係用於說明本發明之半導體封裝之製造方法之說明圖。 Fig. 1B is an explanatory view for explaining a method of manufacturing a semiconductor package of the present invention.
圖1C係用於說明本發明之半導體封裝之製造方法之說明圖。 Fig. 1C is an explanatory view for explaining a method of manufacturing a semiconductor package of the present invention.
圖1D係用於說明本發明之半導體封裝之製造方法之說明圖。 Fig. 1D is an explanatory view for explaining a method of manufacturing the semiconductor package of the present invention.
圖1E係用於說明本發明之半導體封裝之製造方法之說明圖。 Fig. 1E is an explanatory view for explaining a method of manufacturing the semiconductor package of the present invention.
圖1F係用於說明本發明之半導體封裝之製造方法之說明圖。 Fig. 1F is an explanatory view for explaining a method of manufacturing the semiconductor package of the present invention.
本發明之半導體用基板之表面處理方法為如下方法:其包括:水溶性預焊劑處理步驟,其係使用以下說明之水溶性預焊劑,而於半導體用基板之電極墊上形成保護覆膜;及焊劑清洗步驟,其係利用焊劑清洗劑清洗上述基板。 The surface treatment method for a semiconductor substrate of the present invention is a method comprising: a water-soluble preflux treatment step of forming a protective film on an electrode pad of a semiconductor substrate using a water-soluble preflux described below; and a flux A cleaning step of cleaning the substrate with a flux cleaning agent.
又,本發明之半導體封裝之製造方法為如下方法:其包括:水溶性預焊劑處理步驟,其係使用以下說明之水溶性預焊劑,而於半導體用基板之電極墊上形成保護覆膜;焊料凸塊形成步驟,其係將焊膏塗佈於上述基板之一面之電極墊上,進行回焊處理而形成焊料凸塊;晶片接著步驟,其係於焊料凸塊上配置晶片,進行回焊處理而將上述晶片接著於上述基板;及焊劑清洗步驟,其係利用焊劑清洗劑清洗上述基板。 Moreover, the method of manufacturing a semiconductor package of the present invention is a method comprising: a water-soluble preflux treatment step of forming a protective film on an electrode pad of a substrate for a semiconductor using a water-soluble preflux described below; a block forming step of applying a solder paste on an electrode pad on one surface of the substrate and performing a reflow process to form a solder bump; and the wafer is followed by a step of arranging the wafer on the solder bump and performing a reflow process The wafer is followed by the substrate; and a flux cleaning step of cleaning the substrate with a flux cleaning agent.
首先,對用於本發明之半導體用基板之表面處理方法或半導體封裝之製造方法的本發明之水溶性預焊劑進行說明。 First, the water-soluble preflux of the present invention used in the surface treatment method for a semiconductor substrate or the method for producing a semiconductor package of the present invention will be described.
本發明之水溶性預焊劑係含有下述通式(1)所表示之化合物者。 The water-soluble preflux of the present invention contains a compound represented by the following formula (1).
於上述通式(1)中,X及Y分別可相同亦可不同,表示選自由碳數1~7之直鏈或支鏈烷基、鹵素原子、胺基、二低級烷胺基、羥基、低級烷氧基、氰基、乙醯基、苯甲醯基、胺甲醯基、甲醯基、羧基、低級烷氧基羰基及硝基所組成之群中之至少一種。又,n表示0~4之整 數,m表示0~10之整數,p表示0~4之整數。 In the above formula (1), X and Y may be the same or different and each represents a linear or branched alkyl group selected from a carbon number of 1 to 7, a halogen atom, an amine group, a di-lower alkylamino group, a hydroxyl group, At least one of a group consisting of a lower alkoxy group, a cyano group, an ethyl fluorenyl group, a benzamidine group, an amine carbaryl group, a decyl group, a carboxyl group, a lower alkoxycarbonyl group, and a nitro group. Also, n represents the whole of 0~4 The number, m represents an integer from 0 to 10, and p represents an integer from 0 to 4.
並且,於本發明中,必須X及Y中之至少1個為鹵素原子,且該鹵素原子為氯原子、溴原子或碘原子。於X及Y中不存在該等鹵素原子之情形時,保護覆膜對焊劑清洗液之耐性不充分,無法抑制電極墊之表面之氧化。又,就電極墊之焊料潤濕性之觀點而言,鹵素原子更佳為氯原子。 Further, in the present invention, at least one of X and Y is required to be a halogen atom, and the halogen atom is a chlorine atom, a bromine atom or an iodine atom. When such a halogen atom is not present in X and Y, the protective film is insufficient in resistance to the flux cleaning liquid, and oxidation of the surface of the electrode pad cannot be suppressed. Further, from the viewpoint of solder wettability of the electrode pad, the halogen atom is more preferably a chlorine atom.
於上述通式(1)中,較佳為X及Y中之1個或2個為鹵素原子。於X及Y中之3個以上為鹵素原子之情形時,有化合物之溶解性降低之傾向,且有水溶性預焊劑之穩定性降低之傾向。 In the above formula (1), one or two of X and Y are preferably a halogen atom. When three or more of X and Y are halogen atoms, the solubility of the compound tends to decrease, and the stability of the water-soluble preflux tends to decrease.
又,於上述通式(1)中,較佳為Y中之至少1個為鹵素原子。於上述通式(1)中之Y中存在鹵素原子之情況下,有電極墊之焊料潤濕性提昇之傾向。 Further, in the above formula (1), at least one of Y is preferably a halogen atom. In the case where a halogen atom is present in Y in the above formula (1), the solder wettability of the electrode pad tends to increase.
作為上述通式(1)所表示之化合物,可列舉2-(3-氯苄基)苯并咪唑、2-(3,4-二氯苄基)苯并咪唑、4-氯-2-(3-苯基丙基)苯并咪唑、6-氯-2-{(2-硝基苯基)乙基}苯并咪唑及6-乙氧羰基-2-(3-溴苄基)苯并咪唑等。就抑制電極墊之表面之氧化之觀點而言,於該等中,更佳為2-(3-氯苄基)苯并咪唑、2-(3,4-二氯苄基)苯并咪唑、4-氯-2-(3-苯基丙基)苯并咪唑。 Examples of the compound represented by the above formula (1) include 2-(3-chlorobenzyl)benzimidazole, 2-(3,4-dichlorobenzyl)benzimidazole, and 4-chloro-2-( 3-phenylpropyl)benzimidazole, 6-chloro-2-{(2-nitrophenyl)ethyl}benzimidazole and 6-ethoxycarbonyl-2-(3-bromobenzyl)benzo Imidazole and the like. From the viewpoint of suppressing oxidation of the surface of the electrode pad, among these, 2-(3-chlorobenzyl)benzimidazole and 2-(3,4-dichlorobenzyl)benzimidazole are more preferable. 4-Chloro-2-(3-phenylpropyl)benzimidazole.
相對於上述水溶性預焊劑100質量%,上述通式(1)所表示之化合物之含量較佳為0.01質量%以上且10質量%以下,更佳為0.05質量%以上且5質量%以下。藉由使含量為上述下限以上,而易於形成防銹膜等塗膜。又,若含量超過上述上限,則有不溶成分容易變多之傾向,經濟上亦不佳。 The content of the compound represented by the above formula (1) is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less based on 100% by mass of the water-soluble pre-flux. When the content is at least the above lower limit, a coating film such as a rust preventive film can be easily formed. Moreover, when the content exceeds the above upper limit, the insoluble component tends to increase, and it is economically unfavorable.
於上述水溶性預焊劑中,由於上述通式(1)所表示之化合物對中性之水為難溶性,故較佳為使用有機酸或水溶性有機溶劑而使之水溶化。上述有機酸及上述有機溶劑可分別單獨使用,亦可併用。再者, 於上述水溶性預焊劑中,上述通式(1)所表示之化合物或以下說明之其他成分以外之剩餘部分為水。 In the water-soluble pre-flux, the compound represented by the above formula (1) is poorly soluble in neutral water, and therefore it is preferred to use an organic acid or a water-soluble organic solvent to dissolve the water. The above organic acid and the above organic solvent may be used singly or in combination. Furthermore, In the water-soluble preflux, the remainder of the compound represented by the above formula (1) or other components described below is water.
作為上述有機酸,可列舉甲酸、乙酸、丙酸、丁酸、乙醇酸、酒石酸、乳酸、氯乙酸、二氯乙酸、三氯乙酸、溴乙酸及甲氧基乙酸等。於該等中,較佳為使用甲酸、乙酸。又,該等有機酸可單獨使用1種,亦可混合2種以上而使用。 Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, tartaric acid, lactic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, and methoxyacetic acid. Among these, formic acid and acetic acid are preferably used. Further, these organic acids may be used singly or in combination of two or more.
相對於上述水溶性預焊劑100質量%,上述有機酸之含量較佳為1質量%以上且40質量%以下。 The content of the organic acid is preferably 1% by mass or more and 40% by mass or less based on 100% by mass of the water-soluble preflux.
作為上述有機溶劑,可列舉甲醇、乙醇及丙酮等。該等有機溶劑可單獨使用1種,亦可混合2種以上而使用。 Examples of the organic solvent include methanol, ethanol, acetone, and the like. These organic solvents may be used alone or in combination of two or more.
相對於上述水溶性預焊劑100質量%,上述有機溶劑之含量較佳為1質量%以上且40質量%以下。 The content of the organic solvent is preferably 1% by mass or more and 40% by mass or less based on 100% by mass of the water-soluble preflux.
上述水溶性預焊劑亦可進而含有與銅之錯合物覆膜形成助劑。但是,由於若添加與銅之錯合物覆膜形成助劑,則根據條件不同而有於基板之鍍金上亦形成覆膜而產生鍍金之變色之情況,故需要注意。 The water-soluble preflux may further contain a complexing agent for forming a film with copper. However, when a complexing agent for forming a film with copper is added, depending on the conditions, a film is formed on the gold plating of the substrate to cause discoloration of gold plating, and care is required.
作為上述錯合物覆膜形成助劑,可列舉甲酸銅、氯化亞銅、氯化銅、草酸銅、乙酸銅、氫氧化銅、碳酸銅、磷酸銅、硫酸銅、甲酸錳、氯化錳、草酸錳、硫酸錳、乙酸鋅、乙酸鉛、乙酸鎳、乙酸鋇、氫化鋅、氯化亞鐵、氯化鐵、氧化亞鐵、氧化鐵、碘化銅、溴化亞銅及溴化銅等金屬化合物。該等錯合物覆膜形成助劑可單獨使用1種,亦可混合2種以上而使用。 Examples of the complex coating film forming aid include copper formate, cuprous chloride, copper chloride, copper oxalate, copper acetate, copper hydroxide, copper carbonate, copper phosphate, copper sulfate, manganese formate, and manganese chloride. Manganese oxalate, manganese sulfate, zinc acetate, lead acetate, nickel acetate, barium acetate, zinc hydride, ferrous chloride, ferric chloride, ferrous oxide, iron oxide, copper iodide, cuprous bromide and copper bromide And other metal compounds. These complex film forming aids may be used singly or in combination of two or more.
相對於上述水溶性預焊劑100質量%,上述錯合物覆膜形成助劑之含量較佳為0.01質量%以上且10質量%以下,更佳為0.05質量%以上且5質量%以下。 The content of the complex film forming aid is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less based on 100% by mass of the water-soluble pre-flux.
於上述水溶性預焊劑中,亦可進而併用含有對於自上述金屬化合物分離之金屬離子之鹼的緩衝液。 In the above water-soluble preflux, a buffer containing a base for a metal ion separated from the above metal compound may be used in combination.
作為上述緩衝液中之鹼,可列舉氨、二乙胺、三乙胺、二乙醇胺、三乙醇胺、單乙醇胺、二甲基乙醇胺、二乙基乙醇胺、異丙基乙醇胺、氫氧化鈉及氫氧化鉀等。 Examples of the base in the above buffer include ammonia, diethylamine, triethylamine, diethanolamine, triethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, isopropylethanolamine, sodium hydroxide, and hydroxide. Potassium and so on.
就提昇焊接特性之觀點而言,上述水溶性預焊劑亦可進而含有鹵素化合物。 The water-soluble preflux may further contain a halogen compound from the viewpoint of improving soldering properties.
作為上述鹵素化合物,可列舉碘化鉀、溴化鉀、碘化鋅、溴化鋅、溴丙酸及碘丙酸等。該等鹵素化合物可單獨使用1種,亦可混合2種以上而使用。 Examples of the halogen compound include potassium iodide, potassium bromide, zinc iodide, zinc bromide, bromopropionic acid, and iodopropionic acid. These halogen compounds may be used alone or in combination of two or more.
相對於上述水溶性預焊劑100質量%,上述鹵素化合物之含量較佳為0.01質量%以上且10質量%以下,更佳為0.05質量%以上且5質量%以下。 The content of the halogen compound is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less based on 100% by mass of the water-soluble preflux.
其次,對本發明之半導體用基板之表面處理方法及半導體封裝之製造方法進行說明。 Next, a surface treatment method of a semiconductor substrate and a method of manufacturing a semiconductor package of the present invention will be described.
本發明之半導體用基板之表面處理方法係包括水溶性預焊劑處理步驟及焊劑清洗步驟之方法。 The surface treatment method of the substrate for a semiconductor of the present invention includes a water-soluble preflux treatment step and a flux cleaning step.
本發明之半導體封裝之製造方法係包括水溶性預焊劑處理步驟、焊料凸塊形成步驟、晶片接著步驟及焊劑清洗步驟之方法。 The method of fabricating the semiconductor package of the present invention includes a water-soluble preflux processing step, a solder bump forming step, a wafer subsequent step, and a flux cleaning step.
再者,於此處舉出本發明之半導體封裝之製造方法之一實施形態為例,並基於圖式進行說明。圖1A~圖1F係用於說明本發明之半導體封裝之製造方法之圖。再者,以下說明者為半導體封裝之製造方法之一實施形態,本發明之半導體用基板之表面處理方法或本發明之半導體封裝之製造方法並不限定於此。 In addition, an embodiment of a method of manufacturing a semiconductor package of the present invention will be described as an example and will be described based on the drawings. 1A to 1F are views for explaining a method of manufacturing a semiconductor package of the present invention. In addition, the following description is an embodiment of a method of manufacturing a semiconductor package, and the surface treatment method of the semiconductor substrate of the present invention or the method of manufacturing the semiconductor package of the present invention is not limited thereto.
上述實施形態係依序進行(i)水溶性預焊劑處理步驟、(ii)焊料凸塊形成步驟、(iii)第一焊劑清洗步驟、(iv)晶片接著步驟、(v)第二焊劑清洗步驟、(vi)底膠填充步驟、(vii)模塑步驟及(viii)焊料球形成步 驟之方法。 The above embodiment is sequentially performed (i) a water-soluble preflux treatment step, (ii) a solder bump forming step, (iii) a first flux cleaning step, (iv) a wafer subsequent step, and (v) a second flux cleaning step. , (vi) a primer filling step, (vii) a molding step, and (viii) a solder ball forming step The method of the sudden.
於上述(i)水溶性預焊劑處理步驟中,如圖1A所示,於半導體用基板1之電極墊11A、11B上形成保護覆膜。 In the above (i) water-soluble preflux treatment step, as shown in FIG. 1A, a protective film is formed on the electrode pads 11A and 11B of the semiconductor substrate 1.
作為保護覆膜之形成方法,例如可採用如下方法:於實施對處理對象之半導體用基板1之電極墊11A、11B之表面進行脫脂、化學研磨(軟蝕刻)、酸洗、水洗的預處理步驟之後,於10~60℃下將半導體用基板1浸漬於上述水溶性預焊劑1秒鐘~100分鐘(較佳為於20~50℃下浸漬5秒鐘~60分鐘,更佳為於20~50℃下浸漬10秒鐘~10分鐘)。如此,上述通式(1)所表示之化合物附著於電極墊之表面,但越提高處理溫度、越延長處理時間,其附著量越多。此時,若使用超音波則更佳。再者,亦可利用其他塗佈方法、例如噴霧法、毛刷塗裝、輥塗等形成保護覆膜。藉由如此所得之保護覆膜,可抑制電極墊之表面經高溫加熱而劣化。因此,即便電極墊之表面暴露於高溫,亦可維持充分之焊料潤濕性。 As a method of forming the protective film, for example, a pretreatment step of performing degreasing, chemical polishing (soft etching), pickling, and water washing on the surfaces of the electrode pads 11A and 11B of the semiconductor substrate 1 to be processed may be employed. Thereafter, the semiconductor substrate 1 is immersed in the water-soluble preflux at 10 to 60 ° C for 1 second to 100 minutes (preferably at 20 to 50 ° C for 5 seconds to 60 minutes, more preferably 20 seconds). Immerse at 50 ° C for 10 seconds to 10 minutes). As described above, the compound represented by the above formula (1) adheres to the surface of the electrode pad, but the higher the treatment temperature and the longer the treatment time, the greater the amount of adhesion. In this case, it is better to use ultrasonic waves. Further, the protective film may be formed by another coating method such as a spray method, brush coating, roll coating, or the like. By the protective film thus obtained, the surface of the electrode pad can be suppressed from being deteriorated by heating at a high temperature. Therefore, even if the surface of the electrode pad is exposed to a high temperature, sufficient solder wettability can be maintained.
於上述(ii)焊料凸塊形成步驟中,如圖1B所示,將焊膏塗佈於形成保護覆膜後之基板1之一面之電極墊11A上,進行回焊處理而形成焊料凸塊2。 In the above (ii) solder bump forming step, as shown in FIG. 1B, solder paste is applied onto the electrode pad 11A on one side of the substrate 1 on which the protective film is formed, and solder reflow processing is performed to form the solder bump 2 .
作為焊膏之塗佈方法,可適當採用使用有金屬掩模印刷機之方法等公知之方法。 As a method of applying the solder paste, a known method such as a method using a metal mask printer can be suitably employed.
作為回焊處理之條件,可根據焊料凸塊2之焊料合金組成而適當設定。例如於使用含有錫、銀及銅之無鉛焊料合金(SAC(Sn-Ag-Cu)系)之焊膏之情形時,將150~180℃之預熱溫度設為90秒鐘,將波峰溫度設為240℃,並將200℃以上之保持時間設為60秒鐘即可,但並無特別限定。 The conditions for the reflow process can be appropriately set according to the solder alloy composition of the solder bumps 2. For example, when using a solder paste containing a lead-free solder alloy of tin, silver, and copper (SAC (Sn-Ag-Cu) system), the preheating temperature of 150 to 180 ° C is set to 90 seconds, and the peak temperature is set. The temperature is 240 ° C, and the holding time of 200 ° C or more is 60 seconds, but it is not particularly limited.
於上述(iii)第一焊劑清洗步驟中,利用焊劑清洗劑清洗半導體用基板1。半導體用基板1必須藉由焊劑清洗劑去除形成焊料凸塊2時所 產生之焊劑殘渣。為此,需要該第一焊劑清洗步驟。 In the above (iii) first flux cleaning step, the semiconductor substrate 1 is cleaned with a flux cleaning agent. The substrate 1 for semiconductor must be removed by solder cleaning agent to form solder bumps 2 The resulting flux residue. To this end, the first flux cleaning step is required.
作為焊劑清洗劑,可使用公知之焊劑清洗劑(較佳為水系焊劑清洗劑)。作為該焊劑清洗劑,可列舉花王公司製造之CLEANTHROUGH 750HS、CLEANTHROUGH 750K及荒川化學工業公司製造之PINEALPHA ST-100S等。 As the flux cleaning agent, a known flux cleaning agent (preferably a water-based flux cleaning agent) can be used. Examples of the flux cleaning agent include CLEANTHROUGH 750HS, CLEANTHROUGH 750K manufactured by Kao Corporation, and PINELAPHA ST-100S manufactured by Arakawa Chemical Industries Co., Ltd.
清洗半導體用基板時之清洗條件並無特別限定。例如,於清洗劑溫度30~50℃下,將半導體用基板清洗1~5分鐘(較佳為於40℃下清洗3分鐘)即可。 The cleaning conditions in the case of cleaning the substrate for a semiconductor are not particularly limited. For example, the semiconductor substrate may be washed at a cleaning agent temperature of 30 to 50 ° C for 1 to 5 minutes (preferably at 40 ° C for 3 minutes).
於上述(iv)晶片接著步驟中,如圖1C所示,於形成焊料凸塊2後之基板1之焊料凸塊2上配置晶片3,進行回焊處理而將晶片3接著於基板1。 In the subsequent step of the above (iv) wafer, as shown in FIG. 1C, the wafer 3 is placed on the solder bumps 2 of the substrate 1 after the solder bumps 2 are formed, and the wafer 3 is bonded to the substrate 1 by reflow processing.
作為回焊處理之條件,可根據焊料凸塊2之焊料合金組成而適當設定。 The conditions for the reflow process can be appropriately set according to the solder alloy composition of the solder bumps 2.
於上述(v)第二焊劑清洗步驟中,利用焊劑清洗劑再次清洗接著晶片3後之基板1。 In the above (v) second flux cleaning step, the substrate 1 following the wafer 3 is again cleaned with a flux cleaning agent.
作為焊劑清洗劑或清洗條件,可採用與上述第一焊劑清洗劑相同者或相同之清洗條件。 As the flux cleaning agent or cleaning conditions, the same or the same cleaning conditions as the above-described first flux cleaning agent can be employed.
於上述(vi)底膠填充步驟中,如圖1D所示,於清洗焊劑後之基板1上之基板1與晶片3之間隙填充底膠填充劑4。 In the above (vi) primer filling step, as shown in FIG. 1D, the gap between the substrate 1 and the wafer 3 on the substrate 1 after the cleaning of the solder is filled with the underfill filler 4.
作為底膠填充劑4,可適當使用公知之底膠填充劑材料。 As the primer filler 4, a known primer filler material can be suitably used.
作為底膠填充劑4之硬化條件,可根據底膠填充劑材料之種類而適當設定。例如,以溫度120~180℃加熱1~3小時即可。 The curing conditions of the underfill filler 4 can be appropriately set depending on the type of the underfill filler material. For example, it can be heated at a temperature of 120 to 180 ° C for 1 to 3 hours.
再者,於填充底膠填充劑4之前,較佳為以溫度100~150℃實施1~3小時之預加熱處理。 Further, before the underfill filler 4 is filled, it is preferred to carry out a preheating treatment at a temperature of 100 to 150 ° C for 1 to 3 hours.
於上述(vii)模塑步驟中,如圖1E所示,利用模塑劑5密封填充底膠填充劑4後之基板1上之晶片3。 In the above (vii) molding step, as shown in Fig. 1E, the wafer 3 on the substrate 1 after the underfill filler 4 is sealed by the molding agent 5.
作為模塑劑5,可適當使用公知之模塑劑材料。 As the molding agent 5, a known molding agent material can be suitably used.
作為模塑劑5之硬化條件,可根據模塑劑材料之種類而適當設定。例如,以溫度150~200℃加熱2~6小時(較佳為以170~180℃加熱3~5小時)即可。 The curing conditions of the molding agent 5 can be appropriately set depending on the kind of the molding material. For example, it can be heated at a temperature of 150 to 200 ° C for 2 to 6 hours (preferably, heating at 170 to 180 ° C for 3 to 5 hours).
於上述(viii)焊料球形成步驟中,如圖1F所示,於利用模塑劑5密封後之基板1之電極墊11B上配置焊料球,進行回焊處理而形成焊料球6。 In the above (viii) solder ball forming step, as shown in FIG. 1F, a solder ball is placed on the electrode pad 11B of the substrate 1 sealed by the molding agent 5, and a solder ball is subjected to a reflow process to form the solder ball 6.
作為焊料球之配置方法,可適當採用公知之焊料球之搭載方法。又,亦可使用焊膏形成焊料球。於此情形時,作為焊膏之塗佈方法,可適當採用使用有金屬掩模印刷機之方法等公知之方法。 As a method of arranging the solder balls, a known method of mounting solder balls can be suitably employed. Further, solder balls may be formed using solder paste. In this case, as a method of applying the solder paste, a known method such as a method using a metal mask printer can be suitably employed.
作為回焊處理之條件,可根據焊料球6之焊料合金組成而適當設定。 The conditions for the reflow treatment can be appropriately set depending on the solder alloy composition of the solder balls 6.
於本發明之半導體封裝之製造方法中,如上所述,由於在上述水溶性預焊劑處理步驟之後,進行上述第一及第二焊劑清洗步驟,故基板1之電極墊11B上之保護覆膜會被焊劑清洗劑清洗。又,由於自上述焊劑清洗步驟起至上述焊料球形成步驟之前進行上述模塑步驟等之加熱,故電極墊11B之表面長時間暴露於高溫。即便於如上所述電極墊11B之表面易於劣化之情況下,根據本發明,亦可充分地抑制電極墊之表面之氧化。 In the method of manufacturing a semiconductor package of the present invention, as described above, since the first and second flux cleaning steps are performed after the water-soluble preflux treatment step, the protective film on the electrode pad 11B of the substrate 1 is It is cleaned by flux cleaner. Moreover, since the heating of the above-described molding step or the like is performed from the above-described flux cleaning step to the above-described solder ball forming step, the surface of the electrode pad 11B is exposed to a high temperature for a long period of time. That is, in the case where the surface of the electrode pad 11B is easily deteriorated as described above, according to the present invention, the oxidation of the surface of the electrode pad can be sufficiently suppressed.
其次,藉由實施例及比較例進而詳細地說明本發明,但本發明並不受該等例子任何限定。再者,將實施例及比較例中使用之材料示於以下。 Next, the present invention will be described in detail by way of examples and comparative examples, but the invention is not limited by the examples. Further, the materials used in the examples and comparative examples are shown below.
咪唑系化合物A:2-(3-氯苄基)苯并咪唑 Imidazole compound A: 2-(3-chlorobenzyl)benzimidazole
咪唑系化合物B:2-(3,4-二氯苄基)苯并咪唑 Imidazole compound B: 2-(3,4-dichlorobenzyl)benzimidazole
咪唑系化合物C:4-氯-2-(3-苯基丙基)苯并咪唑 Imidazole compound C: 4-chloro-2-(3-phenylpropyl)benzimidazole
咪唑系化合物D:6-氯-2-{(2-硝基苯基)乙基}苯并咪唑 Imidazole compound D: 6-chloro-2-{(2-nitrophenyl)ethyl}benzimidazole
咪唑系化合物E:6-乙氧羰基-2-(3-溴苄基)苯并咪唑 Imidazole compound E: 6-ethoxycarbonyl-2-(3-bromobenzyl)benzimidazole
咪唑系化合物F:4-甲基-2-十一烷基咪唑 Imidazole compound F: 4-methyl-2-undecylimidazole
咪唑系化合物G:4,5-二乙基-2-己基苯并咪唑 Imidazole compound G: 4,5-diethyl-2-hexylbenzimidazole
咪唑系化合物H:2-辛基苯并咪唑 Imidazole compound H: 2-octylbenzimidazole
有機酸A:乙酸 Organic Acid A: Acetic Acid
有機酸B:酒石酸 Organic Acid B: Tartaric Acid
有機酸C:甲酸 Organic acid C: formic acid
有機溶劑:乙醇 Organic solvent: ethanol
錯合物覆膜形成助劑A:氯化鋅 Complex film forming aid A: zinc chloride
錯合物覆膜形成助劑B:乙酸鋅 Complex film forming aid B: zinc acetate
錯合物覆膜形成助劑C:乙酸鎳 Complex film forming aid C: nickel acetate
錯合物覆膜形成助劑D:乙酸鋇 Complex film forming aid D: barium acetate
錯合物覆膜形成助劑E:甲酸錳 Complex composition forming agent E: manganese formate
水:純水 Water: pure water
使0.1質量%之咪唑系化合物A、0.1質量%之有機酸A及0.5質量%之錯合物覆膜形成助劑A溶解於99.3質量%之水,而獲得水溶性預焊劑。再者,所得之水溶性預焊劑係以作為緩衝液之25質量%氨水進行pH值調整,而製成可形成覆膜之處理液。 0.1% by mass of the imidazole-based compound A, 0.1% by mass of the organic acid A, and 0.5% by mass of the complex film-forming aid A were dissolved in 99.3% by mass of water to obtain a water-soluble preflux. Further, the obtained water-soluble preflux was subjected to pH adjustment by using 25 mass% aqueous ammonia as a buffer to prepare a treatment liquid capable of forming a coating.
除按照表1所示之組成而調配各材料以外,與實施例1同樣地獲得水溶性預焊劑。 A water-soluble preflux was obtained in the same manner as in Example 1 except that the materials were blended in accordance with the compositions shown in Table 1.
除按照表2所示之組成而調配各材料以外,與實施例1同樣地獲得水溶性預焊劑。 A water-soluble preflux was obtained in the same manner as in Example 1 except that each material was blended in accordance with the composition shown in Table 2.
除按照表3所示之組成而調配各材料以外,與實施例1同樣地獲得水溶性預焊劑。 A water-soluble preflux was obtained in the same manner as in Example 1 except that each material was blended in accordance with the composition shown in Table 3.
<利用水溶性預焊劑形成之保護覆膜之評價> <Evaluation of Protective Film Formed with Water-Soluble Preflux>
利用如下所述之方法對利用水溶性預焊劑形成之保護覆膜之性能(清洗後之覆膜殘留率、焊料球之接合強度、焊料潤濕時間、焊料擴散率)進行評價或測定。將所得之結果示於表1~表3。 The properties (coating residual ratio after cleaning, bonding strength of solder balls, solder wet time, solder diffusion ratio) after the protective film formed using the water-soluble preflux were evaluated or measured by the method described below. The results obtained are shown in Tables 1 to 3.
(1)清洗後之覆膜殘留率 (1) Residual film retention rate after cleaning
對雙面覆銅積層板(大小:50mm×50mm、厚度:1.6mm、FR-4基材)進行脫脂、軟蝕刻、水洗而清潔表面。然後,於40℃下浸漬於所得之水溶性預焊劑2分鐘,於銅箔表面形成覆膜,並進行水洗、溫風乾燥而獲得試驗基板。 The double-sided copper-clad laminate (size: 50 mm × 50 mm, thickness: 1.6 mm, FR-4 substrate) was degreased, soft-etched, and washed with water to clean the surface. Then, the obtained water-soluble preflux was immersed at 40 ° C for 2 minutes to form a film on the surface of the copper foil, and washed with water and air-dried to obtain a test substrate.
於下述回焊條件下對所得之試驗基板進行2次回焊處理,然後,使用焊劑清洗劑(花王公司製造之「CLEANTHROUGH 750HS」)於下述焊劑清洗條件下進行清洗處理,獲得清洗處理後之試驗基板。 The obtained test substrate was subjected to a reflow treatment twice under the following reflow conditions, and then a flux cleaning agent ("CLEANTHROUGH 750HS" manufactured by Kao Corporation) was used for cleaning under the following flux cleaning conditions to obtain a cleaning treatment. Test the substrate.
關於清洗處理前後之試驗基板,將表面積25cm2之試驗基板上之覆膜萃取於0.5%鹽酸50mL中後,測定由萃取液中之覆膜有效成分產生之極大吸光度。並且,算出清洗處理後之試驗基板之吸光度(A1)相對於清洗處理前之試驗基板之吸光度(A0)的比率(A1/A0×100),作為清洗後之覆膜殘留率(單位:%)。 With respect to the test substrate before and after the cleaning treatment, the film on the test substrate having a surface area of 25 cm 2 was extracted into 50 mL of 0.5% hydrochloric acid, and the maximum absorbance generated by the active ingredient of the film in the extract was measured. Then, the ratio (A 1 /A 0 ×100) of the absorbance (A 1 ) of the test substrate after the cleaning treatment to the absorbance (A 0 ) of the test substrate before the cleaning treatment was calculated as the residual ratio of the coating after washing ( unit:%).
(回焊條件) (reflow condition)
氧濃度:2000ppm以下 Oxygen concentration: 2000ppm or less
預熱:以150~180℃進行80秒鐘 Preheating: 80 seconds at 150~180°C
波峰溫度:240℃(200℃以上之時間為60秒鐘) Peak temperature: 240 ° C (60 seconds above 200 ° C)
(焊劑清洗條件) (flux cleaning conditions)
清洗液溫度:40℃ Cleaning solution temperature: 40 ° C
清洗時間:3分鐘 Cleaning time: 3 minutes
其他:有浸漬搖動及超音波 Other: immersion shaking and ultrasonic
(2)焊料球之接合強度 (2) Bond strength of solder balls
除使用雙面覆銅積層板(大小:30mm×30mm、厚度:1.6mm、FR-4基材)以外,與(1)清洗後之覆膜殘留率之試驗基板同樣地獲得清洗處理後之試驗基板。以170℃對所得之清洗處理後之試驗基板進行5小時之加熱處理,而獲得加熱處理後之試驗基板。 The test after the cleaning treatment was obtained in the same manner as the test substrate of the (1) film residual ratio after the cleaning, except that the double-sided copper-clad laminate (size: 30 mm × 30 mm, thickness: 1.6 mm, FR-4 substrate) was used. Substrate. The obtained test substrate after the cleaning treatment was subjected to heat treatment at 170 ° C for 5 hours to obtain a test substrate after the heat treatment.
於所得之加熱處理後之試驗基板塗佈後焊劑(含有WW松香25質量%)後,搭載焊料球(大小:650μm 、合金組成:Sn/3.0Ag/0.5Cu)。然後,利用空氣回焊使焊料球熔融,並接合試驗基板與焊料球,獲得接合焊料球後之試驗基板。 After the obtained test substrate after the heat treatment, the solder (containing WW rosin (25% by mass)) was coated with a solder ball (size: 650 μm) Alloy composition: Sn/3.0Ag/0.5Cu). Then, the solder balls were melted by air reflow, and the test substrate and the solder balls were bonded to obtain a test substrate after bonding the solder balls.
關於接合焊料球後之試驗基板,使用拉脫強度試驗機(Dage公司製造之「Dage4000」)測定拉脫強度(接合強度,單位:mN)。 The test substrate after bonding the solder balls was measured for the pull-off strength (joint strength, unit: mN) using a pull-off strength tester ("Dage 4000" manufactured by Dage Co., Ltd.).
(3)焊料潤濕時間 (3) solder wetting time
除使用銅板(大小:30mm×7.5mm、厚度:0.3mm)以外,與(1)清洗後之覆膜殘留率之試驗基板同樣地獲得清洗處理後之試驗基板。使用空氣循環式烘箱,以200℃對所得之清洗處理後之試驗基板進行20分鐘之加熱處理,而獲得加熱處理後之試驗基板。 A test substrate after the cleaning treatment was obtained in the same manner as in the test substrate of (1) the residual film coverage after washing, except that a copper plate (size: 30 mm × 7.5 mm, thickness: 0.3 mm) was used. The obtained test substrate after the cleaning treatment was heat-treated at 200 ° C for 20 minutes using an air circulating oven to obtain a test substrate after the heat treatment.
於所得之加熱處理後之試驗基板塗佈後焊劑(含有WW松香25質量%)後,依據JIS Z 3197之焊料潤濕試驗方法(彎面(meniscograph)法)之記載而測定焊料潤濕時間(單位:秒)。 After the obtained test substrate after the heat treatment, the flux (containing WW rosin 25 mass %) was applied, and the solder wettability time was measured in accordance with the solder wet test method (meniscograph method) of JIS Z 3197 ( Unit: second).
(4)焊料擴散率 (4) Solder diffusivity
除使用銅板(大小:50mm×50mm、厚度:0.5mm)以外,與(1)清洗後之覆膜殘留率之試驗基板同樣地獲得清洗處理後之試驗基板。使用空氣循環式烘箱,以200℃對所得之清洗處理後之試驗基板進行20分鐘之加熱處理,而獲得加熱處理後之試驗基板。 A test substrate after the cleaning treatment was obtained in the same manner as the test substrate of (1) the residual film coverage after washing, except that a copper plate (size: 50 mm × 50 mm, thickness: 0.5 mm) was used. The obtained test substrate after the cleaning treatment was heat-treated at 200 ° C for 20 minutes using an air circulating oven to obtain a test substrate after the heat treatment.
依據JIS Z 3197之焊料擴散試驗之記載而測定焊料擴散率(單位:%)。 The solder diffusivity (unit: %) was measured in accordance with the description of the solder diffusion test of JIS Z 3197.
由表1~表3所示之結果亦可知,於使用本發明之水溶性預焊劑於半導體用基板形成保護覆膜之情形(實施例1~16)時,清洗後之覆膜殘留率、焊料球之接合強度、焊料潤濕時間及焊料擴散率均獲得充分之結果。因此,確認:根據本發明,即便於形成保護覆膜後藉由焊劑清洗劑清洗半導體用基板之情形時,亦可充分地抑制電極墊之表面之氧化。 From the results shown in Tables 1 to 3, it is also known that when the protective film is formed on the semiconductor substrate by using the water-soluble preflux of the present invention (Examples 1 to 16), the residual ratio of the film after cleaning and the solder are known. The bonding strength of the ball, the solder wetting time, and the solder diffusion rate all obtained sufficient results. Therefore, according to the present invention, even when the semiconductor substrate is cleaned by the flux cleaning agent after the protective film is formed, the oxidation of the surface of the electrode pad can be sufficiently suppressed.
另一方面,可知:於利用使用有上述通式(1)所表示之化合物以外之咪唑系化合物之水溶性預焊劑而於半導體用基板形成保護覆膜的情形(比較例1~6)時,特別是覆膜殘留率變低,而無法充分地抑制電極墊之表面之氧化。 On the other hand, when a protective film is formed on a semiconductor substrate by using a water-soluble pre-flux of an imidazole-based compound other than the compound represented by the above formula (1), (Comparative Examples 1 to 6), In particular, the residual rate of the coating film is lowered, and the oxidation of the surface of the electrode pad cannot be sufficiently suppressed.
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