WO1999040141A1 - Matiere thermiquement durcissable a une composante et destinee a la technique 'manque de metal' - Google Patents

Matiere thermiquement durcissable a une composante et destinee a la technique 'manque de metal' Download PDF

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Publication number
WO1999040141A1
WO1999040141A1 PCT/DE1999/000292 DE9900292W WO9940141A1 WO 1999040141 A1 WO1999040141 A1 WO 1999040141A1 DE 9900292 W DE9900292 W DE 9900292W WO 9940141 A1 WO9940141 A1 WO 9940141A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
underfill composition
thermally hardenable
epoxy
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/DE1999/000292
Other languages
German (de)
English (en)
Inventor
Klaus Höhn
Georg Bogner
Heiner Bayer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of WO1999040141A1 publication Critical patent/WO1999040141A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/01—Manufacture or treatment
    • H10W74/012—Manufacture or treatment of encapsulations on active surfaces of flip-chip devices, e.g. forming underfills
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/30—Die-attach connectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • H10W74/15—Encapsulations, e.g. protective coatings characterised by their shape or disposition on active surfaces of flip-chip devices, e.g. underfills
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/073—Connecting or disconnecting of die-attach connectors
    • H10W72/07331—Connecting techniques
    • H10W72/07337—Connecting techniques using a polymer adhesive, e.g. an adhesive based on silicone or epoxy
    • H10W72/07338—Connecting techniques using a polymer adhesive, e.g. an adhesive based on silicone or epoxy hardening the adhesive by curing, e.g. thermosetting
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/851—Dispositions of multiple connectors or interconnections
    • H10W72/853—On the same surface
    • H10W72/856—Bump connectors and die-attach connectors

Definitions

  • the invention relates to a thermally curable one-component underfill composition and its use in the field of microelectronics and microoptics.
  • Underfill materials are often used to connect optoelectronic or electronic components using the so-called underfill technology to form micro-bundles.
  • underfill technology In order to keep the costs of the resulting microcomposites or modules low, their production must be efficient, automatable and error-free.
  • the resulting composites should also be high-strength and dimensionally stable.
  • thermoset materials are often used as the underfill compound.
  • mineral fillers such as quartz, quartz powder or aluminum oxide are usually added to the underfill mass. In this way, the thermomechanical behavior of the underfill mass can be adapted to the substrate and its thermal conductivity can be increased, so that heat loss occurring in the application can be dissipated well.
  • the addition of mineral fillers to an underfill mass has the disadvantage that its viscosity increases considerably as a result.
  • Another disadvantage is that due to the unfavorable grain size ratios of the fillers, the filled underfill materials are not suitable for the production of microcomposites in which the substrates to be joined have very small gaps or cavities.
  • the underfill mass provided with fillers penetrates very poorly into small gaps in the micrometer or sub- ⁇ m range, for example in gaps with a size of less than 20 ⁇ m and in particular less than about 3 ⁇ m. That way Microcomposites produced are therefore unsatisfactory in terms of their excitement.
  • Loss of quality can also be expected if multi-component resin-hardener systems are used to manufacture microcomposites. Only extremely small amounts of underfill mass are required to manufacture the very small composites. If you don't want to buy that too big
  • underfill materials are to be used for optoelectronic purposes, is that they should be transparent after curing.
  • underfill materials which are suitable for producing microcomposites, in particular in the microelectronic and optoelectronic field, and which can be used before they can also be used to connect components which have very fine gaps in the micrometer and sub- ⁇ m range.
  • the underfill masses should be too 3 high-strength and dimensionally stable connections, deliver good results with regard to their thermomechanical properties and ensure sufficient bond strength even at briefly occurring high temperatures.
  • the underfill materials should be easy and safe to process and, in particular, should have a processing time that may also enable additional joining steps.
  • the underfill mass should be transparent, in particular for use in the optoelectronic field. The object of the invention is accordingly to provide such underfill materials.
  • the problem is solved with the underfill mass according to claim 1.
  • the underfill mass according to the invention is an Em component mass.
  • the underfill composition according to the invention is thermally hardenable, which is why it can be stored at room temperature or below for a long time without any problems. It can also be processed at room temperature without any problems, and various joining steps can be carried out in succession without the underfill compound curing prematurely.
  • the underfill composition according to the invention consists of a low-viscosity epoxy resin, alcohol and / or sugar and a cationic initiator. If desired, adhesion promoters and / or auxiliaries may also be present.
  • the individual components of the underfill mass according to the invention are selected so that the underfill mass has a viscosity of less than 1000 mPas at room temperature before it is crosslinked.
  • the low viscosity ensures, on the one hand, that the underfill composition according to the invention can be metered and processed without problems even at room temperature. Due to its low viscosity, the underfill mass according to the invention penetrates without difficulty even into the very distant gaps of the substrates to be processed.
  • the epoxy-based underfill composition according to the invention cures to form a generally transparent thermoset which has excellent shape and temperature stability. Even temperatures of up to 320 ° C can be tolerated for a short time.
  • thermomechanical properties, the bond strength, the dimensional and temperature stability of the cross-linked, thermosetting compound and the reological properties of the non-cross-linked system can be set in a targeted manner by suitable selection of the individual components.
  • the type and amount of alcohol or sugar in the underfill mass is of particular importance.
  • the underfill composition according to the invention can be used for the components mentioned for all those compounds which are usually used in Em component epoxy resins.
  • no thixotropic agents and no mineral fillers are expediently used in connection with the underfill composition according to the invention in order to ensure that their viscosity at room temperature is below 1000 mPas.
  • an epoxy resin is preferably used, the viscosity of which is below 700 mPas at room temperature.
  • the epoxy is not restricted in terms of its chemical nature.
  • the epoxy includes at least one cyclic aliphatic epoxide and / or at least one epoxide produced by epoxidation of double bonds of long-chain alkenes and / or at least one epoxide derived from hydrogenated bisphenol A derivatives.
  • Cyclic aliphatic epoxides are, for example, those with a cyclohexane or cyclopentane skeleton.
  • the starting materials for the epoxidized long-chain alkenes are, for example, those with more than eight and in particular more than twelve carbon atoms.
  • the epoxides derived from long-chain alkenes are preferably not used alone, but in a mixture with other epoxides, for example of the type mentioned above.
  • 3,4-epoxy-cyclohexylmethyl-3 ', 4' -epoxycyclohexane-carboxylate can be mentioned, which is commercially available under the name CY179 from the company CIBA-GEIGY.
  • the amount of epoxy resin in the under ⁇ fill composition according to the invention is preferably 60 to 97.8% by weight.
  • the alcohol and / or sugar plays a special role in the underfill composition according to the invention with regard to the setting of the chemical and physical properties of the composition.
  • the proportion of alcohol and / or sugar in the underfill composition according to the invention will expediently be about 2 to 32% by weight.
  • it is predominantly composed of one or more polyhydric alcohols.
  • polyhydric alcohols can be used either alone or in a mixture. Both aliphatic and aromatic alcohols can be used. Bi- or tricyclic aliphatic alcohols are suitable, for example.
  • 3 (4), 8 (9) - bis (hydroxymethyl) -tricyclo [5.2.1.0 2,6 ] -decane can be mentioned, which is commercially available from HOECHST under the name TCD-alcohol DM .
  • the composition of the sugar which can be used instead of the polyhydric alcohol or in a mixture with it in the underfill composition according to the invention, is also not restricted. Mixtures of different sugars can also be used here.
  • the desired properties of both the non-crosslinked Em component system and the crosslinked thermoset can be set particularly effectively by the suitable choice of the type and amount of the polyhydric alcohol and / or sugar.
  • the properties that can be varied in a targeted manner are, in particular, the rheological properties of the non-crosslinked system, the so-called low stress properties of the thermoset (in particular elastic modulus, CTE, the stress relaxation capacity, etc.), the bond strength as well as the dimensional and temperature stability of the networked system.
  • the procedure is fundamentally known to the person skilled in the art and need not be explained in more detail here. Simple tests are sufficient to obtain Em component systems with the desired properties.
  • Suitable monohydric alcohols are, for example, aliphatic alcohols such as 1-butanol.
  • a cationic initiator is added to it.
  • the proportion of the cationic initiator in the composition is advantageously 0.2 to 3% by weight.
  • Halonium and in particular sulfonium salts have proven to be particularly suitable as cationic initiators.
  • a sulfonium salt 7 can be called S-benzylthiolanium hexafluoroantimonate, which is commercially available from ALDRICH.
  • Adhesion promoters and other aids can also be present as optional components of the underfill composition according to the invention. Basically, all adhesion promoters and auxiliaries known in connection with epoxy resins can be addressed here. A prerequisite for their use, however, is that they do not lead to an increase in the viscosity of the uncrosslinked underfill mass to over 1000 mPas at room temperature. Mineral fillers and thixotropic agents are therefore expediently not used in the underfill composition according to the invention.
  • adhesion promoters with the composition according to the invention are used, their proportion is advantageously a maximum of 2% by weight.
  • suitable adhesion promoters are alkoxysiloxane compounds, such as, for example, 3-glycidyloxypropyltrimethoxysilane, commercially available from HÜLS under the name A187.
  • the flow aids known in the prior art can be addressed as aids.
  • Their proportion suitably amounts to a maximum of 3% by weight m of the underfill mass according to the invention.
  • the Em component underfill composition according to the invention can be processed without problems even at room temperature. Gaps in the ⁇ m and sub- ⁇ m range can be filled without any problems.
  • the underfill composition according to the invention is generally stable in storage at room temperature for several months and at 5 to 7 ° C. for at least 1 year. It can be linked to a polyether network by supplying thermal energy according to a cationic mechanism. Crosslinking generally takes place at temperatures above 120 ° C. This ensures a long processing time at room temperature. After thermal crosslinking a compact thermoset material is obtained, which is generally transparent. It has excellent low stress behavior, high bond strength and good dimensional and temperature stability. These desired properties can also be specifically set by selecting the type and quantity of the components.
  • the glass transition temperature can be specifically varied by varying the polyhydric alcohol. It is readily possible to set the glass transition temperature between 150 and 230 ° C., which is particularly suitable for use in the microelectronic and micro-optical field.
  • the ⁇ -transition m dynamic-mechanical examinations which plays a role for the molding material properties of the thermoset, is generally at 1 Hz about 15 ° C above the glass transition temperature from dynamic scanning calorimetry measurements.
  • the excellent thermal stability of the underfill composition according to the invention is particularly advantageous.
  • the mass degradation is less than 2% by weight up to about 300 ° C.
  • the underfill materials according to the invention also pose no problems in terms of work hygiene and safety.
  • Tg glass transition temperature
  • S.T.E. Coefficient of thermal expansion
  • DTA differential thermal analysis 11
  • DTG first derivative of the curve TG / DTA
  • the Em component underfill mass according to Table 1 already has a very low viscosity at room temperature, which can be reduced even further by increasing the temperature. This ensures excellent workability of the underfill mass over a longer period of time without the mass already curing, and ensures that even the smallest gaps are completely filled with the underfill mass.
  • Curing begins at around 120 ° C, the onset temperature is 131 ° C (see DSC). Curing can therefore already be carried out at around 120 ° C. In order to shorten the curing time, the curing is preferably carried out at 130 ° or above. The underfill mass is largely cured after just 10 minutes at 130 ° C. After an hour there is no residual reaction.
  • the thermal and mechanical properties of the crosslinked molding material indicated under the heading of molding material properties demonstrate its extraordinarily good bond strength, dimensional and temperature stability, which make the underfill composition according to the invention particularly suitable for use in the field of microelectronics and microoptics. 12
  • underfill composition according to the invention there are preferred uses of the underfill composition according to the invention in these fields and in particular in the production of fiber-optic components and in the area of the assembly of microelectronic components.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

L'invention concerne une matière thermiquement durcissable à une composante et destinée à la technique "manque de métal". Cette matière à base d'époxy est composée d'une résine époxy de faible viscosité, d'alcool et/ou de sucre, d'un initiateur cationique et éventuellement d'un promoteur d'adhérence et/ou d'auxiliaires. Par sa faible viscosité avant réticulation, inférieure à 1000 mPas à température ambiante, la matière à manque de métal convient particulièrement à la production de composants et de complexes microélectroniques et optoélectroniques dans lesquels des cavités et des fentes de fine structure de l'ordre du mu m et du sub- mu m doivent être remplies.
PCT/DE1999/000292 1998-02-05 1999-02-03 Matiere thermiquement durcissable a une composante et destinee a la technique 'manque de metal' Ceased WO1999040141A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19804595.6 1998-02-05
DE19804595A DE19804595A1 (de) 1998-02-05 1998-02-05 Thermisch härtbare Ein-Komponenten-Underfill-Masse

Publications (1)

Publication Number Publication Date
WO1999040141A1 true WO1999040141A1 (fr) 1999-08-12

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PCT/DE1999/000292 Ceased WO1999040141A1 (fr) 1998-02-05 1999-02-03 Matiere thermiquement durcissable a une composante et destinee a la technique 'manque de metal'

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Country Link
DE (1) DE19804595A1 (fr)
WO (1) WO1999040141A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007017341A1 (fr) * 2005-08-11 2007-02-15 Siemens Aktiengesellschaft Agents d'encapsulation fondants - resines de coulee a base de resines epoxydes cationiquement durcissables pour applications de montage direct de puces

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10232636A1 (de) * 2002-07-18 2004-02-12 Delo Industrieklebstoffe Gmbh & Co. Kg Verfahren und Klebstoff zur Flip-Chip-Kontaktierung

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4480059A (en) * 1982-08-26 1984-10-30 General Electric Company Epoxy adhesives for poly(butylene terephthalate)
EP0321820A2 (fr) * 1987-12-23 1989-06-28 Siemens Aktiengesellschaft Résine liquide, durcissable par rayonnement, utilisée comme revêtement secondaire pour des conducteurs optiques
DE3743996A1 (de) * 1987-12-23 1989-07-13 Siemens Ag Fluessiges, strahlenhaertbares harz zur isolierung duenner leitungen
EP0439171A2 (fr) * 1990-01-25 1991-07-31 Shin-Etsu Chemical Co., Ltd. Composition de résine époxy et dispositif semi-conducteur ainsi encapsulé
EP0527107A1 (fr) * 1991-06-19 1993-02-10 Ciba-Geigy Ag Nouveaux systèmes de résines ayant une basse température de moulage
WO1998003606A1 (fr) * 1996-07-18 1998-01-29 Siemens Aktiengesellschaft Systeme d'adhesif de faible viscosite a un composant durcissable thermiquement a proprietes de stockage ameliorees

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19541075C1 (de) * 1995-11-03 1997-04-24 Siemens Ag Photohärtbares Harz mit geringem Schwund und dessen Verwendung in einem Stereolithographieverfahren
JP3592825B2 (ja) * 1996-02-07 2004-11-24 東レ・ダウコーニング・シリコーン株式会社 硬化性エポキシ樹脂組成物および電子部品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4480059A (en) * 1982-08-26 1984-10-30 General Electric Company Epoxy adhesives for poly(butylene terephthalate)
EP0321820A2 (fr) * 1987-12-23 1989-06-28 Siemens Aktiengesellschaft Résine liquide, durcissable par rayonnement, utilisée comme revêtement secondaire pour des conducteurs optiques
DE3743996A1 (de) * 1987-12-23 1989-07-13 Siemens Ag Fluessiges, strahlenhaertbares harz zur isolierung duenner leitungen
EP0439171A2 (fr) * 1990-01-25 1991-07-31 Shin-Etsu Chemical Co., Ltd. Composition de résine époxy et dispositif semi-conducteur ainsi encapsulé
EP0527107A1 (fr) * 1991-06-19 1993-02-10 Ciba-Geigy Ag Nouveaux systèmes de résines ayant une basse température de moulage
WO1998003606A1 (fr) * 1996-07-18 1998-01-29 Siemens Aktiengesellschaft Systeme d'adhesif de faible viscosite a un composant durcissable thermiquement a proprietes de stockage ameliorees

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007017341A1 (fr) * 2005-08-11 2007-02-15 Siemens Aktiengesellschaft Agents d'encapsulation fondants - resines de coulee a base de resines epoxydes cationiquement durcissables pour applications de montage direct de puces

Also Published As

Publication number Publication date
DE19804595A1 (de) 1999-08-12

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