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Introduction
Organic polymers are widely used as structural materials and as processing aids in the electronics industry. The widespread use of polymeric materials in electronics is due to the ease in which desired engineering properties can be designed into materials by the manipulation of polymer structures and formulary compositions. In addition, the wide range of fabrication processes by which polymers can be formed into nished articles and the frequently lower fabrication costs of polymers compared to metals or ceramics have contributed to ubiquitous use of polymers in electronic assemblies. The Electronic Packaging Hierarchy. Electronic packaging is broadly dened as the physical interconnection of electronic and electromechanical components to provide an enclosed system that provides for power and signal distribution, allows heat dissipation, and protects the components from the environment (1). Efcient construction and conguration of an electronic system is obtained through the packaging hierarchy (1) shown in Figure 1. The rst level of assembly begins with assembling one or more integrated semiconductor devices or chips, each of which may contain millions of transistors fabricated in multiple layers of active devices, insulating layers, and metal interconnection layers (2), into a discrete module or rst level package. The goals of rst level packaging are to provide reliable electrical connections between the devices on one or more chips and the external metal conductors on the package, protect the delicate chip from the environment, and provide electrical and mechanical connection to the next level of assembly. High humidity, salts, certain gases such as the oxides of nitrogen and sulfur, radiation, static electrical discharges, and mechanical shock are all common environmental stresses that are harmful to

Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.

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Video Monitor Personal Computer Third Level Package Printer

253

Modem Semiconductor Chip

Keyboard

Mouse

Single Chip Package First Level Package

Circuit Card Second Level Package Networked System Fourth Level Package

Fig. 1. The electronic packaging assembly hierarchy.

integrated circuits. First level packages are attached to a substrate or second level package bearing metal conductors that provide interconnections between the rst level components. The most familiar example of second level packages is the ubiquitous ber glass-epoxy laminate circuit board found in a wide range of consumer electronics and computer systems. Second level packages often have a dened, modular function such as memory cards, disk drive controller cards, and video cards. In other instances, the second level package is a system and is mounted in a protective case to produce a modular component that is used directly, for example, an automotive ignition module or the electronics of a consumer product such as a cellular telephone. A group of second level packages are frequently assembled on a larger card, termed a motherboard or backplane and the resulting assembly is housed in a cabinet or case. This assembly produces a third level package that provides electrical interconnection between cards and other board or cabinet mounted components such as power supplies and disk drives and provides connectivity to input devices, such as a keyboard and mouse, to output devices, such as printers and video monitors, and to inputoutput devices such as modems. An easily recognizable third level package is a personal computer. Fourth level packages are obtained through interconnection of third level systems to provide more complex systems such as the familiar ofce network or large mainframe computer system. Electronic packaging makes use of a wide variety of polymer material classes to fulll a diverse range of engineering uses. Table 1 provides a segmentation

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of commonly used polymeric materials by engineering use and polymer class (3,4).

Polymers in First Level Packages

One of the most common and recognizable rst level packages is the plastic dual in-line package (DIP) as shown in Figure 2. This package provides a convenient case example for further discussion of the polymers and polymer processing used in rst level electronic packaging. The sequential assembly (Fig. 3) of a DIP (1) begins by attaching the chip, which often bears a top-side polymeric passivation or stress buffer coating, to a metal lead frame substrate by using a die attach adhesive formulation. A linear array of aluminum alloy contacts or bond pads are arranged along the periphery of the chip. Typical bond pads are squares with dimensions in the 50200 m range and are the termini for the internal chip wiring. The bond pads are connected to contact points on the lead frame by 2550 mm diameter gold or aluminum wire using ultrasonic, thermocompression, or thermosonic bonding (5). The wire-bonded lead frame-chip assemblies are then loaded into cavity molds and a molten, encapsulation resin composition is transferred into the mold under heat and pressure. Assembly is completed by applying lead nish plating, marking component identifying information on the package, singulating the packages, forming the leads into the required geometry by precision bending, and nal packing for shipment to the second level package assembler. The single-chip plastic package appears in a variety of sizes and pin counts, depending upon the chip size, the number of leads required to connect the chip, and the amount of space allocated on the circuit board for the package (Fig. 4). For example, the DIP was designed for insertion into plated-through holes on a circuit board while the

Encapsulant Resin Bond Pad

Stress Buffer Coating Wire Bond

Lead Frame

Die Attach Adhesive (a) (b)

Fig. 2. (a) An exterior view line drawing of a DIP (1). (b) A schematic cross section of a DIP showing the components of construction.

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Table 1. Polymeric Materials Used in Electronic Packaging Segmented by Engineering Use and Polymer Classa Engineering use Adhesive Polymer class Acrylic Epoxy silicone Epoxy novalac Epoxy bisphenol A Epoxy polyimide Epoxy polyurethane Polyimide Silicones Polyetherketone Polyetheretherketone Polysulfone Polyethersulfone Polyester Epoxy and lled epoxy Silicones and lled silicones Bis-maleimide triazine (BT) resin BT-Epoxy E-glass laminate Epoxy-E-glass laminate Polyimide-E-glass laminate Poly(tetrauoroethylene)-E-glass laminate Polyimide-E-glass laminate Polyester lm Polyimide lm Poly(tetrauoroethylene) lm Polyamide lm Poly(vinyl chloride) lm Poly(vinyl uoride) lm Polyethylene lm Polypropylene lm Polycarbonate lm Polysulfone lm Poly(parabanic acid) lm Poly(ethersulfone) lm Poly(amide-imide) Poly(benzocyclobutene)BCB Polybenzoxazole Polyimide RTV Silicone Poly(benzocyclobutene)BCB Polybenzoxazole Polyimide Poly(norbornene) Triazine blend resin

255

Encapsulation

Substrate

Stress buffer coating

Interlayer dielectric

a From

Refs. 3 and 4.

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Apply Stress Buffer Coat Wafer Thinning Wafer Dicing

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Wafer

Die Attach

Wire Bonding

Encapsulation

Lead Finish

Marking

Singulation

Lead Forming

Packing

Fig. 3. Assembly sequence for plastic packages.

SOJ or Small Outline J-lead

SOP or Small Outline Package

PLCC or Plastic Leaded Chip Carrier

SQFP or Square Quad Flat Package

VSOP or Very Small Outline Package

Fig. 4. Exterior view line drawings showing other types of plastic packages. From Ref. 7, with permission.

packages shown in Figure 4 were designed for surface mounting to a circuit board. Surface mounting technology, or SMT, allows internal board space to be used for routing connections and reduces the board size by eliminating the space needed for the plated-through holes. Package size reduction is a major industry trend and is driven by the space constraints imposed by personal electronic products such as cellular phones, laptop computers, and personal digital assistants. This trend has resulted in the recent development of several new package types with the

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goal of obtaining package geometries that are as close as possible to the size of the chip itself. These technologies are collectively know as chip scale packaging or CSP (6). Stress Buffer Coatings. The top or device surface of semiconductor chips is frequently coated with a polymeric passivation coating that acts as a protective stress buffer layer (Fig. 2b). While stress buffer coatings (SBCs) are applied in the last steps of the wafer fabrication process, they have been shown to provide several important benets to packaged device yield and reliability (810) and are considered herein as packaging materials. The SBC protects the chip from mechanical damage during package assembly and provides a relatively soft and ductile material on the chip that prevents chip cracking from the shear stresses that occur during encapsulant molding. The SBC also provides a mechanism for distributing stress over the surface of the chip and greatly reduces chip failures due to locally high stresses. Shear stress at the chip surface can cause movement or sliding of the underlying metal lines chip, cracking in silicon oxide and silicon nitride passivation layers, and parametric shifts in the electrical characteristics of the chip (8). The incidence of stress-related failure modes are frequently higher in larger chips and packages because of the larger distances over which thermal stress can be developed. As a consequence, most current memory and logic devices use SBCs to improve the yield of packaged devices and to lower lifetime failure rates. Finally, SBCs provide a barrier to alpha-particle radiation, which can lead to soft errors (11) in the device. Stress buffer coat lms require lm mechanical properties that result in strong, tough lms that resist mechanical damage but are soft enough to absorb stress. Successful materials generally have an elastic modulus in the range of 2 4 GPa (290,000580,000 psi), a yield strain of 510%, and a tensile failure strain of 25% or greater. The use of low modulus materials runs a risk of wire bond breakage due to creep. Film thermal stability is important in that the materials must be dimensionally stable at the process temperatures frequently required in latter process steps and must not outgas volatiles during these operations. This thermal stability requirement leads to a need for materials with a glass-transition temperature T g of 260 C or greater, with some assembly processes requiring T g s greater than 350 C. Silicon is a low expansion material with a coefcient of thermal expansion (CTE) of 3.2 ppm/ C. Because polymers typically have CTEs that are higher than the CTE of silicon, there is a signicant CTE mismatch between the chip and the stress buffer coat, resulting in tensile coating stress that is large enough to bend or bow the chip. The extent of bow is largely determined by the thickness ratio of the coating to the chip, the magnitude of CTE mismatch, the coating thermal history, the elastic modulus of coating and substrate, and by the extent of in-plane coating shrinkage during cure (12). In general, the CTE of the SBC should be matched as closely as possible to the CTE of the package components with which it is adhered. The adhesion of the SBC to the chip must be exceptionally good so that delamination does not occur during package assembly or during the operational lifetime of the package. Finally, the SBC chemistry must promote adhesion to the encapsulating resin so that adhesion failures do not occur at the SBCencapsulant interface. Stress buffer coats are applied to semiconductor devices by two commonly used methods. The rst method is termed glob-top coating and involves

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dispensing a drop of polymer solution or neat resin formulation onto the chip after wire bonding. Multiheaded syringe systems that dispense material on many parts at once are commonly used for this purpose. The dispensed material is heated to cure the resin and to remove solvents. The second method is to apply the coating at the wafer level using standard wafer fabrication spin coating equipment. Materials applied at the wafer level by spin coating have largely replaced glob-top coating in the manufacture of many device types including large memory and logic devices, with small power devices remaining as the major application for drop-on coatings. This trend is due to the greater throughput of the spin coating process where hundreds of chips are processed at once on a single wafer and to the reduction in device mechanical damage that is obtained by applying the top coat prior to processing the wafers into packages. Materials for Stress Buffer Coatings. Stress buffer coating formulations have been prepared using polymers from several classes including polyimides, polybenzoxazoles, polybenzocyclobutenes, and polysiloxanes. Polyimides are the most commonly used buffer coat materials, and commercial formulations are available from several suppliers. Polyimides offer several advantages as SBCs including high thermal stability, good dielectric properties, good chemical resistance, and excellent lm mechanical properties. The adhesion of formulated polyimide materials to silicon oxide and silicon nitride is excellent as most materials feature chemical modications designed to promote adhesion to these surfaces. Two types of modication strategies are used to improve adhesion: modication of the polymer backbone by incorporating siloxane-containing monomers or by adding adhesion-promoting additives such as aminosiloxanes. In addition, the processability of formulated polyimide products has greatly improved over the last 10 years and materials are available that have been optimized for high throughput on current semiconductor factory tool sets and process methods. Finally, commercial materials are available with low trace metal and halogen content demonstrating the maturity of the supply chain in providing electronic grade materials. As a class, polyimides have relatively high moisture absorbance which limits their use in some applications where stable dielectric properties or low tolerance for absorbed moisture are important considerations. StructureProperty Relationships in Polyimides. Electronic polyimides are obtained from the polymerization of aromatic or aliphatic diamines with aromatic dianhydrides or derivatives of the dianhydrides. Table 2 provides selected physical properties of several structurally diverse polyimides derived from the monomer units shown in Figure 5. The thermal and mechanical properties of polyimide lms are readily modied in a designed approach by selecting the dianhydridediamine pairs needed to provide the desired lm properties. An additional degree of property optimization may be obtained through the copolymerization of one or more dianhydrides with one or more diamines. In general, the selection of rigid monomers provides materials with a high modulus and high T g and a low CTE while selection of monomers with exible spacer groups, such as ether linkages, between the imide bearing aromatic rings provides materials with a lower modulus and lower T g and a higher CTE, with copolymers demonstrating properties predicted by the rule of mixtures. While most aromatic polyimides are

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Table 2. Thermal and Mechanical Properties of Selected Polyimides.a Diamines Dianhydrides PMDA Property Tg , C Modulus, GPab CTEc , ppm/ C Tg , C Modulus, GPa CTE, ppm/ C Tg , C Modulus, GPa CTE, ppm/ C Tg , C Modulus, GPa CTE, ppm/ C Tg , C Modulus, GPa CTE, ppm/ C

ODA 380400 3 3540 306 46 280 42.8 268 2.9 55 285

pPPD 360 11 2.6 21 342 6.4 326

mPPD 32 40 300 29 297

DAPI >400 384 45 331 3.3 54 295 331 55

BPDA

BTDA

ODPA

6-FDA

a From

Refs. 1317. modulus. To convert GPa to psi, Multiply by 145,000. c Coefcient of thermal expansion in units of ppm/ C.
b Tensile

not soluble in common solvents and must be processed using soluble precursors, solvent-soluble materials can be prepared using monomers that contain several exible linkages, have strongly dissymmetric structures, or have bulky pendent groups. Polyimide SBCs can be grouped into four classes based on both the chemistry of their precursors and the processing strategy used to pattern their coatings. These classes are polyamic acids, solvent-soluble polyimides, solventdeveloped, photosensitive materials, and aqueous-base developed, photosensitive materials. Polyamic Acids. Polyamic acids are commonly prepared by the step-growth polymerization of one or more aromatic dianhydrides and one or more aromatic or aliphatic diamines in N-methylpyrrolidinone (NMP) solvent to yield 1525% solids solutions which are typically used without isolation of the polymer. While numerous polyamic acids have been reported in the literature (18,19), only a few are in common use in stress buffer formulations as many of the monomers reported in the literature are not available in commercial quantities. Special care must be taken to use the purest materials available so that the product is free of metallic and organic contaminants, especially surface-active materials, that may cause coating defects or lead to poor adhesion. The polymer molecular weight may be controlled by conventional methods, either by adjusting the stoichiometry of the reactants (20) or by using monofunctional anhydrides or amines to limit chain growth. Molecular weight control is of great importance because the mechanical properties and thermal stability of the cured lm are functions of molecular weight (21) and because the thickness of the spin-coated lm depends on both the viscosity and the solids loading of the polymer solution. The need for

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Fig. 5. The chemical structures of some common aromatic dianhydride (a) and aromatic diamine (b) monomers used in the synthesis of electronic-grade polyimides.

control of these parameters is demonstrated by Figure 6 which shows plots of spin coat lm thickness vs solution solids content and the relationship between solids content and viscosity obtained from measurements on a PMDAODA polyamic acid solution. Prior to use, polyamic acid solutions must be ltered to remove particulate matter to prevent lm defects that will cause problems in subsequent processing.

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Fig. 6. (a) Relationship between lm thickness and solution solids content. (b) Relationship between solution viscosity and solution solids content. , Cured thickness; , Soft baked thickness. Data are from a PMDAODA polyamic acid solution.

The polyamic acid lm is prepared by spin-coating the solution on a wafer and then baking the wet lm at 85150 C on a hot plate to yield a tack-free lm that can be handled by automated wafer handling equipment without perturbing the coating thickness. Imidization or curing of the polyamic acid lm to form a polyimide lm is completed by heating the polyamic acid to temperatures ranging from 250 to 400 C in a nitrogen atmosphere, resulting in cyclodehydration and evaporation of solvent (Fig. 7). In order to permit wire bonding, openings must be patterned through the SBC so that metallurgical contact can be made with the aluminum pads on the device. The required openings are readily patterned in polyamic acid lms using a photolithographic, bilayer patterning and base etch process (22,23) (Fig. 8). In this process, the polyamic acid solution is dispensed onto the center of a rotating silicon wafer using a metering pump. After dispensing is complete, the wafer is accelerated to a higher speed and then held at constant speed for 2030 s. The wafer is then moved to a programmable hot plate and soft-baked at temperatures ranging from 85 to 150 C to yield a tack-free lm with a coating thickness and etch

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Fig. 7. Synthesis and cyclodehydration of PMDAODA polyamic acid to yield PMDA ODA polyimide.

Coat & Bake Polyamic Acid

Coat Photoresist

Mask

Image Photoresist

Develop Photoresist

Etch Polyamic Acid

Strip Resist & Cure Polyamic Acid

Fig. 8. Bilayer process for patterning polyamic acid lms.

rate dened by the soft bake time and temperature program. This process results in a coating of dened thickness and, if the process is optimized, lm thickness variation is less than 2% of the lm thickness. The dried and partially imidized polyamic acid lm is then coated with a resist layer formed by spin coating and baking a diazonapthaquinone-novalac photoresist lm (24) on the polyamic acid lm. The photoresist is imaged by exposure to uv light through a photomask (25). Treatment of the exposed resist with an aqueous hydroxide base solution such as tetramethylammonium hydroxide develops the latent resist image and yields a positive-tone relief image of the mask. The development process is then allowed to continue, resulting in an isotropic etch that transfer the resist relief image into the

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Fig. 9. A stress buffer coat pattern formed in PMDAODA polyamic acid using the bilayer process shown in Figure 8. Courtesy of Arch Chemicals, Inc.

polyamic acid lm by solubilizing the polyamic acid through the combined effects of soluble salt formation and chain hydrolysis. Next, the photoresist lm is removed by dissolving the resist in a solvent, such as acetone, that is compatible with the polyamic acid lm. The process is completed by heating the lm at 300400 C, which completes the imidization reaction and removes the water of imidization and residual solvent. Figure 9 shows a photograph of a patterned lm where the small square features are bond pad openings and the large open lines or dicing streets are formed to allow passage of the diamond saw blade used to singulate chips from the wafer without blade fouling from adhered polymer. The polyamic acid patterning process described above has been used for many years. However, the process has several drawbacks. First, the number of process steps involved reduces process throughput, produces a signicant amount of waste, and increases the possibility of process defects. Second, pattern resolution is limited to a maximum feature width that is about 50% of the polyamic acid lm thickness. Third, processing polyamic acid lms greater than 10 m in thickness is difcult owing to thickness uniformity in spin-coating polyamic lms to lm thicknesses greater than 10 m in one coating operation and to chipping of the resist etch mask during long etch times which causes defects in the pattern. Finally, the process etch rate is sensitive to the bake temperature and time used to set the polyamic acid lm which can cause reproducibility problems in etch rate. In consequence, the dimensional tolerances of the pattern are affected resulting in a deviation, or bias, from the mask dimensions. Electronic grade polyamic acid products are available from several supplies including Arch Chemicals, Inc., HD Microsystems, and Toray Industries. Commercial materials are generally formulated to provide reproducible coating thickness over a certain range of coating thickness or spin speeds. Solvent-Soluble Polyimides. Materials in this class are also termed preimidized polyimides because the lm-forming polymer is a polyimide rather than a polyimide precursor such as a polyamic acid. Thus, the curing process for these materials involves only removal of solvent. In some instances, a high

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temperature post-cure above T g can be used to cross-link the polymer and impart increased resistance to solvents. The best known examples are polyamideimides prepared by the step condensation of 4,4 -methylenebis(phenyl isocyanate) with trimellitic acid (26), polyimidesiloxanes, and polyimides derived from trimethylphenyl diaminophenylindane (DAPI) monomers (15,27,28). Use of these materials for stress buffer applications is generally restricted to glob-top applications. However, the materials may be spin-coated and patterned using a hard mask etch process. The hard mask process is an extension of the bilayer process in which a layer of oxygen plasma etch-resistant material, such as aluminum or silicon dioxide, is coated on the cured polyimide lm prior to applying the photoresist. The resist is applied and imaged as usual resulting in a positive relief image over the hard mask. Next, the hard mask is patterned using a plasma or wet chemical etchant that is selective for the hard mask material. The process is completed by transferring the pattern into the polyimide lm using a oxygen reactive ion etch process followed by removal of the resist and hard mask. This process is seldom used as it is even more time consuming and expensive than the bilayer process. However, the process has an important advantage in that it can be used to dene very high aspect ratio structures and it is generally applicable to a wide variety of polymers. Commercial examples of solvent-soluble polyimide include the DurimideTM 32 and DurimideTM 200 series materials (Fig. 10) available from Arch Chemicals, Inc. (29). A compilation of commercially available nonphotosensitive stress buffer coat materials is shown in Table 3 (2934). Table 4 provides selected physical data for some of the materials shown in Table 3. Solvent-Developed Photosensitive Materials. Many of the limitations of the bilayer polyamic acid process have been overcome through the use of photosensitive polyimides (9). Formulated photosensitive products have been developed that result in improved process capability resulting in increased pattern resolution, improved soft bake time and temperature process latitude, and improved lithographic process latitude and throughput while maintaining desired lm physical properties. Moreover, the lm patterning process requires fewer steps

Fig. 10. (a) The structure of a solvent-soluble polyimide based on DAPI monomer. (b) The structure of a solvent-soluble polyamide-imide.

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Table 3. Non-photosensitive Stress Buffer Coat Formulations Available from Various Suppliers Supplier Arch Chemicals Trade name Durimide Durimide Durimide Durimide Durimide Durimide Durimide Durimide Pyralina Pyralin Pyralin Pyralin Pyralin Pyralin Pyralin Pyralin Pyralin Pyralin Pyralin Pyralin
a

Product code 32 32A 112A 114A 115A 116A 116 200 PI-2525 PI-2545 PI-2555 PI-2556 PI-2562 PI-2575 PI-2579B PI-2610 PI-2611 PI-2616 PI-5811 PI-5878G PIX-1400 PIX-3476 PIX-5200 PIX-5500 L110SX PIX 6400 SP-811 SP-341 SP-483 SP-042

Comments Poly(amide-imide), AP Poly(amide-imide), SP PAA, SP, high T g PAA, SP, high T g PAA, SP, high T g PAA, SP, high T g PAA, AP, high T g Preimidized, AP PAA, AP PAA, AP PAA, AP PAA, AP PAA, AP PAA, SP PAA, SP PAA, AP, low CTE PAA, AP, low CTE PAA, AP, low CTE PAA, AP, low CTE PAA, AP PAA, SP PAA, SP PAA, SP PAA, SP PAA, SP, low CTE PAA, SP PAA, SP PAA, SP PAA, SP PAA, SP, low CTE

HD Microsystems

Toray

Semiconea Semicone Semicone Semicone

a PAA

= polyamic acid; AP = adhesion primer required; and SP = self-priming formulation, no adhesion primer required. b Durimide is a trademark, and Pyralin and Semicone are registered trademarks.

resulting in reduced costs and increased yields. Consequently, photosensitive materials are rapidly replacing polyamic acids as SBC materials. Two approaches for the synthesis of photosensitive polyimide precursors are in common use today. The rst approach was pioneered at Siemens (3537) and is based on polyamic acid esters wherein the ester group is a radiation crosslinkable group such as 2-hydroxyethylmethacrylate (Fig. 11). Materials based on the ester chemistry are often described as covalent-type photosensitive polyimides. The second approach, developed by Toray Industries, involves combining a polyamic acid solution with a tertiary amine bearing radiation cross-linkable groups (38) (Fig. 12). The tertiary amine forms a salt with the polyamic acid and the resulting ionic interactions are of sufcient strength to provide solubility discrimination in the imaging process. Materials based on the amine salt chemistry

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Table 4. Selected Physical Properties of Polyimide Films Derived from Nonphotosensitive Polyimide Precursors Supplier Arch Chemicals Product code 32 115A 200 PI-2525 PI-2545 PI-2562 PI-2611 PIX-1400 PIX-3476-4L L110SX SP-811 SP-341 SP-483 SP-042 Tg , C 300 370 309 325 400 325 360 290 310 300 330 300 Modulus, GPaa 3.3 3.3 3.3 2.5 1.4 2.5 8.5 3.0 3.1 2.9 2.9 2.7 eb , % 56 80 75 70 80 20 20

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CTE, ppm/ C 53 32 54 50 20 50 5 50 40 40 40 40 17

HD Microsystems

Toray

a To

convert GPa to psi, multiply by 145,000.

are commonly referred to as ionic-type photosensitive polyimides (39). The ionic approach provides the additional advantages of a simple synthesis starting from polyamic acids. Material suppliers have made steady improvements during the last 15 years, resulting in formulations with improved lithographic performance and nal lm properties (4042). Following exposure to uv light, both the covalent- and ionic-type materials undergo photoinitiated radical cross-linking reactions between the ester groups. This reaction provides the differential solubility between the exposed and unexposed area of the lm that is necessary for forming relief images (Fig. 13). The photoinitiated cross-linking reaction of a 2-hydroxyethyl methacrylate polyamic ester bearing a 13 C label at the methacrylate -carbon has been studied using a solids nmr method (43). The nmr spectra showed that the percentage of methacrylate groups reacted varied with exposure dose and processing conditions. Photosensitive precursor polymers are formulated in a suitable solvent such as N-methylpyrrolidinone or -butyrolactone with a radical photoinitiator and a variety of additives such as glycol acrylates to improve image contrast and photospeed; functionalized silane coupling agents to improve adhesion of silicon and silicon nitride; photosensitizers to improve photosensitivity; substituted phenolic stabilizers to improve formulation working life and storage stability; and leveling agents to improve coating quality and uniformity. The single-layer imaging process for photosensitive polyimides is represented in Figure 14, which, in comparison to Figure 8, clearly shows the simplication of the patterning process compared to the polyamic acid etch process. Because the solubility of the exposed lm is less than the solubility of the unexposed lm, the relief image is a negative image of the mask. In contrast to the bilayer polyamic acid etch process, the single-layer photosensitive process readily provides images with a pattern aspect ratio of 2:1, and if care is taken, resolution can be extended to an aspect ratio of 3:1. Because of their decreased

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Fig. 11. Synthesis of a covalent-type photosensitive polyimide precursor based photoreactive polyamic esters.

hydrogen bonding compared to polyamic acids, photosensitive polyamic esters are particularly suited to the processing of thick lms as their solutions have lower viscosities than polyamic acids at equivalent molecular weights and solids loading. Thus, high solids content solutions that are suitable for casting thick lms can be formulated at viscosities suitable for spin coating. Robust patterning processes have been demonstrated in 50-m thick lms which yield 25-m thick lms after curing (44). Recently, detailed characterization studies on the lithographic process latitude of covalent-type materials processed using modern, stepper exposure tools have been reported (45,46). Figure 15 shows some examples of relief structures patterned in a photosensitive polyamic ester lm. The process is completed by curing the imaged polyamic ester at 300400 C in an inert atmosphere, which results in imidization with the loss of the photoreactive groups as volatile products (Fig. 13). The imaged lm shrinks by 4050% in thickness

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Fig. 12. Synthesis of an ionic-type photosensitive polyimide precursor based on tertiary amine-polyamic acid salts containing photoreactive groups.

during the curing process, leading to cured lm aspect ratios ranging from 1.0 to 1.5. Autophotosensitive, preimidized polyimides (Fig. 16) represent a third approach to negative tone materials and are based on the inherent photosensitivity of polyimides containing benzophenone tetracarboxylic dianhydride (BTDA) derived segments together with ortho-alkyl-substituted diamine segments (47). The photochemical basis for imaging is believed to be radical cross-linking initiated by a benzophenone ketyl radical to yield cross-linked photoproducts (48,49). The most interesting feature of these materials is that they do not require formulation with the photoinitiators, photosensitizers, contrast enhancing agents, and stabilizers commonly found in the additive packages used in the formulation of covalent- and ionic-type materials. Accordingly, lms prepared from autophotosensitive materials show substantially less shrinkage during cure than do covalent or ionic materials (26). However, autophotosensitive materials have not been extensively used in SBC applications because of their low photosensitivity and long developing times as compared to covalent and ionic materials. Commercial examples of autophotosensitive materials are the Probimide 400 series from OCG Microelectronic Materials and the Ultradel 7500 series from Amoco. A separate group of negative tone materials based on the thermal polymerization of benzocyclobutenes (BCB) has been developed by the Dow Chemical Co. (50,51) and have been used as SBCs (52). The chemistry is based on the in situ generation of reactive, ortho-quinodimethane dienes that undergo facile polymerization to form a thermoset network (Fig. 17). The physical properties of the materials can be tailored by modication of the connecting group X. One such modied

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Fig. 13. Photochemical cross-linking of a covalent-type photosensitive polyimide precursor.

monomer is divinylsiloxane-bis-benzocyclobutene (DVS-bis-BCB). Photosensitive formulations are obtained by combining B-staged, or partially polymerized DVSbis-BCB, with aromatic bisazide compounds in solvent. Such formulations can be spin-coated and are processable using the negative tone process described in Figure 14. Processing of the patterned lms is completed by heating to convert the photocross-linked, B-staged lm into the cured thermoset. BCB derived lms have attracted much interest in electronic packaging owing to their low dielectric constants and low moisture uptake. The BCB materials are marketed under the trade name Cyclotene .

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Mask

Coat & Bake

Image Pattern

Develop Image & Cure

Fig. 14. Single-layer imaging process for negative tone photosensitive polyimide precursors.

Fig. 15. Negative tone relief patterns formed in a covalent-type photosensitive polyamic ester lm using the process shown in Figure 11. (a) Resolution test pattern showing 40 m features in a 40-m lm, (b) Resolution of 5 m lines and space patterns in a 18-m lm. Courtesy of Arch Chemicals, Inc.

Fig. 16. The generic structure of autophotosensitive polyimides where R1 and R2 are alkyl groups.

Aqueous-Developed Materials. During the last 5 years, aqueous developable materials have been introduced as a new class of photosensitive SBCs. Development of these materials is an area of intense current activity and is driven by industry needs for materials with improved cost of ownership and improved compatibility with semiconductor factory process strategies and materials. One of the drawbacks of most negative tone materials is that they require organic solvents for image development. Organic solvents impose a signicant cost penalty on semiconductor factories for several reasons. First, high purity, electronic grade solvents are expensive to purchase. Second, standard process equipment must be modied to allow the safe use of solvent sprays, and the modied equipment is not generally usable for other coating processes such as positive photoresists. Many factories must obtain VOC emission permits to use solvent-processed materials.

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Fig. 17. The benzocylcobutene cure reaction and the structure of DVS-bis-BCB monomer.

Finally, factories must collect and segregate spent solvent waste as a separate waste stream and thus incur additional cost. These cost of ownership issues are substantially decreased through the use of aqueous, metal-ion free developers based on tetramethylammonium hydroxide which are the semiconductor industry standard for developing positive photoresists. Both negative and positive tone aqueous developable materials have been introduced. Negative tone materials have been derived from the covalent-type polyamic ester precursors through the use of additives that enhance solubility of the unexposed lm in aqueous developers (53). Positive tone materials are based on either polyamic ester precursors containing carboxylic acid (54) or phenolic oxygen substituents (55,56) or on aromatic poly(ortho-hydroxyamides) as precursors to polybenzoxazoles (57,58), a class of high temperature stable, heterocyclic polymers with thermal and mechanical lm properties similar to polyimides (Fig. 18). In both approaches, the acidbase reaction of the phenolic or carboxylic

Fig. 18. Generic structures of positive tone, aqueous processable precursors for polyimide (a) and polybenzoxazole (b) based materials.

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substituents with base provides the mechanism for solubilizing the precursor in an aqueous developer. When formulated with diazonaphthaquinone-containing photoactive compounds (DNQ-PACs), the resulting formulations function as positive photoresists. The DNQ-PAC inhibits the solubility of the precursor polymer in base. When the DNQ-PAC is exposed to uv light, the DNQ moeity undergoes a formal Wolff rearrangement to form a ketene as the primary photoproduct which undergoes reaction with environmental water to form an indene carboxylic acid derivative (59). The indene carboxylic acid photoproducts increase the dissolution rate of the exposed lm relative to the unexposed lm. Thus, the photolithographic contrast of the system is obtained from the dissolution rate difference between the unexposed and exposed lms (Fig. 19). Processing this class of materials retains the cost and simplicity benets of the single-layer process used for solvent-developed negative tone materials and adds the benet of positive tone imaging, which results in higher image resolution and a decreased sensitivity to pattern defects due to particles on the surface of the lm (60). Commercial photosensitive SBC formulations are available from several suppliers and provide a range of materials differentiated by wavelength photosensitivity, chemistry type, and lm properties. A list of commercial photosensitive SBC formulations is shown in Table 5 (29,30,32,6163). Table 6 shows a compilation of selected lm physical property data selected from those listed in Table 5.

Polymer + exposed PAC

Film Dissolution Rate

Polymer

Dissolution rate difference provides contrast

Add PAC Polymer + PAC

O N2 h H 2O R R

COOH + N2

Fig. 19. Chemical basis for image contrast in positive tone buffer coat materials based on DNQ-PAC chemistry.

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Table 5. Commercial Photosensitive SBC Formulations Supplier Arch Chemicals Trade name Durimide
a

Product code 7800 7520 7410 7320 7000 348 HTR3 9000 G-7600s I-8300s I-8600s TL-530s 4024-40 4026-46 PI-2720 PI-2730 PI-2770 HD-4000 HD-8000 UR-3100E UR-3800 UR-5100FX UR-5400 BG-2400 BG-7730 BG-8000 PW-1000 CRC-8000

Characteristics C, N, I, BB, S, high resolution C, N, I, BB, S, high sensitivity, thick lms C, N, I, BB, S, for reective substrates C, N, I, BB, S, for Cu substrate C, N, G, BB, S, high T g C, N, G, BB, S, thick lms C, N, G, BB, S, thick lm plating stencil P, G, I, BB, A C, N, G, BB, S C, N, I, BB, S C, N, I, BB, S C, N, G, BB, S I,S I,S C, N, G, BB, S C, N, G, BB, low stress N, G, I, A C, N, I, BB, S, high T g P, G, I, BB, A IN, G, H, S IN, G, H, S, high sensitivity IN, N, G, BB, S, low stress IN, G, H, S, low stress IN, G, BB, S, low stress IN, G, BB, S, fast developing IN, I, S P, I, G, A P, G, I, BB, A

Asahi Chemical

Pimela

Dow Chemical HD Microsystems

Cyclotenea Cyclotene

Toray

Photoneecea

Sumitomo-Bakelite Excel
aC

= covalent-type photosensitive polyimide precursor; IN = ionic-type photosensitive polyimide precursor; N = negative image tone; P = positive image tone; G = sensitive to g-line (436 nm) of Hg lamp; H = sensitive to h-line (406 nm) of Hg lamp; I = sensitive to i-line (365 nm) of Hg lamp; BB = sensitive to unltered output of Hg lamp; S = developed using solvent mixtures; and A = developed using aqueous bases. b Durimide and Pimel are trademarks, and Cyclotene and Photoneece are registered trademarks.

Die Attach Adhesives. After completion of SBC processing, the nished wafers are electrically tested and nonfunctional chips are marked for discard. It is a common occurrence that the wafer and fabrication packaging facilities are separate factories or even different companies and cassettes of wafers are routinely shipped from the wafer fabrication plant to the packaging plant for assembly. At the packaging plant, the wafers are rst thinned using a grinding and polishing process that removes bulk silicon from the backside of the wafer. Substantial thickness reduction is necessary to allow assembly into the thin packages commonly used in board assembly. For example, a 200-mm wafer 725 m thick is commonly thinned to a thickness of 250 m and sometimes to as thin as 80 m (64). The

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Table 6. Selected Physical Properties of Stress Buffer Coat Films Derived from Photosensitive Precursors Supplier Arch Chemicals Product code Durimidec 7500 Durimide 7000 Durimide 9000 G-7600s I-8300s I-8600s TL-530s Cyclotenec 4000 PI-2720 PI-2730 PI-4000 HD-8000 UR-3100 UR-5100FX UR-5440 BG-2400 BG-7730 BG-8000 PW-1000 CRC-8000 Tg , C 285 >350 320 355 280 >350 310 350 350 300 285 >350 >350 255 290 260 290 300 Modulus, GPaa 2.5 2.9 2.5 3.3 2.8 2.9 2.5 4.7 3.5 2.5 3.2 4.8 4.2 3.9 3.0 3.5 3.0 2.45 CTE, ppm/ C 55 27 32 4050 50 50 1020 52 57 16 33 47 40 20 16 25 45 39 36 55 Coating stress, MPab 33 30 40 3540 3540 2030 2832 39 13.5

Asahi Chemical

Dow Chemical HD Microsystems

Toray

Sumitomo-Bakelite
a To b To

convert GPa to psi, multiply by 145,000. convert MPa to psi, multiply by 145. c Durimide is a trademark and Cyclotene is a registered trademark.

SBC layer provides both protection and support during the thinning process. The thinned wafer is then mounted, with their active device side up, onto a tacky adhesive release tape xed in a steel ring. The mounted wafer is then singulated or diced into chips using a high speed diamond wet saw. To allow for the cutting kerf, the blade passes between device boundaries known as saw streets that were established during wafer fabrication (see Fig. 9). In high volume factories, the processes of wafer thinning and singulation are highly automated assembly line operations. After dicing, the chips are removed from the release tape using a vacuum tool, which then places the die onto the metal lead frame to which has been applied die attach adhesive material in the form of a paste or lm. Most die attach adhesives in use today are formulated products based on epoxies, thermoplastic polyimides, or thermoplastics such as bismaleimides, polysulfone, polyphenylene sulde, and polyesters. The polymers may be used separately or as blends. Die attach adhesives usually contain inorganic metal or metal oxide llers that impart electrical and/or thermal conductivity to the adhesive bond, thus creating an electrical connection to the lead frame and improving package heat dissipation by allowing better heat transfer from the device to the lead frame. High speed, automated dispense equipment is used to dispense and place the adhesive with a

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high degree of accuracy with a cycle time of 2 s per chip placement (65). The lead frames are then loaded into magazines and placed in ovens to cure the adhesive. Typical curing cycles are 1 h at 150 C for epoxy-based formulations and 30 min at 150 C followed by 30 min at 275 C for polyimide-based formulations. Rapid or snap curing materials are now available that can be cured in one minute and can thus allow integration of the adhesive cure process into the dispense line. In addition to excellent adhesion, critical design considerations for die attach adhesives may be segregated into those involving processability, thermal properties, electrical properties (insulating or conductive), and thermal conductivity. The viscosity, thixotropic index, and working life are important parameters with respect to the dispense method used. Dispense methods include needle dispensing, stamping or pin transfer, and screen or stencil printing. Needle dispensing is the most common method and allows uniform deposition of material at high speeds. The glass-transition temperature, thermal stability, shear strength, modulus, and fatigue resistance of the cured adhesive determine the strength and stress characteristics of the bond. The choice of ller material determines electrical and/or thermal conductivity, and formulations are available with metallic llers, such as silver and gold, to provide electrical conductivity, or with mineral oxides that provide thermal conductivity but are electrically insulating. Curing conditions are chosen to optimize the bond strength and physical properties of the adhesive while providing maximum efciency of assembly. The most commonly used materials are silver-lled conductive epoxies. Because of steady improvements, manufacturers provide materials with optimized physical properties and processing characteristics. In recent years, low modulus materials have been developed for use with larger chips and great attention has been given to developing formulations with fast or snap cure chemistry that increase throughput through the assembly line by allowing adhesive cure to be integrated into the adhesive dispense line. A list of die attach materials and their formulation type is shown in Table 7 along with selected physical property data. Encapsulation Resins. Encapsulation is the general process of surrounding the wire bonded chip with an electrically insulating material that protects the circuit from the environment, provides mechanical support for the chip lead frame assembly, and assists in conducting heat out of the package. Plastic encapsulation materials are in widespread use throughout the microelectronic industry and the majority of plastic packages are encapsulated using formulated epoxy molding compounds in a transfer molding process. In the molding process, lead frames are loaded into cavity molds and the mold halves are pressed together in a molding press. The molding compound charge is heated in a transfer pot until it is sufciently soft to be transferred under pressure through the mold runners and gates into the cavities. The mold compound is then held for a short period of time in the heated mold to allow curing to proceed. The mold halves are then separated and the molded lead frames are ejected and loaded into magazines for post-curing in a batch oven for 14 h at 175 C. The objective of post-curing is to complete resin cure such that the optimal thermomechanical properties of the resin are obtained. Parameters that are critical to the success of the process include mold pressure, compound viscosity, transfer pressure, mold temperature, and the geometry of the mold.

Table 7. Die Attach Adhesives and Their Formulation Type with Selected Physical Property Dataa Thermal conductivity, Thixotropic Modulus, Viscosity, Conductiveb T g , C W/mK index GPac m Pas (= cP) E E E T E E E E T I E E E I E E E E E E E E E T 240 67 30 70 193 120 25 20 68 87 10 1 64 35 50 78 68 99 >80 >80 >90 >100 >200 92 2 2 0.7 22 2.7 2.5 1.1 20 0.5 2.0 2.8 1.5 0.3 25 3.5 3.7 2.8 29 1.6 1.3 2.0 2.0 1.5 2.9 1.6 5 4.3 2.7 5.6 5.1 4.8 4.3 2.5 4.6 3.5 4.8 5.0 4.0 4.5 4.9 3.7 3.40 5.30 1.63 3.30 3.80 3.94 0.71 3.00 3.67 6.10 0.86 1.8 0.10 0.30 2.0 7.0 7.4 6.6 14,000 19,000 9,000 7,500 3,800 8,000 9,000 8,600 8,100 20,000 10,700 9,000 8,200 7,800 5,500 7,000 7,500 7,500 2,700 3,300 10,000 3,000 8,000 13,000

Supplier

Designation

Resin

Filler

Cure Oven Oven Snap Oven Snap Oven Fast oven Fast oven Oven Oven Snap Snap Snap Snap Oven Oven or snap Oven or snap Oven or snap Oven Oven Oven Fast oven Oven Snap

Ablestik Ablebond 71-1 Polyimide Silver Ablebond 826-1DS Epoxy Silver Ablebond 8322A Abletherrm 2600L Ablebond 979-1A Ablebond 84-1LMISR4 Epoxy Silver Ablebond 8340 Ablebond 8325L Abletherm 2600K Ablebond 84-3J Dexter QMI 505MT BMI Silver QMI 509 BMI Silver QMI 518 BMI Silver QMI 534 BMI Teond QMI 5030 Resin blend Silver Hysold K0110 Epoxy Silver Hysol K0111 Epoxy Silver Hysol K0120 Epoxy Silver Epotek H20E Epoxy Silver H20E-175 Epoxy Silver P 1011 Polyimide Silver E 3001 E 3081 T 6116 Alumina
a From bE

276

Refs. 6668. = Electrically conductive; T = thermally conductive; I = insulating. c To convert GPa to psi, multiply by 145,000. d Teon and Hysol are registered trademarks.

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Table 8. Generic Molding Compound Compositionb Component Epoxy resin Curing agent Cure accelerators Up to 60 <1 Concentration (wt% of resin) Binder Polymerization Catalyze cure Function Typical agents Epoxy cresol novalac (ECN resin) Acid anhydrides, amines, phenols Amines, imidazoles, organophosphines, Lewis acids Ground fused silica, alumina

Filler

6880

Decrease CTE Increase thermal conductivity Increase modulus Reduce resin bleed Reduce shrinkage Reduce residual stress Retard ammability

Flame retardant Mold-release agent

10 Trace

Adhesion promoter Coloring agent Stress-relief additives additives

Trace 0.5 Up to 25

Brominated epoxy, antimony trioxide Aids in release from mold Silicones, uorocarbon waxes, organic acid salts Enhance adhesion to IC Silanes, titanates Reduce photonic activity Carbon black Reduce device visability Inhibit crack propagation Silicones, acrylonitrile butadiene elastomers, poly(butyl acrylate) Reduce crack initiation Reduce CTE

a From

Ref. 69.

Modern epoxy molding compounds are multicomponent formulations whose exact compositions are highly proprietary. However, most materials are variations on the general composition (69) shown in Table 8. Commercial formulation are carefully formulated to provide materials that adhere strongly to all interfaces; have thermal and mechanical properties optimized to minimize stress arising from thermal expansion mismatch between the encapsulant, lead frame, and chip; have low moisture absorbance; have low shrinkage during molding; and have processing characteristics that provide for good moldability and short post-cure times. Early resin materials used in mold compound formulations were silicones, phenolic resins, and bisphenol-A or bisphenol-F epoxies. Because of shortcomings in performance, these materials have been displaced by epoxy phenol or cresol novalac resins (ECN resins) and by the biphenyl- and tris(triphenylmethane)type epoxies (70) (Fig. 20). The high cross-link density of ECN-based materials results in low moisture absorption rate and higher thermal stability than

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Fig. 20. General structures of epoxy resins used in semiconductor mold compounds.

bisphenol A epoxies. The choice of curing agent and cure accelerator not only determines the structure of the cured resin but also affects viscosity and reactivity. Anhydrides and amines are the most commonly used curing agents. Accelerators are catalysts that control the composition gel and cure times and can, as the case of Lewis acid catalysts, promote linear polymerization to form polyether linkages and thus modify the modulus of the resin by decreasing the number of network crosslinks. Filler materials are used to modify resin properties and are essential components in obtaining desired encapsulant properties (71). The preferred ller material is ground, fused quartz which has a CTE of 0.5 ppm/ C. A silica ller loading of 6870% reduces the CTE of the neat resin from 4050 ppm/ C to 2024 ppm/ C. Improved resins and spherical ller technology has allowed an increase in loading up to 85%, resulting in reduction of CTE to 1015 ppm/ C. Decreased CTEs provide improved thermal stability and thermal-shock resistance during wide temperature uctuations. Additional benets of increased ller loading are increased thermal conductivity, reduced moisture absorbance, and reduced shrinkage during molding. While generally increasing the encapsulant elastic modulus, llers decrease the exural and tensile strength and do not usually provide signicant enhancement to T g or to package heat distortion properties. Filler size, shape, and loading determine the rheology of the molten encapsulant. Filler materials are treated with adhesion promoters to increase the adhesion of the resin to

Table 9. Selected Properties of Commercial Semiconductor Molding Compounds Thermal conductivity, J/cms C 7.5 10 3 7.5 10 3 8.4 10 3 9.6 10 3 8.8 10 3 6.7 10 3 8.4 10 3 7.1 10 3 8.8 10 3 9.6 10 3 6.7 10 3 6.7 10 3 6.7 10 3 6.7 10 3 CTE 1 , ppm/ C 19 17 15 11 10 7 8 7 18 13 16 8 6 20 18 16 13 CTE 2 , ppm/ C 65 70 11 50 70 49 65 32 25 65 65 Flexural strength, MPa 138 131 138 118 107 137 167 167 177 147 137 127 118 118 Flexural modulus, GPa 16.6 15.2 16.6 20.5 16.9 26.5 25.5 27.5 13.2 18.6 16.2 27.0 27.5 15.7 12.7 12.7 11.3 Moisture absorption, wt% 0.43b 0.47b 0.46b 0.28b 0.39b 0.32c 0.30c 0.23c 0.6d 0.3d 0.35e 0.17d 0.18d 0.30 0.30 Resin type ECN Blend ECN ECN Blend ECN ECN BP BP

Supplier Dexter

Designation Hysola MG36F-25A Hysol MG46F Hysol MG52F-99B Hysol GR810 Hysol GR8800 CEL-9120 CEL-9200 CEL 9600 MP-8000A MP-8000C MP-7000 MP-7410TA HC-100-X1 EME 1100H2 EME 62002 EME 6300H1 EME 67101

Tg , C 170 160 155 155 200 135 120 145 158 150 125 120 160 155 165 168 175

Hitachi Chemical

279

Nitto Denko

Sumitomo-Bakelite (76)

a Hysol b After

is a registered trademark. 168 h at 85 C/85% rh. c After 20 h pressure cooker. d After boiling 48 h. e After 120 h at 85 C/85% rh.

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the ller, resulting in improved encapsulant mechanical strength and decreased moisture absorption. Commonly used adhesion promoters include organosilanes and organotitanates. Stress-relief additives, such as silicones and acrylonitrile butadiene elastomers, are often added to reduce the elastic modulus, improve toughness and exibility, and lower the compound CTE (72). The nal components added to the mold compound formulation are mold-release agents that aid in releasing the molded packages from the mold; ame retardants to reduce ammability; and coloring agents, generally carbon-black, that reduce device visibility and serve to distinguish one device type from another. Table 9 shows a listing of some commercial semiconductor molding compounds with selected physical data (7376).

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WILLIAM D. WEBER Arch Chemicals