Abstract:
A sprayable adhesive composition having a viscosity within the range of 0.5 Pa.s to 5.0 Pa.s, containing at least one colored filler present in an amount up to 50% by weight of the adhesive composition, is suitable for marking identifications or fiducials on semiconductor dies or wafers. The preferred resins include epoxy resins or combinations of an electron donor resin and an electron acceptor resin.

Description:
FIELD OF THE INVENTION 
     This invention relates to a material for laser marking semiconductor wafers, dies and devices. 
     BACKGROUND OF THE INVENTION 
     In the fabrication of microelectronic devices, many of the operations are performed using machines with machine-vision technology. Semiconductor dies and packaged semiconductor dies are marked with fiducials and identification marks that are readable by these machines, allowing the dies to be accurately identified and positioned on a chosen substrate, such as a circuit board. A preferred method of marking is to use a laser to inscript the fiducial or identification mark. This can be done on the inactive face of the die, which changes the color of the silicon, or on a marking film applied to the inactive face of the die or wafer. As dies and wafers become thinner, their physical integrity can be compromised by either of these methods; thus, there is a need for a marking medium that can be applied without physically jeopardizing the die or wafer. 
     SUMMARY OF THE INVENTION 
     This invention is an adhesive solution or dilute paste that can be applied to a die or wafer without physically contacting the die or wafer, and be inscripted by a laser for marking or identification. The adhesive solution or paste contains one or more colored fillers and is applied by spraying onto the non-active surface of the wafer or single die. The adhesive can be any adhesive that is currently used under similar fabrication steps for semiconductor packages, although epoxies or electron donor and electron acceptor adhesive systems are preferred. In addition to facilitating laser marking, the adhesive provides mechanical support, and protection from electrostatic shock and light induced bias. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Suitable fillers can be either light or dark colored pigments or dyes that are inert, have a particle size under 50 microns, preferably under 1 micron, are easily dispersible, nonabrasive and ionically clean. A preferred light colored filler is titanium dioxide; a preferred dark colored filler is carbon black, grade channel black. Alternatively, colored pigments and dyes can be used as fillers, and in those cases, color instead of symbols can act as the identifying mark. The following table lists various colors and the chemical composition of the pigment or dye to give those colors. 
     
       
         
               
               
             
           
               
                   
               
             
             
               
                 Crimson 
                 Anthraquinonoid, Dioxazine 
               
               
                 Crimson 
                 Anthraquinone 
               
               
                 Crimson 
                 Anthraquinone 
               
               
                 Crimson 
                 1:2 Dihydroxyanthraquinone Lake 
               
               
                 Crimson 
                 Quinacridone Pyrrolidone 
               
               
                 Crimson 
                 Quinacridone Pyrrolidone, Quinacridone 
               
               
                 Black 
                 Specified Carbon Black 
               
               
                 Black 
                 Carbon Black 
               
               
                 Blue 
                 Copper Phthalocyanine 
               
               
                 Blue 
                 Phthalocyanine Blue 
               
               
                 Blue 
                 Ultramarine Blue 
               
               
                 Ultramarine Blue 
                 Complex Silicate of Sodium and Aluminum with 
               
               
                   
                 Sulfur 
               
               
                 Deep Blue 
                 Phthalocyanine Complex 
               
               
                 Deep Blue 
                 Complex of Sodium—Aluminum—Silica containing 
               
               
                   
                 Sulphur, Phthalocyanine Alpha 
               
               
                 Light Blue 
                 Phthalocyanine, Titanium [Dioxide] 
               
               
                 Light Blue 
                 Titanium Dioxide, Chlorinated Phthalocyanine, 
               
               
                   
                 Phthalocyanine Beta 
               
               
                 Light Blue 
                 Zinc Oxide, Phthalocyanine Beta 
               
               
                 Blue Violet 
                 Dioxazine, Quinacridone 
               
               
                 Bright Green 
                 Arylide Yellow 10G, Chlorinated Copper 
               
               
                   
                 Phthalocyanine, Zinc Oxide 
               
               
                 Brown 
                 Monoazo Complex 
               
               
                 Brown 
                 Benzimidazolone 
               
               
                 Carmine 
                 Napthol Carbamide 
               
               
                 Carmine 
                 Naphthol ITR 
               
               
                 Carmine 
                 Quinacridone Red 
               
               
                 Carmine 
                 Quinacridone Pyrrolidone 
               
               
                 White 
                 Zinc Oxide 
               
               
                 Cyan 
                 Phthalocyanine Blue 
               
               
                 Dark Yellow 
                 Arylide Yellow RN 
               
               
                 Geranium 
                 Quinacridone, Anthraquinone 
               
               
                 Geranium 
                 Chlorinated Para Red, Quinacridone 
               
               
                 Green 
                 Phthalocyanine Green, Diarylide Yellow 
               
               
                 Green 
                 Phthalo Green, Arylide Yellow 10G 
               
               
                 Green 
                 Phthalo Green, Zinc White 
               
               
                 Green 
                 Phthalocyanine Green 
               
               
                 Green 
                 Phthalo Green, Monoazo Yellow 
               
               
                 Green 
                 Cadmium Sulfide, Cobalt Oxide 
               
               
                 Green 
                 Zinc Oxide, Titanium Dioxide Rutile, Stable 
               
               
                   
                 Monoazo, Phthalocyanine 
               
               
                 Green 
                 Arylamide Yellow, Synthetic Iron Oxide, 
               
               
                   
                 Chlorinated Copper Phthalocyanine 
               
               
                 Green 
                 Hydrated Chromium Oxide, Cadmium Sulfide 
               
               
                 Green 
                 Hansa Yellow 10G, Phthalocyanine Beta 
               
               
                 Green 
                 Disazo Pigment, Copper Phthalocyanine, Nickel- 
               
               
                   
                 Antimony Titanate 
               
               
                 Green 
                 Benzimidazolone, Phthalocyanine Green 
               
               
                 Green 
                 Polychloro Copper Phthalocyanine, Nickel- 
               
               
                   
                 Antimony Titanate, Monoazo Pigment 
               
               
                 Green 
                 Nickel-Antimony Titanate, Disazo Pigment, 
               
               
                   
                 Polychloro Copper Phthalocyanine 
               
               
                 Green 
                 Nickel-Antimony Titanate, Monoazo Pigment, 
               
               
                   
                 Copper Phthalocyanine 
               
               
                 Deep Green 
                 Nickeltitanium, Phthalocyanine 
               
               
                 Deep Green 
                 Phthalocyanine Green, Arylide Yellow FGL, 
               
               
                   
                 Titanium Dioxide 
               
               
                 Deep Green 
                 Chlorinated Phthalocyanine, Arylide Yellow, 
               
               
                   
                 Titanium Dioxide 
               
               
                 Deep Green 
                 Chlorinated Copper Phthalocyanine, Arylamide 
               
               
                   
                 Yellow 
               
               
                 Deep Green 
                 Polychloro Copper Phthalocyanine 
               
               
                 Deep Green 
                 Phthalocyanine with Extender 
               
               
                 Deep Green 
                 Trisulfonated Copper Phthalocyanine Lake, 
               
               
                   
                 Monoazo Pigment, Polychloro Copper 
               
               
                   
                 Phthalocyanine 
               
               
                 Deep Green 
                 Zinc Sulfide/Barium Sulfate, Monoazo Yellow, 
               
               
                   
                 Phthalocyanine Blue, Metal Complex 
               
               
                 Deep Green 
                 Chlorinated Copper Phthalocyanine, Arylamide 
               
               
                   
                 Yellow 
               
               
                 Deep Green 
                 Zinc Sulfide/Barium Sulfate, Monoazo Yellow, 
               
               
                   
                 Phthalocyanine Green 
               
               
                 Deep Green 
                 Arylide Yellow, Chlorinated Copper 
               
               
                   
                 Phthalocyanine 
               
               
                 Deep Green 
                 Disazo Pigment, Copper Phthalocyanine 
               
               
                 Deep Green 
                 Zinc Oxide, Titanium Dioxide Rutile, Synthetic 
               
               
                   
                 Ultramarine B29, Phthalocyanine, Stable Di- 
               
               
                   
                 Arylide 
               
               
                 Deep Green 
                 Hydrated Chromium Oxide, Phthalocyanine Green 
               
               
                 Deep Green 
                 Chlorinated Copper Phthalocyanine, Arylamide 
               
               
                   
                 Yellow 
               
               
                 Deep Green 
                 Chlorinated Phthalocyanine, Complex of Sodium— 
               
               
                   
                 Aluminum—Silica containing Sulphur, Cadmium 
               
               
                   
                 Sulfide 
               
               
                 Deep Green 
                 Chlorinated Phthalocyanine, Phthalocyanine 
               
               
                   
                 Alpha, Hansa Yellow 10G 
               
               
                 Deep Green 
                 Complex of Sodium—Aluminum—Silica containing 
               
               
                   
                 Sulphur, Chlorinated Phthalocyanine 
               
               
                 Deep Green 
                 Hydrated Chrome Oxide 
               
               
                 Deep Green 
                 Arylide, Copperphthalocyanine 
               
               
                 Deep Green 
                 Arylide, Copperphthalocyanine 
               
               
                 Light Green 
                 Phthalocyanine, Arylamide 
               
               
                 Light Green 
                 Arylide Yellow, Chlorinated Copper 
               
               
                   
                 Phthalocyanine 
               
               
                 Light Green 
                 Concentrated Cadmium Zinc Sulfide, Chlorinated 
               
               
                   
                 Copper Phthalocyanine 
               
               
                 Light Green 
                 Phthalocyanine, Titanium [Dioxide] 
               
               
                 Light Green 
                 Cadmium Sulfide, Chlorinated Phthalocyanine 
               
               
                 Light Green 
                 Titanium Dioxide, Arylamide Yellow, Copper 
               
               
                   
                 Phthalocyanine, Arylamide Yellow 
               
               
                 Light Green 
                 Arylide Yellow, Phthalo Green, Zinc White 
               
               
                 Light Green 
                 Chlorinated Copper Phthalocyanine, Arylamide 
               
               
                   
                 Yellow 
               
               
                 Light Green 
                 Monoazo Pigment, Polychloro Copper 
               
               
                   
                 Phthalocyanine 
               
               
                 Light Green 
                 Monoazo Pigment, Polychloro Copper 
               
               
                   
                 Phthalocyanine 
               
               
                 Light Green 
                 Zinc Sulfide/Barium Sulfate, Monoazo Yellow, 
               
               
                   
                 Phthalocyanine Green 
               
               
                 Light Green 
                 Chlorinated Copper Phthalocyanine, Arylamide 
               
               
                   
                 Yellow 
               
               
                 Light Green 
                 Monoazo Yellow, Phthalocyanine Blue 
               
               
                 Light Green 
                 Phthalo Green, Monoazo Yellow 
               
               
                   
               
             
          
         
       
     
     Either a single colored or light or dark filler, or one or more contrasting colored fillers, may be used. In those adhesives where more than one color pigment or dye is used, the different colors, after being blended into the adhesive, will naturally tend to segregate together making distinct layers by physical or chemical affinities. In most cases, the separation and segregation will occur due to gravity. 
     In the case where a single colored filler is used, the filler is preferably a dark colored filler because the laser energy is absorbed more strongly by a dark layer than by a light layer. This increased energy absorption makes it faster to cut through a dark layer than through a light layer. When two or more contrasting colored fillers are used, the lighter or lightest colored filler should be chosen to be heaviest or densest filler so that it settles proximate to the die or wafer. Because a dark filler is cut or burned out by the laser easier and faster than a light filler would be, when the laser reaches the light colored filler the laser cut or burn out will slow considerably or halt. As a result, the depth of the laser cut or burn is to some extent self-regulating. 
     As will be recognized by those skilled in the art, different pigments and dyes have different refractive indices and energy absorption rates. Therefore, the laser chosen for accomplishing the marking or identification can be tuned to an appropriate energy for the pigment or dye present in the adhesive. If the laser energy is fixed, the pigment or dye can be chosen based on a refractive index that will correspond to the wavelength of the laser. Conventionally, the lasers used within the microelectronics industry for marking semiconductor dies and packages have a wavelength of 1064 nm or 532 nm. 
     Fluorescent color brighteners can be added to enhance the optical clarity and optical pick-up recognition of the fillers. An example of a fluorescent brightener or color enhancer is Calcofluor M2R, supplied by Sigma-Aldrich, with a preferred loading level of 0.1 to 2.0% by weight. The structure of Calcofluor is: 
     
       
                 
         
             
             
         
      
     
     The colored filler or fillers are dispersed into the adhesive resin by using a high shear mixer (in the range of 3000 to 5000 rpm) and/or a triple roll mixer. Shearing continues until the filler is stabilized within the adhesive. Preferred loading levels range from 5 to 50 percent by weight for each of the dark and light fillers and can be varied by the practitioner depending on the color configuration desired. The higher loading range typically would be used for higher levels of UV or light shielding required for some photosensitive devices. The filled adhesive is applied by spraying onto the wafer or individual dies. A preferred spray head is Asymtek EFD 780S-ss spray head. Deposition can be accomplished by spraying in a back and forth motion conforming to the shape of the wafer or die, or in concentric circles. With minimal practice, the limits of the spray motion can be determined so that excess adhesive does not contaminate the active surface of the wafer or die. Sufficient adhesive is deposited to leave a layer after cure within the range of 12.5 μm to 150 μm; a referred range is 25 μm to 50 μm. 
     Preferred adhesives include epoxy resins; acrylic resins; and bismaleimide resins in combination with vinyl ethers, vinyl silanes, styrenic compounds, or cinnamyl compounds. 
     Examples of epoxy resins include glycidyl ethers, such as those based on bisphenol A (commercially available from Resolution Technology) or bisphenol F (commercially available from CVC Specialty Chemicals of Maple Shade, N.J., under the designation 8230E, and from Resolution Performance Products LLC under the designation RSL1739); a blend of bisphenol-A and bisphenol-F (commercially available from Nippon Chemical Company under the designation ZX-1059; polyglycidyl ethers of phenol or cresol novolacs (commercially available from Vantico as EPN 1138); biphenyl epoxy resin (made by reaction of biphenyl resin with epichlorohydrin); epoxy resins based on dicyclopentadiene; epoxy resins based on naphthalene; epoxy functional butadiene/acrylonitrile copolymers; epoxy functional polydimethyl siloxane; cycloaliphatic epoxy resins (such as, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate); vinylcyclohexene dioxide; 3,4-epoxy-6-methyl cyclohexyl methyl-3,4-epoxycyclohexane carboxylate; and dicyclopentadiene dioxide. 
     Other suitable resins for making sprayable adhesive include compounds with the following structures (in which C 34  is a linear or branched hydrocarbon chain with 34 carbon atoms): 
     
       
                 
         
             
             
         
      
     
     For these epoxy resins, a suitable catalyst, in addition to those commercially available, is an imidazole-anhydride adduct. Preferred imidazoles for forming the adduct include non-N-substituted imidazoles, such as, 2-phenyl-4-methyl imidazole, 2-phenyl imidazole, and imidazole. Other useful imidazole components for the adduct include alkyl-substituted imidazoles, N-substituted imidazoles, and mixtures of those. 
     Suitable acrylic resins include those available from Sartomer. Suitable bismaleimide resins include those available from Ciba Specialty Chemicals or National Starch. Suitable vinyl ethers and vinyl silanes are easily available commercially, for example, from Aldrich. 
     Suitable cinnamyl compounds for use in combination with maleimides include: 
                                
in which C 36  represents a linear or branched alkyl of 36 carbons derived from linoleic and oleic acids.
 
     Suitable styrenic compounds for use in combination with maleimides include: 
                                
in which C 36  represents a linear or branched alkyl of 36 carbons derived from linoleic and oleic acids.
 
     Curing agents such as free radical initiators, thermal initiators and photoinitiators will be present in an effective amount to cure the composition. In general, those amounts will range from 0.1% to 30%, preferably 1% to 20%, by weight of the total organic material (that is, excluding any inorganic fillers) in the composition. The actual cure profile will vary with the components and can be determined without undue experimentation by the practitioner. Suitable curing methods for the adhesive are thermal cures or radiation cures, such as UV curing. 
     Solvents can be utilized to modify the viscosity of the composition, and if used should be chosen so that they are compatible with the adhesive resin and so that they evaporate during curing of the resin. Examples of suitable solvents include 1-methoxy-2-propanol, propylene glycol methyl ether acetate, glycol ether, glycol acetate, glycol alcohol, and dipropylene glycol methyl ethyl ether. A workable viscosity range for the filled adhesive is 0.5 to 5.0 Pa.s, although the preferred viscosity is under 0.5 Pa.s. 
     The adhesive compositions may further comprise nonconductive or thermally or electrically conductive fillers. Suitable nonconductive fillers are particles of vermiculite, mica, wollastonite, calcium carbonate, titania, sand, glass, fused silica, fumed silica, barium sulfate, and halogenated ethylene polymers, such as, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidene chloride, and vinyl chloride. Suitable conductive fillers are carbon black, graphite, gold, silver, copper, platinum, palladium, nickel, aluminum, silicon carbide, diamond, and alumina. If used, fillers generally will be present in amounts up to 90% by weight of the adhesive composition. 
     EXAMPLES  
     Two formulations were prepared as follows: Formulation A contained by weight 23% solid epoxy resin, 9% liquid epoxy resin, 10% phenolic hardener, 0.1% imidazole catalyst, 50% solvent, 0.1% silane adhesion promoter, 6.2% carbon black and 0.1% blue pigment (to enrich the black). Formulation A had a viscosity of 0.58 Pa.s. Formulation B contained by weight 22% solid epoxy resin, 9% liquid epoxy resin, 10% phenolic hardener, 0.5% imine catalyst, 49% solvent, 0.1% silane adhesion promoter, 6% carbon black, 3% titanium dioxide and 0.2% blue pigment. Formulation B had a viscosity of 0.33 Pa.s. 
     Formulations A and B were sprayed onto the inactive surface of a five inch silicon wafer using an Asymtek EFD 780S-ss spray head to a thickness of 50 μm. The adhesives were heated on the wafer for 10 minutes at 130° C. to evaporate the solvent and then cured by heating at 150° C. for 30 minutes. The wafer was then diced into four quadrants and each quadrant attached to a lead frame ball grid array semiconductor device. Each quadrant was marked with an identification mark using a Rofin sinar RSG 1010-4 laser at 18 A current, 680 mm/sec, 65 KHz. Legibility was good in all cases with differences between the marking and surface of the coating being the color and contrast of the mark.