This disclosure relates generally to curable and patternable materials for use in electronic devices, such as ultra-large scale interconnect (ULSI) structures. More specifically, this disclosure relates to patternable dielectric and conductive inks, the use of these inks in the structure of an electronic device and a method of forming said structure via a soft lithographic process.
Photolithography is process that can provide submicron-sized patterned features that serve as a template for the etching and deposition of functional thin films during the production of electronic circuitry. The general process associated with forming a structure using this technique involves multiple steps as depicted in
Soft lithographic processes provide an alternative printing and patterning technique. Soft lithography generally involves a patterning process that uses non-light sensitive chemicals and a non-photo mask with a variety of different patterning techniques, such as printing, stamping, molding or embossing. The most common material used in soft lithography as the means through which patterns are transferred during the process is a block of polydimethylsiloxane (PDMS). Several of the types of patterning techniques used in soft lithography include micro-contact printing (μCP), micro-molding in capillaries (MIMIC), replica molding (REM), micro-transfer molding (μTM), solvent assisted micro-molding (SAMM), and decal transfer microlithography (DTM). A more complete discussion of various soft lithographic processes used for the deposition of thin films is provided in U.S. Patent Publication 2007/0166479A1. Unfortunately, conventional soft lithographic processes suffer from problems associated with the reproducibility of patterned features.
In satisfying the above need, as well as overcoming the enumerated drawbacks and other limitations of the related art, the present invention generally provides a curable and patternable ink, along with a method of using the ink as part of a structure that performs a function in an electronic device. In addition, the present invention also provides a soft lithographic method of forming said structure on a substrate for use within the electronic device.
According to one aspect of the present disclosure, a soft lithographic method of forming a structure on a substrate for use in an electronic device is provided. This method generally comprises the steps of printing a patternable ink onto the surface of the substrate in a predetermined pattern to form a patterned ink layer, curing the patterned ink layer; metalizing at least a portion of the surface of the patterned ink layer; and forming a structure on the substrate capable of performing a function in the electronic device. The patternable ink comprises an aryl functionalized resin component dispersed in an organic solvent, such that the aryl functionalized resin component includes a predetermined combination of curable aryl functionalized silsesquioxane resins and linear aryl functionalized polysiloxanes. Alternatively, the aryl groups are phenyl groups, tolyl groups, xylyl groups, naphthyl groups, or mixtures thereof. The patternable ink may also further comprise at least one of a cure accelerator or catalyst, a low molecular weight cross-linker, an adhesion promoter, and an inhibitor.
The step of printing the patternable ink may comprise the use of roll printing, micro-contact printing, or nano-imprinting techniques. The performance of these techniques basically involves transferring the patternable ink onto the surface of a polydimethylsiloxane (PDMS) layer; forming the patterned ink layer on the PDMS layer; drying or gelling the interface between the patterned ink layer and the PDMS layer; bringing the patterned ink layer in contact with the surface of a substrate; and transferring the patterned ink layer from the PDMS layer to the surface of the substrate.
The drying or gelling of the interface is facilitated by absorption of the organic solvent of the patternable ink into the PDMS layer, while the transferring of the patterned ink layer from the PDMS layer to the surface of the substrate is facilitated by an incompatibility between the patterned ink layer and the PDMS layer. In general, this incompatibility represents a difference in surface energy exhibited by the patterned ink layer and the PDMS layer. More specifically, the surface energy exhibited by the patterned ink layer is higher than the surface energy exhibited by the PDMS layer. This difference in surface energy between the patterned ink layer and the PDMS layer is caused by the aryl functionalized resin component in the patternable ink comprising at least one aryl group up to approximately 20 mole % of aryl groups relative to the resin component. The curing of the patterned ink layer is generally accomplished via a hydrosilylation, hydrogenative coupling, or hydrolysis and condensation pathway.
According to another aspect of the present disclosure, an electronic device is provided that comprises a substrate; a cured ink layer located proximate to the surface of the substrate in a predetermined pattern; and at least one metallization layer. The cured ink layer comprises an aryl resin layer defined by TR, DRR, MRRR, and Q structural units according to the formula:
(TR)a(DRR)b(MRRR)c(Q)d
where (TR)a represents structural units of (R)SiO3/2; (DRR)b represents structural units of (R)2SiO2/2; (MRRR)c represents structural units of (R3)SiO1/2; and (Q)d represents structural units of SiO4/2, such that each R group is independently selected to be an aryl group; and the subscripts (a-d) represent the mole fraction of each structural unit according to the relationship (a+b+c+d)=1 with the subscripts (a) and (b) being greater than zero. The aryl groups are present in the aryl resin layer in an amount ranging from one aryl group up to approximately 20 mole % relative to the resin molecule. Alternatively, the aryl groups are phenyl groups.
The electronic device may be an ultra-large scale interconnect structure (ULSI), a plasma display panel (PDP), a thin film transistor liquid crystal display (TFT-LCD), a semiconductor device, a printed circuit board (PCB), or a solar cell. The electronic device may further comprise at least one of an encapsulation layer, a passivation layer, a solder bump, or a wire such that the cured ink layer reduces stress induced by the incorporation of the metallization layer or the solder bump into the structure.
According to yet another aspect of the present disclosure, a curable and patternable ink for use in forming a structure in an electronic device is provided. The curable and patternable ink generally comprises a first portion defined by structural units of (R)SiO3/2; a second portion defined by structural units of (R)2SiO2/2; and an organic solvent. Alternatively, the patternable ink further comprises a third portion defined by structural units of (R)3SiO1/2 and/or a fourth portion defined by structural units of SiO4/2. The R group is independently selected to be an aryl group, a methyl group, or a cross-linkable group with the number of aryl groups being present in an amount that is between one aryl group and approximately 20 mole % of aryl group relative to the patternable ink. The aryl groups are selected as phenyl groups, tolyl groups, xylyl groups, naphthyl groups, or mixtures thereof. The cross-linkable group is selected as a vinyl, Si—H, silanol, or alkoxy moiety that is capable of undergoing a hydrosilylation, hydrogenative coupling, or hydrolysis/condensation reaction. Alternatively, the curable and patternable ink further comprises at least one of a cure accelerator or catalyst, a low molecular weight cross-linker, an adhesion promoter, a conductive filler, a nonconductive filler, or an inhibitor.
The organic solvent in the curable and patternable ink has a boiling point greater than 130° C. The organic solvent may be selected to be diethylene glycol methyl ethyl ether propylene carbonate, propylene glycol methyl ether acetate, carbitol acetate, diethylene glycol ethyl ether or carbitol, ethyl lactate, r-butyrolactone, n-methyl 2-pyrrolidinone (NMP), n-butyl carbitol or a mixture thereof.
Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.
The following description is merely exemplary in nature and is in no way intended to limit the present disclosure or its application or uses. It should be understood that throughout the description and drawings, corresponding reference numerals indicate like or corresponding parts and features.
The present disclosure generally provides curable, patternable inks used in the fabrication of an electronic device exemplified by ultra-large scale interconnect (ULSI) structures. Alternatively, the present disclosure provides patternable inks suitable for reducing the stress induced by the metallization or solder bump incorporated into the structure. These patternable inks are preselected to be dielectric or conductive in nature and generally comprise a curable, aryl functionalized resin component dispersed in a solvent. Alternatively, the patternable ink further comprises at least one of a cure accelerator (e.g., catalyst), a low molecular weight cross-linker, or other additives, such as adhesion promoters, conductive fillers, and inhibitors. As used herein, the aryl groups present in the aryl functionalized resin component may, include, but not be limited to, phenyl groups, tolyl groups, xylyl groups, naphthyl groups, and mixtures thereof. Alternatively, the aryl groups present in the resin component are phenyl groups.
Referring to
In the representative example shown in
The aryl functionalized resin component generally comprises a predetermined combination of aryl functionalized silsesquioxane (SSQ) resins, and linear aryl functionalized polysiloxanes. Aryl functionalized SSQ resins and aryl functionalized polysiloxanes typically undergo crosslinking reactions, including but not limited to, hydrosilylation, hydrogenative coupling, or hydrolysis/condensation. Thus these aryl SSQ resins and aryl polysiloxanes may incorporate one or more of vinyl functionality, Si—H, silanol, and/or alkoxy functionality in order to undergo crosslinking via a catalyzed hydrosilylation, hydrogenative coupling, or hydrolysis and condensation pathway. The aryl functionalized resin component may also include low molecular weight cross-linkable molecules, including but not limited to aryl rich Si—H cross-linkers, to facilitate such crosslinking reactions. The patternable inks include a predetermined number of aryl groups in order to prevent the migration of the ink into the polydimethylsiloxane (PDMS) layer or block used in a soft lithographic process.
The aryl functionalized resin component in the patternable ink comprises a first portion defined by structural units of (R)SiO3/2 and a second portion defined by structural units of (R)2SiO2/2. Alternatively, the aryl functionalized resin component may further comprise a third portion defined by structural units of (R)3SiO1/2. The aryl functionalized resin may optionally include yet a fourth portion defined by structural units of SiO4/2. The aryl functionalized resin component may have a molecular weight within a range whose lower limit is 1000, alternatively 2000, or alternatively 3000 grams/mole, and the upper limit is 10,000, alternatively 15,000, or alternatively 20,000 grams/mole.
The R group is independently selected to be an aryl group, a methyl group, or a cross-linkable group with the number of aryl groups being predetermined to ensure that incompatibility between the ink and the PDMS substrate used in the printing process exists. The predetermined number of aryl groups present in the aryl functionalized resin component may range from at least one aryl group up to about 20 mole % of the cured patternable ink; alternatively up to about 15 mole %; alternatively up to about 10 mole %.
Crosslinking within the aryl functionalized resin component may be induced by at least one of the R groups in the resin component being a cross-linkable moiety, such as a vinyl, Si—H, silanol, or alkoxy moiety in order for the ink to undergo crosslinking via a hydrosilylation, hydrogenative coupling, or hydrolysis/condensation reaction. Crosslinking may also be induced in the aryl functionalized resin component through the addition of a low molecular weight, aryl rich cross-linker molecule, such as a phenyl rich, Si—H cross-linker (e.g., dimethyl hydrogen terminated phenyl silsesquioxane) to the curable, patternable ink. Such cross-linking reactions occur during the thermal cure or baking step associated with a soft lithographic process.
According to another aspect of the present disclosure, the curable, patternable inks are applied in a pattern to a substrate using a soft lithographic process 99 as shown in
Still referring to
Polydimethylsiloxane (PDMS) is used for the transfer layer or medium because of its low surface energy and release capability for the patternable ink. Resins used in the patternable ink layer, which include a predetermined amount of aryl functionality, are incompatible with the PDMS transfer layer. By incompatibility, reference is being made to the chemical and physical properties of each layer being such that the layers do not adhere to one another, such that the layers may be separated from one another when desired. For example, the ink layer exhibits a higher surface energy than PDMS. This difference in surface energy allows the ink to be released from the surface of the PDMS layer during the printing process.
Still referring to
Once the curable ink is transferred 102 to the surface of the PDMS layer, an ink layer is formed 104. The absorption of the solvent from the ink layer into the PDMS layer assists in the “drying” or “gelling” 106 of the ink layer at the interface between this layer and the PDMS layer. The properties exhibited by PDMS layers that are generally used as a transfer medium are described in more detail in Table 1(A-B). More specifically, the PDMS layer exhibits a hardness value on the order of about 20-30 Shore A, a tensile stress between about 2.4×105-5.5×106 Pa (35-800 psi), and an elongation factor in excess of 200%. The PDMS layer is highly acceptable to the absorption of organic solvents, such as terpineol, methylethyl carbitol, and carbitol acetate. Upon the absorption of the solvent from the ink layer by the PDMS layer, the dried or gelled ink layer is then capable of being transferred 108 to substrates, such as for example, glass or wafers. Once transferred 108 to the surface of the substrate, the dried or gelled ink layer may be cured by hard baking 110.
According to yet another aspect of the present disclosure, upon hard baking 110 the patternable ink, an aryl resin layer is formed that comprises TR, DRR, MRRR, and Q structural units according to the formula (F-1):
(TR)a(DRR)b(MRRR)c(Q)d (F-1)
wherein (TR)a represents structural units of (R)SiO3/2; (DRR)b represents structural units of (R)2SiO2/2; (MRRR)c represents structural units of (R)3SiO1/2; and (Q)d represents structural units of SiO4/2. Each R group is independently selected to be an aryl group, alternatively each R group is a phenyl group; and the subscripts (a-d) represent the mole fraction of each structural unit according to the relationship (a+b+c+d)=1 with the subscripts (a) and (b) being greater than zero.
The following specific examples are given to illustrate the disclosure and should not be construed to limit the scope of the disclosure. Those skilled-in-the-art, in light of the present disclosure, will appreciate that many changes can be made in the specific embodiments which are disclosed herein and still obtain alike or similar result without departing from or exceeding the spirit or scope of the disclosure.
One specific example, among many, of a patternable ink prepared according to the teachings of the present disclosure comprises an aryl functionalized resin component that includes structural units defined by a mixture of a phenyl (Ph) silsesquioxane (SSQ) resin as stored in a carbitol acetate solvent, a phenyl (Ph) linear polysiloxane, fumed silica, and a phenyl (Ph) rich, Si—H cross-linker. The SSQ resin provides structural units of (Ph)SiO3/2; the linear polysiloxane provides structural units of (Ph)2SiO2/2; the phenyl rich cross-linker provides structural units of (Ph)3SiO1/2; and the fumed silica provides structural units of SiO4/2. The aryl functionalized resin component is combined and mixed with a platinum catalyst, an adhesion promoter, and an inhibitor in a propylene glycol phenyl ether solvent. More specific information regarding the various amounts of the different resins, additives, and solvents that are combined to form the patternable ink formulation is provided in Table 2. The patternable ink is stored until applied to a substrate via a printing process.
In this Example, the patternable ink of Example 1 is applied to a substrate in a printing process 100 that is a form of roll printing known as Gravure Offset printing. Referring now to
Referring now to
In this Example, the patternable ink of Example 1 is applied during the construction of an electronic device via soft lithography 99 using a printing process 100 known as 3-D nano-imprinting. Referring now to
Once the patterned ink becomes imprinted onto the surface of the substrate, subsequent steps in the photolithographic process 99 can take place, including but not limited to hard baking 110 and metallization 115. Alternatively, additional steps may be performed, such as grinding, passivation, and application of solder balls.
A person skilled in the art will recognize that the measurements described are standard measurements that can be obtained by a variety of different test methods. The test methods described in the examples represents only one available method to obtain each of the required measurements.
The foregoing description of various embodiments of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Numerous modifications or variations are possible in light of the above teachings. The embodiments discussed were chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.
Filing Document | Filing Date | Country | Kind |
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PCT/US13/24727 | 2/5/2013 | WO | 00 |
Number | Date | Country | |
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61596316 | Feb 2012 | US |