CN114555674A - Photosensitive composition and application thereof - Google Patents

Photosensitive composition and application thereof Download PDF

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CN114555674A
CN114555674A CN201980101333.4A CN201980101333A CN114555674A CN 114555674 A CN114555674 A CN 114555674A CN 201980101333 A CN201980101333 A CN 201980101333A CN 114555674 A CN114555674 A CN 114555674A
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bis
group
diyl
photosensitive composition
methyl
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B·卡纳普
C·伯恩斯
C·谢尔格
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Promerus LLC
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    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
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    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
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    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/016—Diazonium salts or compounds
    • G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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    • C08G2261/10—Definition of the polymer structure
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Abstract

The present invention relates to a photosensitive composition comprising Polynorbornene (PNB) polymer and specific additives useful for forming microelectronic and/or optoelectronic devices and components thereof, and more particularly to a composition comprising PNB and specific multifunctional crosslinking agent and two or more phenolic compounds, which is resistant to thermo-oxidative chain degradation and exhibits improved mechanical properties.

Description

Photosensitive composition and application thereof
Technical Field
Embodiments in accordance with the present invention generally relate to a Polynorbornene (PNB) composition comprising various additives useful in forming microelectronic and/or optoelectronic devices and components thereof, and more particularly to a composition comprising a PNB having at least one norbornene-type repeating unit comprising a terminal functionalized polyether, wherein such composition exhibits improved thermal, mechanical and optoelectronic properties.
Background
Organic polymeric materials are increasingly used in a variety of applications in the microelectronics and optoelectronics industries. Uses for such organic polymer materials include, for example, interlayer dielectrics, redistribution layers, stress buffer layers, leveling or planarization layers, alpha particle barrier layers, and passivation layers for microelectronic and optoelectronic devices. Since such organic polymeric materials are photosensitive and self-imageable, there is an additional advantage of reducing the number of processing steps required for the use of such layers and structures made from such materials. In addition, such organic polymer materials can be directly bonded to devices and device components to form a variety of structures. Such devices include micro-electromechanical systems (MEMS) and micro-opto-electromechanical systems (MOEMS).
While Polyimide (PI), Polybenzoxazole (PBO) and benzocyclobutane (BCB) compositions have been the materials of choice for these various applications because they generally have good thermal stability and mechanical strength, each of these materials is formed during curing from precursors that react to alter the backbone (PI and PBO) of the polymer or form the backbone (BCB), and thus typically require specific processing conditions during curing to remove by-products formed during curing and/or to remove oxygen or water vapor that can prevent curing. Furthermore, curing of such materials typically requires process temperatures in excess of 250 ℃ (some materials are as high as 400 ℃), resulting in excessive or unnecessary process costs. Thus, such materials may not be suitable for applications such as redistribution and interlayer dielectric layers, and direct bonding that covers transparent covers over image sensing arrays.
Accordingly, it is believed that there is a need to provide a material useful for forming the above-described structures that exhibits thermal stability and mechanical strength equivalent to known PI, PBO and BCB compositions, wherein such material has a fully formed polymer backbone that is capable of curing at temperatures below 200 ℃. In addition, such advantageous materials should be tunable in properties to provide appropriate levels or values of stress, modulus, dielectric constant, elongation at break, and permeability to water vapor for the application. Furthermore, it is advantageous that such materials are self-imageable. Also, several compositions currently available may not be suitable for some applications because these do not have the desired Dissolution Rate (DR) characteristics including resolution and photospeed as described in further detail below.
Although the polynorbornene-based photosensitive compositions described in U.S. Pat. nos. 9,341,949 and 9,696,623 have successfully overcome some of the above problems, there is still a need to provide suitable flexible materials having the necessary adhesive strength and mechanical strength, particularly in terms of wafer shear strength for the manufacture of various micro-optoelectronic devices such as display devices.
Accordingly, there remains a need to develop a self-imageable photopolymer composition having desirable thermal properties, dissolution rates, orthogonality to the various solvents used in different steps in the device manufacturing process, adhesion, and most importantly, integration into all relevant process steps.
Drawings
Embodiments according to the present invention are described below with reference to the following drawings and/or images. The accompanying drawings, which are simplified portions of various embodiments of the present invention, are provided for illustration purposes only.
FIGS. 1A-1D show lithographic images formed from compositions of the present invention at various exposure doses.
Figure 2 shows the wafer shear strength of the inventive composition compared to a comparative composition.
Detailed Description
Embodiments in accordance with the present invention relate to a self-imageable composition comprising norbornene-type polymers and films, layers, structures, devices, or components that can be formed using such compositions. Some embodiments include self-imageable compositions that are capable of providing positive tone images after imagewise exposure of a film formed from the composition, followed by development of the images using an aqueous alkaline developing solution.
In addition, embodiments described herein generally provide a film having a desired thickness in the range of about 2 to 5 micrometers (μm) or more, where the image exhibits isolated line/groove resolution with an aspect ratio greater than 1: 2. Films, layers and structures formed from polymers of embodiments of the present invention are particularly useful for interlayer dielectrics, redistribution layers, stress buffer layers, leveling or planarization layers, alpha particle barrier layers, and for forming chip stacks and for fixedly attaching transparent covers over image sensing arrays used in microelectronic and optoelectronic devices and components formed therefrom.
The terms used in this specification have the following meanings:
unless otherwise indicated, all numbers, values, and/or expressions referring to amounts of ingredients, reaction conditions, polymer compositions, formulations, and the like used in the specification are in any event modified by the term "about" because the numbers are approximations that inherently reflect the various uncertainties in the measurements made at the time the values are obtained. Further, unless otherwise indicated, when numerical ranges are disclosed in this specification, such ranges are continuous and include every value from the minimum to the maximum of the range. Further, when these ranges refer to integers, each integer from the minimum to the maximum is included unless otherwise specified. Also, where multiple ranges are provided to illustrate a single feature or characteristic, the ranges can be combined to illustrate the feature or characteristic.
As used in this specification, the articles "a" and "an" and "the" include plural referents unless expressly limited to one referent.
It is to be understood that, as used in this specification, the phrase "microelectronic device" includes "micro-optoelectronic devices" and "optoelectronic devices". Thus, references to microelectronic devices or microelectronic device assemblies include optoelectronic devices and micro-optoelectronic devices and assemblies thereof. Likewise, microelectromechanical systems (MEMS) include micro-opto-electromechanical systems (MOEMS).
It should be understood that the term "redistribution layer" (RDL) refers to an electrical signal routing insulating material having the desired reliable characteristics. The term RDL may also be used interchangeably to describe a desired buffer coating, such as a stress relief or buffer layer between a solder ball and a fragile low K structure.
As used in this specification, the term "polymer" is to be understood as a molecule comprising a backbone of more than one different type of repeating unit (the smallest constitutional unit of the polymer), which polymer comprises, in addition to the polymer itself, residues from initiators, catalysts and other elements that accompany the formation of these polymers, wherein these residues are not normally considered to be covalently bonded thereto, but may be covalently bonded to the front or back end of the polymer chain as in some catalyst-initiated polymerizations. In addition, although these residues and other elements are typically removed during post-polymerization purification, they are typically mixed or blended with the polymer and thus, when transferred between vessels or between solvents or dispersion media, typically leave a small amount of residue.
As used herein, the term "polymer composition" is meant to include at least one synthetic polymer, as well as materials added after polymerization to provide or improve specific properties. Exemplary materials that can be added include, but are not limited to, solvents, photoactive compounds (PACs), dissolution rate inhibitors, dissolution rate enhancers, dissolution promoters, crosslinking moieties, reactive diluents, antioxidants, adhesion promoters, and plasticizers.
As used in this specification, the term "modulus" is to be understood as the ratio of stress to strain, and unless otherwise specified, means the young's modulus or tensile modulus measured in the linear elastic region of the stress-strain curve. Modulus values are typically measured according to ASTM method DI 708-95. It is believed that films with low modulus also have low internal stress.
The term "photosensitive" refers to a property of a material or material composition, such as a polymer or polymer composition according to embodiments of the present invention, which itself will be formed into a patterned layer or structure. In other words, the "photosensitive layer" does not require the use of another material layer, such as a photoresist layer, formed thereon to form the patterned layer or structure described above. It will be further appreciated that polymer compositions having such properties are typically used in patterning schemes to form patterned films/layers or structures. It should be noted that such schemes include "imagewise exposure" of the photosensitive material or layer formed therefrom. This imagewise exposure refers to exposing selected portions of the layer to actinic radiation while protecting the unselected portions from such actinic radiation exposure.
As used in this specification, the term "self-imageable composition" will be understood to mean a material that is photosensitive and therefore capable of providing a patterned layer and/or structure after direct imagewise exposure of a film formed from the composition, followed by development of the image on the film using a suitable developer.
As used herein, "hydrocarbyl" refers to a radical or group containing only carbon and hydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl groups. The term "halohydrocarbyl" refers to a hydrocarbon group in which at least one hydrogen atom is replaced with a halogen atom. The term "perhalohydrocarbyl (perhalocarbyl)" refers to a hydrocarbyl group in which all hydrogens are replaced with halogens. The term "heterohydrocarbyl" refers to any of the above hydrocarbyl, halohydrocarbyl and perhalohydrocarbyl groups in which at least one carbon atom of the carbon chain is substituted with N, O, S, Si or a P atom.
As used in this specification, the term "a", "an", "the" or "the" is intended to mean,
Figure BDA0003596213870000041
denotes a structure according to the indicated radical with another repeating unit or anotherThe position at which the bonding of an atom or molecule or group or part occurs.
As used in this specification, the expression "alkyl" refers to a saturated straight or branched hydrocarbon substituent having the specified number of carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, tert-butyl and the like. Derivatisation expressions such as "alkoxy", "thioalkyl", "alkoxyalkyl", "hydroxyalkyl", "alkylcarbonyl", "alkoxycarbonylalkyl", "alkoxycarbonyl", "diphenylalkyl", "phenylalkyl", "phenylcarboxyalkyl" and "phenoxyalkyl" are to be interpreted accordingly.
As used in this specification, the expression "cycloalkyl" includes all known cyclic aliphatic radicals. Representative examples of "cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Derivatizing terms such as "cycloalkoxy", "cycloalkylalkyl", "cycloalkylaryl" and "cycloalkylcarbonyl" are to be construed accordingly.
As used in this specification, the expression "alkenyl" refers to an acyclic, straight or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond, and includes ethenyl and straight or branched propenyl, butenyl, pentenyl and hexenyl. Likewise, the expression "alkynyl" refers to an acyclic, linear or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon triple bond, and includes ethynyl and propynyl as well as linear or branched butynyl, pentynyl and hexynyl groups.
As used herein, the expression "acyl" shall have the same meaning as "alkanoyl", which can also be structurally represented by "R-CO-", wherein R is "alkyl" as defined herein having a particular number of carbon atoms. Further, "alkylcarbonyl" shall have the same meaning as acyl defined in the specification. Specifically, "(C)1-C4) Acyl "shall mean formyl, acetyl (acetyl or ethanoyl), propionyl, n-butyryl and the like. The expressions derived such as "acyloxy" and "acyloxyalkyl" are to be interpreted accordingly.
As used in this specification, the expression "perfluoroalkyl" means that all hydrogen atoms in the above alkyl group are replaced by fluorine atoms. Illustrative examples include trifluoromethyl and pentafluoroethyl, straight or branched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl. The expression "perfluoroalkoxy" should be interpreted accordingly.
As used in this specification, the expression "aryl" refers to a substituted or unsubstituted phenyl or naphthyl group. Specific examples of the substituted phenyl group or the substituted naphthyl group include o-, p-, m-tolyl group, 1,2-, 1,3-, 1, 4-xylyl group, 1-methylnaphthyl group, 2-methylnaphthyl group and the like. "substituted phenyl" or "substituted naphthyl" also includes any possible substituent as further defined in the specification or known in the art. The expression "arylsulfonyl" for derivatization should be interpreted accordingly.
The expression "arylalkyl" or "aralkyl" is used interchangeably in the present description, in particular "(C)6-C10) Aryl radical (C)1-C4) Alkyl or (C)7-C14) Aralkyl group "means (C) shown in the present specification6-C10) Aryl is further bonded to (C) described in the specification1-C4) An alkyl group. Representative examples include benzyl, phenethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.
As used in this specification, the expression "heteroaryl" includes all known heteroatom-containing aromatic groups. Representative 5-membered ring heteroaryls include furyl, thienyl (thienyl or thiophenyl), pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl and the like. Representative 6-membered ring heteroaryls include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like. Representative examples of bicyclic heteroaryl groups include benzofuranyl, benzothienyl, indolyl, quinolinyl, isoquinolinyl, cinnamyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl, and the like.
As used in this specification, the expression "heterocyclic" includes all known reduced heteroatom containing cyclic groups. Representative 5-membered heterocyclic groups include tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, and the like. Representative 6-membered heterocyclyl groups include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like. Various other heterocyclic groups include, but are not limited to, aziridinyl (aziridyl), azepanyl (azepanyl), diazepanyl (diazepanyl), diazabicyclo [2.2.1] hept-2-yl, triazacyclooctanyl (triazacyclocanyl), and the like.
"halogen" or "halo (halo)" refers to chlorine, fluorine, bromine and iodine.
In a broad sense, the term "substituted" can include all permissible substituents of organic compounds. In some embodiments disclosed in the specification, the term "substituted" refers to substitution with one or more substituents independently selected from the group comprising: (C)1-C6) Alkyl, (C)2-C6) Alkenyl, (C)1-C6) Perfluoroalkyl, phenyl, hydroxy, -CO2H. Ester, amide, (C)1-C6) Alkoxy group, (C)1-C6) Thioalkyl, (C)1-C6) Perfluoroalkoxy, NH2Cl, Br, I, F, NH lower alkyl and-N (lower alkyl)2. However, any other suitable substituent known to those skilled in the art can also be suitable for use in these embodiments.
As used in this specification, the term Organic Field Effect Transistor (OFET) is to be understood as including a sub-class of such devices known as Organic Thin Film Transistors (OTFTs).
It should be understood that the terms "dielectric" and "insulating" are used interchangeably in this specification. Thus, reference to an insulating material or layer includes a dielectric material or layer and vice versa. Furthermore, as used in this specification, the term "organic electronic device" should be understood to include the term "organic semiconductor device" and several embodiments of such a device, such as an Organic Field Effect Transistor (OFET).
As used in this specification, the terms "orthogonal" and "orthogonality" are understood to mean chemical orthogonality. For example, an orthotropic solvent refers to a solvent in which a layer of a material dissolved therein is deposited on a previously deposited layer without dissolving or swelling the previously deposited layer.
As used in this specification, the terms "polycycloolefin," "poly (cyclo) olefin," and "polynorbornene-type" are used interchangeably to refer to polymers formed from addition polymerizable monomers, repeating units in the resulting polymers, or compositions comprising such polymers, wherein the repeating units of the resulting polymers comprise at least one norbornene-type moiety. The simplest norbornene-type polymerizable monomer included according to the embodiment of the present invention is norbornene itself, that is, bicyclo [2.2.1] hept-2-ene shown below.
Figure BDA0003596213870000061
However, the terms norbornene-type monomer, norbornene-type repeating unit or norbornene-type Polymer (PNB) used in the present specification are not limited to containing only a portion of norbornene itself, but also include substituted norbornenes or substituted or unsubstituted higher cyclic derivatives derived therefrom.
Certain additives are known to significantly improve the performance of the compositions when used in combination with the compositions of the present invention in forming thick or thin films that can be used in a variety of applications including, but not limited to, mechanical, electronic, or electromechanical devices, including chip-on-chip applications, as dam structures for redistribution layer (RDL) and Complementary Metal Oxide Semiconductor (CMOS) image sensors, and various other MEMS and MOEMS containing devices.
Thus, according to an embodiment of the present invention, there is provided a photosensitive composition comprising:
a) a polymer having:
a first type of recurring unit of formula (IA) derived from a monomer of formula (I):
Figure BDA0003596213870000071
a second type of recurring unit of formula (IIA) derived from a monomer of formula (II):
Figure BDA0003596213870000072
and
a third type of recurring unit of formula (IIIA) derived from a monomer of formula (III):
Figure BDA0003596213870000073
wherein:
Figure BDA0003596213870000074
indicates a position bonded to another repeating unit;
a is an integer of 0-3;
b is an integer of 1-4;
c is an integer of 1-4;
R1selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl and n-butyl, wherein more than one methylene is CH2The radicals may optionally be selected from (C)1-C4) Alkyl, phenyl and phenyl (C)1-C4) The groups in the group of alkyl groups are independently substituted;
R18is selected from- (CH)2)s-、-(CH2)t-OCH2-or- (CH)2)t-(OCH2CH2)u-OCH2-, wherein
s is an integer of 0 to 6,
t is an integer of 0 to 4,
u is an integer of 0 to 3,
R19is- (CH)2)v-CO2R20Wherein v is an integer of 0 to 4, and
R20is hydrogen or C1-C4An alkyl group;
b) a photoactive compound comprising a diazoquinone moiety of the general formula (a):
Figure BDA0003596213870000081
c) a multifunctional crosslinker selected from the group comprising:
a compound of the general formula (IV):
Figure BDA0003596213870000082
and
a compound of the general formula (V):
Figure BDA0003596213870000083
wherein:
n is an integer of 5-8;
a is selected from the group consisting of C, CH- (CR)2)d-CH and substituted or unsubstituted aryl, wherein d is an integer from 0 to 4 and R is selected from the group comprising hydrogen, methyl, ethyl, n-propyl, isopropyl and n-butyl;
b is selected from the group consisting of substituted or unsubstituted (C)2-C6) Alkylene and substituted or unsubstituted aryl;
wherein said substituents are selected from the group consisting of halogen, methyl, ethyl, straight or branched chain (C)3-C6) Alkyl, (C)3-C8) Cycloalkyl, (C)6-C10) Aryl group, (C)7-C12) Aralkyl, methoxy, ethoxy, straight or branched chain (C)3-C6) Alkoxy group, (C)3-C8) Cycloalkoxy, (C)6-C10) Aryloxy group and (C)7-C12) A group of aralkyloxy groups;
d) a phenolic compound selected from the group comprising:
Figure BDA0003596213870000091
Figure BDA0003596213870000092
and
Figure BDA0003596213870000093
e) a compound of the general formula (VI):
Figure BDA0003596213870000101
wherein d and e are integers of 1 to 4;
f and g are integers of 0 to 4;
R2and R3Are the same or different and are each independently selected from hydrogen, methyl, ethyl, straight or branched C3-C6Alkyl radical, C3-C8Cycloalkyl radical, C6-C10Aryl and C7-C12Aralkyl group; or
R2And R3Together with the carbon atom to which they are attached form a 5-to 8-membered substituted or unsubstituted carbocyclic ring, wherein the substituents are selected from C1-C8An alkyl group;
R4and R5Are identical or different and are each independently selected from hydrogen, methyl, ethyl, linear or branched (C)3-C6) Alkyl, (C)3-C8) Cycloalkyl group, (C)6-C10) Aryl and (C)7-C12) An aralkyl group.
In some embodiments, the polymers of the present invention comprise a repeat unit of formula (IIIA), wherein R is20Typically hydrogen. However, in some embodiments polymers comprising a mixture of repeating units having the general formula (IIIA), wherein a portion of the repeating units having the general formula (IIIA) have R20As hydrogen and having R in the other part of the repeating unit of the formula (IIIA)20As (C)1-C4) An alkyl group. Thus, those skilled in the art will appreciate that these variations are all present inventionsIn the clear.
Non-limiting examples of monomers that can be used to form the first repeat unit of the present invention include the following:
Figure BDA0003596213870000102
5- ((2- (2-methoxyethoxy) ethoxy) methyl) bicyclo [2.2.1] hept-2-ene, also known as trioxononenorbornene (NBTON);
Figure BDA0003596213870000103
1- (bicyclo [2.2.1] hept-5-en-2-yl) -2,5,8, 11-tetraoxadodecyl, also known as tetraoxadodecyl Norbornene (NBTODD);
Figure BDA0003596213870000111
5- (3-methoxybutoxy) methyl-2-norbornene (NB-3-MBM);
Figure BDA0003596213870000112
5- (3-methoxypropanyloxy) methyl-2-norbornene (NB-3-MPM);
Figure BDA0003596213870000113
5- (2- (2-ethoxyethoxy) ethyl) bicyclo [2.2.1] hept-2-ene; and
Figure BDA0003596213870000114
5- (2- (2- (2-propoxyethoxy) ethoxy) bicyclo [2.2.1] hept-2-ene; non-limiting examples of monomers that can be used to form the second repeat unit of the present invention include the following:
Figure BDA0003596213870000115
norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);
Figure BDA0003596213870000116
4- (bicyclo [2.2.1]]Hept-5-en-2-yl) -1,1, 1-trifluoro-2- (trifluoromethyl) butan-2-ol (HFACH)2NB); and
Figure BDA0003596213870000117
5- (bicyclo [2.2.1]]Hept-5-en-2-yl) -1,1, 1-trifluoro-2- (trifluoromethyl) pent-2-ol (HFACH)2CH2NB)。
Non-limiting examples of monomers that can be used to form the second repeat unit of the present invention include the following:
Figure BDA0003596213870000121
ethyl 3- (bicyclo [2.2.1] hept-2-en-2-yl) propionate (EPEsNB);
Figure BDA0003596213870000122
3- (bicyclo [2.2.1] hept-5-en-2-yl) acetic acid (NBMeCOOH);
Figure BDA0003596213870000123
norbornenylpropionic acid (nbetoh); and
Figure BDA0003596213870000124
bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (alcohol NB);
it should be noted that the photosensitive composition of the present invention can be prepared by using a polymer derived from any three monomers listed above within the range of the monomers of the general formulae (I) to (III). In addition, any amount of monomers of formulas (I) - (III) can be used to form a polymer that provides the desired benefits and objectives as described below. All of these possible monomer ratios are therefore part of the present invention.
In some embodiments of the present invention, the photosensitive composition of the present invention is prepared by using a terpolymer comprising any three monomers described in the present specification.
In general, polymers according to embodiments of the present invention include more than one of the first, second, and third different types of repeat units described above, and as will be seen below, other repeat units included in such polymer embodiments are selected in such a way as to impart properties to such polymer embodiments that contribute to the utility of such embodiments, and thus such polymer embodiments are suitable for various specific applications.
For example, polymer embodiments typically require at least one repeat unit for providing imageable properties. Thus, carboxylic acids R having pendant groups may be included in the different types of repeating units represented by formula (IIIA)19. However, any other functional group that brings acidic side groups can be used instead. The pendant carboxylic acid groups are generally useful for reacting with appropriately selected additives or other repeating units capable of fixing positive tone images by post-development thermal crosslinking. Thus, similar side groups including, but not limited to, phenolic groups, sulfo groups, and other functional groups may also function in embodiments of the present invention. It should also be noted that one skilled in the art would readily understand that such polymer compositions containing acidic side groups can be prepared by post-polymerization using appropriate monomers. For example, polymers comprising NBEtCOOH monomeric repeat units can generally be prepared as follows: first forming the polymer with EPEsNB, and thenThe ester functions of the obtained polymer are hydrolyzed by any method known in the art. Thus, a certain balance of ester monomer repeat units may be consistently present in the polymers used in this specification. That is, when polymers comprising recurring units such as NBEtCOOH are used, these polymers may still comprise some monomeric recurring units derived from EPEsNB, i.e., the starting monomers.
It should also be noted that more than one different type of monomer of formulas (I) - (III) can be used in any molar ratio to form the polymer of the present invention. That is, the polymer of the present invention can be formed using one or more monomers of formula (I), one or more monomers of formula (II), and one or more monomers of formula (III) at the same time. Accordingly, the polymers of the present invention typically incorporate from about 1 mole% to about 98 mole% of recurring units of formula (IA). The remaining repeat units are derived from a combination of more than one repeat unit of formula (IIA) and (IIIA). Thus, in some embodiments, the terpolymer comprises any combination of monomeric repeat units of formula (IA), (IIA), and (IIIA), wherein the molar ratio of repeat units can be 40:30:30, 40:40:20, 50:20:30, 50:25:25, 50:30:20, 50:40:10, 50:45:5, 60:20:20, and the like. In other embodiments, the molar ratios of the monomers (I) to (II) to (III) used to form the polymer may be in the range of 1:1:98 to 98:1:1 to 1:98:1, respectively, wherein the molar ratios of the repeating units of formula (IA) to (IIA) to (IIIA) are substantially the same. In other embodiments, the ratios include 30:40:30, 40:30:30, 40:40:20, 40:45:15, 40:50:10, 45:40:15, 45:35:20, 50:35:15, 50:40:10, or any combination thereof.
It is believed that polymers that typically comprise monomeric repeat units having acidic side groups, typically of formula (IIIA), advantageously provide particular benefits to the photosensitive compositions of the invention. Thus, in some embodiments of the invention, the polymer used in the composition of the invention comprises from about 10 to about 80 mole%, and in still other embodiments from about 20 to about 70 mole%, of monomeric repeat units comprising pendant acid groups. In still other embodiments, the mole% of the monomeric repeat units of formula (IA) in the polymer may be from about 0 to 80 mole%, from 10 to 80 mole%, and in still other embodiments from about 20 to 70 mole%. In still other embodiments, the mole% of the monomeric repeat units of formula (IIA) in the polymer can be about 0 to 80 mole%, 10 to 80 mole%, and in still other embodiments about 20 to 70 mole%.
It should also be noted that not all three of the above monomers need be included to form a polymer to bring about the desired results described in this specification. It is believed that homopolymers comprising a repeat unit of any of formulae (IA), (IIA) or (IIIA) may also function in the present invention. In addition, copolymers having either of the two repeating units of formula (IA), (IIA) or (IIIA) may also function as the polymer resin in the composition of the invention. More specifically, HFANB and NBEtCO are considered2The copolymer of H can be used for the photosensitive composition of the present invention. Also, as noted above, terpolymers are used in some embodiments of the invention.
The weight average molecular weight (M) of the polymer used in the photosensitive composition according to the inventionw) Typically at least about 5,000. In still other embodiments, M of the polymers used in the present inventionwAt least about 7,000. In still other embodiments, M of the polymerwAt least about 500,000. In addition, in one embodiment of the present invention, the weight average molecular weight of the polymer used in the present specification is 5,000 to 500,000, or 7,000 to 200,000, or 8,000 to 100,000. The weight average molecular weight (M) is usually determined by Gel Permeation Chromatography (GPC), using polystyrene calibration standardsw) And number average molecular weight (M)n). However, any known method can also be used to determine MwAnd Mn. From this it is also possible to determine the polydispersity index (PDI) (M) of the polymerw/Mn)。
In another aspect of the present invention, the photosensitive composition of the present invention comprises a photoactive compound that typically has a photoactive diazoquinone moiety. Such photoactive compounds (PACs) are known to undergo photo-rearrangement upon exposure to actinic (or electromagnetic) radiation of an appropriate wavelength, for example 254, 365, 405 or 436nm, and by using a suitable light source the wavelength of the radiation can be varied depending on the nature of the PAC used. For example, the PACs used in some embodiments of the invention comprise one or more diazoquinone moieties represented by the general formulae (C), (D), or (E), respectively:
Figure BDA0003596213870000141
Figure BDA0003596213870000151
typically, the structures of formula (C), (D) and/or (E) are incorporated into the photosensitive composition as esterification products of sulfonyl chlorides (or other reactive moieties) and phenolic compounds, respectively, such as one of structures b-1 to b-6 shown below, which are commonly referred to as photoactive compounds or PACs, respectively, as described above. Thus, any one or any combination of two or more of these PACs are combined with a polymer to form a positive tone composition of embodiments of the present invention. In the general formulae (b-1) to (b-6), Q represents any structure of the general formulae (C), (D) or (E). Advantageously, upon exposure of a portion of the film or layer of the photosensitive composition to suitable actinic or electromagnetic radiation, these esterification products produce carboxylic acids that enhance the solubility of these exposed portions in aqueous base as compared to any unexposed portions of these films. Typically, these photosensitive materials are incorporated into the composition in an amount of 5 to 50pphr of polymer, where the specific ratio of photosensitive material to polymer is a function of the dissolution rate of the exposed portions compared to the unexposed portions and the amount of radiation required to achieve the desired dissolution rate difference. Advantageous photosensitive materials that can be used in accordance with embodiments of the present invention are shown in the following general formulae b-1 to b-6; other useful photosensitive materials are exemplified in items 14-20 of U.S. patent No. 7,524,594B2, relevant portions of which are incorporated herein by reference:
Figure BDA0003596213870000152
Figure BDA0003596213870000161
Figure BDA0003596213870000162
and
Figure BDA0003596213870000163
wherein at least one Q is a group of formula (C) or (D) and any remaining Q is hydrogen. Examples of such photoactive compounds include TrisP-3M6C-2(4) -201 from Toyo Gosei Co., Ltd.
Any amount of photoactive compound that brings about the desired results described in the present specification can be used in the photosensitive composition of the present invention. These amounts are usually in the range of 1 to 25 parts by mass per 100 parts by mass (pphr) of the polymer (i.e., resin) described in the present specification. In other embodiments, these amounts may range from 5 to 30 pphr.
Advantageously, it is believed that the use of at least one suitable polyfunctional crosslinker of formula (IV) or (V) as described in the present specification in the photosensitive composition of the invention can provide beneficial effects to the composition of the invention. These benefits include, but are not limited to, improvements in mechanical and thermal properties, and the like.
Any amount of crosslinking agent of formula (IV) or (V) that will provide the desired benefit can be used in the compositions of the present invention. In some embodiments, the amount of the one or more compounds of formula (IV) or (V) used in the composition of the present invention is in the range of 8 to 30 parts by mass per 100 parts by mass (pphr) of the resin, i.e., the polymer used in the composition. In other embodiments, the amount is in the range of about 10 to 25 pphr; in still other embodiments, the amount is in the range of about 12 to 20 pphr; in still other embodiments, the amount is in the range of 14 to 18 pphr. It is to be noted, however, that especially when more than one compound of the formula (IV) or (V) is used, it is also possible to use more than 30pphr of a compound of the formula (IV) or (V).
Non-limiting examples of multifunctional crosslinking agents of formula (IV) or (V) that can be used in the present invention include the following:
Figure BDA0003596213870000171
2,2' - (((2, 2-bis ((oxiran-2-ylmethoxy) methyl) propane-1, 3-diyl) bis (oxy)) bis (methylene)) bis (ethylene oxide) commercially available as PEGE from AlfaAesar;
Figure BDA0003596213870000172
2,2' - (((2- (1, 3-bis (oxiran-2-ylmethoxy) propan-2-yl) propan-1, 3-diyl) bis (oxy)) bis (methylene)) bis (oxiran);
Figure BDA0003596213870000173
1,1,2, 2-tetrakis (4- ((oxiran-2-ylmethoxy) methyl) phenyl) ethane;
Figure BDA0003596213870000174
1,2,4, 5-tetrakis ((oxiran-2-ylmethoxy) methyl) benzene; and
Figure BDA0003596213870000181
2,2' - (((2- (1, 3-bis (oxido-2-ylmethoxy) propan-2-yl) -2- ((oxido-2-ylmethoxy) methyl) propan-1, 3-diyl) bis (oxy)) bis (methylene)) bis (oxiranes).
Other suitable cross-linking agents include the following:
Figure BDA0003596213870000182
wherein n is 1 to 3(OXBP), for example, when n is 1,4, 4 '-bis (((3-ethyloxetan-3-yl) methoxy) methyl) -1,1' -biphenyl;
Figure BDA0003596213870000183
bis (4- (oxiran-2-ylmethoxy) phenyl) methane;
Figure BDA0003596213870000184
a phenol-formaldehyde polymer glycidyl ether, wherein n is 1-10 (EPON 862);
Figure BDA0003596213870000191
triglycidyl ethers of poly (oxypropylene) epoxy ethers of glycerol, commercially available from Momentive Specialty Chemicals Inc. as Heloxy84 or GE-36; and
Figure BDA0003596213870000192
and
Figure BDA0003596213870000193
Heloxy107。
it is believed that the use of more than one phenolic compound of formulae a-1 to a-6 provides further beneficial benefits to the compositions of the present invention. Some of these phenolic compounds are commercially available, for example, as TrisP-3M6C-2Ballast from ToyoGoseiCo. In addition, one or more phenolic compounds of the general formulae a-1 to a-6 which bring about the desired results described in the present specification can be used in an arbitrary amount in the photosensitive composition of the present invention. These amounts are usually in the range of 1 to 25 parts by mass per 100 parts by mass (pphr) of the polymer (i.e., resin) described in the present specification. In other embodiments, these amounts may range from 3 to 20pphr, and in still other embodiments, these amounts may range from 5 to 15 pphr.
As mentioned above, more than one compound of formula (VI) can also be used in the composition of the invention.
Non-limiting examples of compounds of formula (VI) may be listed below:
2,2' -methylenediphenol (also known as 2,2' -bis (hydroxyphenyl) methane or o, o ' -BPF);
4,4' -methylenediphenol;
2,2' - (ethane-1, 1-diyl) diol;
4,4' - (ethane-1, 1-diyl) diphenol;
2,2' - (propane-1, 1-diyl) diol;
4,4' - (propane-1, 1-diyl) diol;
2,2' - (propane-2, 2-diyl) diol;
4,4' - (propane-2, 2-diyl) diol;
2,2' - (4-methylpentane-2, 2-diyl) diol;
4,4' - (4-methylpentane-2, 2-diyl) diphenol;
2,2' - (5-methylheptane-3, 3-diyl) diol;
4,4' - (5-methylheptane-3, 3-diyl) diphenol;
4,4' - (propane-2, 2-diyl) bis (2-cyclohexylphenol);
4,4' - (2-methylpropane-1, 1-diyl) bis (2-cyclohexyl-5-methylphenol);
5,5'- (cyclohexane-1, 1-diyl) bis (([1,1' -biphenyl ] -2-ol));
4,4' - (cyclohexane-1, 1-diyl) bis (2-cyclohexylphenol);
4,4' - (4-methylcyclohexane-1, 1-diyl) diol;
2-cyclohexyl-4- (2- (4-hydroxyphenyl) propan-2-yl) -5-methylphenol;
6,6' -methylenebis (2- (tert-butyl) -4-methylphenol);
6,6' - (2-methylpropane-1, 1-diyl) bis (2, 4-dimethylphenol);
4,4' - (2-methylpropane-1, 1-diyl) bis (2- (tert-butyl) -5-methylphenol);
4- (4-hydroxybenzyl) benzene-1, 2, 3-triol (also known as 1,2, 3-trihydroxy-4- [ (4' -hydroxyphenyl) methyl ] benzene;
and mixtures thereof in any combination.
In addition, one or more compounds of the general formula (VI) which bring about the desired results described in the present specification can be used in an arbitrary amount in the photosensitive composition of the present invention. These amounts are usually in the range of 1 to 25 parts by mass per 100 parts by mass (pphr) of the polymer (i.e., resin) described in the present specification. In other embodiments, these amounts may range from 7 to 20pphr, and in still other embodiments, these amounts may range from 9 to 15 pphr.
The photosensitive composition of the present invention further comprises an additive capable of bonding to acidic side groups of the polymer resin. Such materials include additives containing one or more epoxy groups such as glycidyl, epoxycyclohexyl, oxetanyl, and the like; oxazolinyl such as 2-oxazolin-2-yl, hydroxymethyl such as N-hydroxymethylaminocarbonyl, or alkoxymethyl such as N-methoxymethylaminocarbonyl, but the present invention is not limited thereto. Typically, the aforementioned bonding to the acidic side groups of the polymer is a crosslinking reaction initiated by heating to a suitable temperature, typically at a temperature above 110 ℃ for a suitable time. Accordingly, in some embodiments of the present invention, the photosensitive composition of the present invention comprises one or more epoxy compounds selected from the group consisting of, but not limited to:
Figure BDA0003596213870000211
2,2' - (((2-ethyl-2- ((oxiran-2-ylmethoxy) methyl) propane-1, 3-diyl) bis (oxy)) bis (methylene)) bis (oxiranes) commercially available as DenacolEX x321 (Nagase);
Figure BDA0003596213870000212
(2R,3R,4R,5S) -1,3,5, 6-tetrakis (oxido-2-ylmethoxy) hexane-2, 4-diol (also known as tetra-O- (oxiranylmethyl) -D-glucitol) (Denacolex-614 by Nagase); and
Figure BDA0003596213870000213
1, 2-bis (oxiran-2-ylmethoxy) ethane.
Other exemplary crosslinkable or crosslinkable materials that can be used as additives for forming the photosensitive composition of the present invention include bisphenol a epoxy resins, bisphenol F epoxy resins, silicon-containing epoxy resins, and the like, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycidoxypropyltrimethoxysilane, polymethyl (glycidoxypropyl) cyclohexane, and the like; oxazoline ring-containing polymers, for example, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 1, 3-bis (2-oxazoline-2-yl) benzene, 1, 4-bis (2-oxazoline-2-yl) benzene, 2' -bis (2-oxazoline), 2, 6-bis (4-isopropyl-2-oxazoline-2-yl) pyridine, 2, 6-bis (4-phenyl-2-oxazoline-2-yl) pyridine, 2' -isopropylidenebis (4-phenyl-2-oxazoline), (S, S) - (-) -2,2' -isopropylidenebis (4-tert-butyl-2-oxazoline), Poly (2-propenyl-2-oxazoline) and the like; n-methylol acrylamide, N-methylol methacrylamide, furfuryl alcohol, benzyl alcohol, salicyl alcohol, 1, 2-benzenedimethanol, 1, 3-benzenedimethanol, 1, 4-benzenedimethanol, resol type phenolic resin or a mixture thereof. Such materials are generally considered effective when using from 5pphr polymer to 40pphr polymer. However, it is understood that greater or lesser amounts of addition may also prove effective, as at least some of these effects depend on the nature of the polymer used and the mole% of the repeat units comprising the crosslinking side groups.
In another aspect of the present invention, the photosensitive composition comprises a compound or a mixture of compounds that improve the properties of the composition, including but not limited to, improving the speed of exposure and dissolution properties, and other various uses. Advantageously, it is believed that the compounds of formula (VII) can be used as additives in accordance with the practice of the present invention.
Figure BDA0003596213870000221
Wherein x and y are integers of 0 to 4. R21And R22Are the same or different and are each independently selected from hydrogen, halogen, methyl, ethyl, straight or branched C3-C18Alkyl radical, C1-C18Perfluoroalkyl, methoxy, ethoxy, straight or branched chain C3-C18Alkoxy radical, C3-C16Cycloalkyl radical, C6-C16Bicycloalkyl radical, C8-C16Tricycloalkyl radical, C6-C10Aryl radical, C7-C18Aralkyl, - (CH)2)wCO2R23,-(CH2)zOR24。Ar1And Ar2Are the same or different and are each independently selected from C6-C10Aryl radical, C7-C18Aralkyl, wherein aryl or aralkyl can be further substituted with substituents known to those skilled in the art. Z is selected from the group consisting of a bond, O, S, P, -NR-, -C (═ O) -O-, -C (═ O) -NR-, -SO2-,-SO2NH-alkyl or any carbocyclic bridging group including cycloalkyl, heterocycloalkyl, aryl, aralkyl, and the like. Wherein any cycloalkyl, bicycloalkyl or tricycloalkyl ring may contain more than one heteroatom selected from O, S, N, P and Si. Wherein w is an integer of 0 to 8, R23Is hydrogen, methyl, ethyl, straight or branched C3-C18An alkyl group. Wherein z is an integer of 0 to 8, R24Is hydrogen, methyl, ethyl, straight or branched C3-C18An alkyl group. Wherein R is hydrogen, methyl, ethyl, straight chain or branched chain C3-C18Alkyl radical, C1-C18Perfluoroalkyl group, C3-C16Cycloalkyl radical, C6-C16Bicycloalkyl radical, C8-C16A tricycloalkyl group.
It is contemplated that various other phenolic compounds can also be used in the compositions of the present invention. Non-limiting examples of such compounds may be selected from the group comprising:
a compound of the general formula (VIII):
Figure BDA0003596213870000231
wherein h is an integer of 0-4;
i is 1 or 2;
R6independently hydrogen, methyl, ethyl, straight or branched C3-C16Alkyl radical, C3-C8Cycloalkyl radical, C6-C10Aryl radical, C7-C12Aralkyl or-CO2H；
A compound of formula (IX):
Figure BDA0003596213870000232
wherein j and k are integers of 1 to 4;
l and m are integers of 0 to 4;
R7and R8Are the same or different and are each independently selected from hydrogen, methyl, ethyl, straight or branched C3-C6Alkyl radical, C3-C8Cycloalkyl radical, C6-C10Aryl and C7-C12Aralkyl group; and
a compound of the general formula (X):
Figure BDA0003596213870000233
wherein n and o are integers of 1 to 4;
p and q are integers of 0 to 4;
R9、R10、R11and R12Are the same or different and are each independently selected from hydrogen, methyl, ethyl, straight or branched C3-C6An alkyl group; or
R13Is- (CH)2)rWhen is, R9Or R10And R11Or R12One of these andthe bonded carbon atoms together form a 5-to 8-membered substituted or unsubstituted carbocyclic ring, wherein the substituents are selected from C1-C6An alkyl group;
R13is- (CH)2)r-or phenylene, wherein r is 1 to 2; and is
R14And R15Are the same or different and are each independently selected from hydrogen, methyl, ethyl, straight or branched C3-C6Alkyl radical, C3-C8Cycloalkyl radical, C6-C10Aryl and C7-C12An aralkyl group.
Non-limiting examples of additives comprised by the compound of formula (VIII) can be cited as follows:
2-cyclohexylphenol;
4-cyclohexylphenol;
2-cyclohexyl-5-methylphenol;
2, 4-di-sec-butylphenol;
2, 6-di-tert-butyl-4-methylphenol;
2, 4-di-tert-butylphenol;
4-dodecylphenol;
4-ethyl resorcinol;
2-propylresorcinol;
4-butylresorcinol;
4-hexylresorcinol (also known as 4-hexylbenzene-1, 3-diol);
and mixtures thereof in any combination.
Non-limiting examples of additives comprised by the compound of formula (IX) can be cited as follows:
[1,1' -biphenyl ] -2,2',4,4' -tetraol;
2' -methyl- [1,1' -biphenyl ] -2,3,4,4' -tetraol;
[1,1' -biphenyl ] -2,2',4,4', 6-pentanol;
[1,1' -biphenyl ] -2,2',3,4,4' -pentanol;
and mixtures thereof in any combination.
Non-limiting examples of additives comprised by the compound of formula (X) can be cited as follows:
4,4',4 "- (butane-1, 1, 3-triyl) tris (2- (tert-butyl) -5-methylphenol);
4,4' - (4-isopropyl-1-methylcyclohexane-1, 3-diyl) diol;
4,4' - (1, 4-phenylenebis (propane-2, 2-diyl)) bis (2-cyclohexyl-5-methylphenol);
4,4' - (1, 3-phenylenebis (propane-2, 2-diyl)) bis (2-cyclohexyl-5-methylphenol);
4,4' - (1, 4-phenylenebis (propane-2, 2-diyl)) bis (2-cyclohexylphenol);
4,4' - ([1,1' -bi (cyclohexane) ] -4,4' -diyl) diphenol;
4- (4- (4-hydroxyphenyl) cyclohexyl) -2-methylphenol;
and mixtures thereof in any combination.
Various other compounds that can be used in the compositions of the invention are listed below:
Figure BDA0003596213870000251
1, 4-dimethylpiperazine-2, 5-dione (also known as creatinine);
1-ethyl-4-methylpiperazine-2, 5-dione;
1, 4-diethylpiperazine-2, 5-dione;
1-methyl-4-propylpiperazine-2, 5-dione;
1-ethyl-4-propylpiperazine-2, 5-dione;
1-ethyl-4-isopropylpiperazine-2, 5-dione;
and mixtures thereof in any combination.
In other embodiments, the following compounds can also be used in the compositions of the present invention:
bis (oxiran-2-ylmethyl) cyclohexane-1, 2-dicarboxylate;
bis (oxiran-2-ylmethyl) cyclohexane-1, 3-dicarboxylate;
bis (oxiran-2-ylmethyl) cyclohexane-1, 4-dicarboxylate;
bis (oxiran-2-ylmethyl) phthalate;
bis (oxiran-2-ylmethyl) isophthalate;
bis (oxiran-2-ylmethyl) terephthalate;
and mixtures thereof in any combination.
In general, the various compounds and additives listed in the present specification improve the overall performance of the photosensitive composition of the present invention, thus providing a clear light pattern structure having various uses including chip stack applications, redistribution layers, and dam structures for forming CMOS image sensors. Advantageously, it is understood that some of the additives described in this specification may have more than one function. For example, some of the additives listed above not only exhibit specific solubility enhancing activity, but also may function as a crosslinking agent to promote as described above. Therefore, the additives used in the present specification do not limit the activity of these compounds to only one of these characteristics, but can also promote other functions of the photosensitive composition of the present invention.
It should also be noted that any of the additives represented by structural formulae (VI) to (X) described above can be used alone, that is, as any single compound and/or a combination of more than one compound, can be used in any combination thereof. That is, for example, in some embodiments, more than one compound of formula (VI) may be used in combination with other compounds of formulae (VII) to (X), such as a compound of formula (VI) in combination with a compound of formula (VII) or a compound of formula (IX) or a compound of formula (X), and the like. The amount of the additive that can be used depends on the result expected for the photosensitive composition of the present invention. Thus, any amount that will bring about the desired result can be used in the present invention. In general, the amount of additives that can be used can range from 0.5 to 20pphr, and in some embodiments, these amounts can range from 1 to 12 pphr.
It is understood that various other compounds represented by structural formulae (XIa) to (XIh) can be used as one or more additives alone or in any combination with the compounds of general formulae (VI) to (X) listed above to form the photosensitive composition of the present invention. It should also be noted that these additives, i.e., the compounds represented by structural formulae (XIa) - (XIh), can be used alone or as a mixture thereof in any combination in any desired amount.
Figure BDA0003596213870000261
Aurintricarboxylic acid (XIa);
Figure BDA0003596213870000262
5,5' -methylenedisalicylic acid (XIb);
Figure BDA0003596213870000263
5,5' -thiodisalicylic acid (XIc);
Figure BDA0003596213870000264
3,3,3',3' -tetramethyl-1, 1 '-spiroindane-5, 5',6,6',7,7' -hexanol (XId);
Figure BDA0003596213870000271
p-toluenesulfonyl-p-toluidine (XIe);
Figure BDA0003596213870000272
reducing phenolphthalein (XIf);
Figure BDA0003596213870000273
biphenyldicarboxylic acid (XIg); and
Figure BDA0003596213870000274
4- (5',6' -dihydroxy-1 ',3',4',9a ' -tetrahydrospiro [ cyclohexane-1, 9' -xanthene ] -4a ' (2' H) -yl) benzene-1, 2, 3-triol, also commonly known as pyrogallol-fz (xih).
In another aspect of the invention, various other additives suitable for use with the compositions of the invention include, but are not limited to, the following:
Figure BDA0003596213870000275
d-sorbitol;
Figure BDA0003596213870000281
absolute stereochemistry, rotation (+)
(+) -N, N' -tetramethyl-L-tartaric acid diamide;
Figure BDA0003596213870000282
lactide;
Figure BDA0003596213870000283
a diphenolic acid;
Figure BDA0003596213870000284
2,3, 4-trihydroxybenzoic acid;
Figure BDA0003596213870000285
2,4, 6-trihydroxybenzoic acid (hydrate);
Figure BDA0003596213870000291
4, 5-dihydroxymethyl-2-phenylimidazole.
The photosensitive composition of the present invention further contains a compound which is particularly useful as an adhesion promoter, an antioxidant, a crosslinking agent, a coupling agent, a curing agent, or the like. Non-limiting examples of such compounds are selected from the group consisting of the following, and commercially available materials are indicated by such trade names.
Figure BDA0003596213870000292
Triethoxy (3- (oxiran-2-ylmethoxy) propyl) silane, also commonly referred to as 3-glycidoxypropyltriethoxysilane (3-GTS or (KBE-403 of Shin-etsu chemical co., ltd.));
Figure BDA0003596213870000293
trimethoxy (3- (oxiran-2-ylmethoxy) propyl) silane, also commonly referred to as 3-glycidoxypropyltrimethoxysilane (Shin-etsu chemical co., ltd. KBM-403);
C6H5(CH3O)3Si
phenyltrimethoxysilane
C6H5(C2H5O)3Si
Phenyltriethoxysilane (KBE-103, commercially available from Gelest, Inc. or Shin-Etsu chemical Co., Ltd.)
Figure BDA0003596213870000301
3,3,10, 10-tetramethoxy-2, 11-dioxa-3, 10-disilodecane (SIB-1832 by Gelest, inc.);
Figure BDA0003596213870000302
undec-10-en-1-silane (SIU 9048.0);
Figure BDA0003596213870000303
3- (dimethoxy (methyl) silyl) propane-1-thiol (SIM 6474.0);
Figure BDA0003596213870000304
2,2' - ((3- (triethoxysilyl) propyl) azepinyl) bis (ethan-1-ol) (SIB 1140.0);
Figure BDA0003596213870000305
n, N' -bis [ (3-triethoxysilylpropyl) aminocarbonyl ] polyethylene oxide (SIB-1824.84 of Gelest, inc.);
Figure BDA0003596213870000306
4,4,13, 13-tetraethoxy-3, 14-dioxa-8, 9-dithia-4, 13-disilahexadecane;
Figure BDA0003596213870000311
triethoxy (3-thiocyanatopropyl) silane (SIT7908.0)
Figure BDA0003596213870000312
3,3,12, 12-tetramethoxy-2, 13-dioxa-7, 8-dithia-3, 12-disiltetradecane (Si-75 or Si-266 from Evonik industries AG);
Figure BDA0003596213870000313
2,2' - ((2-hydroxy-5-methyl-1, 3-phenylene) bis (methylene)) bis (4-methylphenol) (antioxidant AO-80 of TCI Japan);
Figure BDA0003596213870000314
4,4' - ((2-hydroxy-5-methyl-1, 3-phenylene) Bis (methylene)) Bis (2, 6-dimethylphenol) (Bis26X-PC)
Figure BDA0003596213870000315
6,6' -methylenebis (2- (2-hydroxy-5-methylbenzyl) -4-methylphenol) (4-PC);
Figure BDA0003596213870000321
pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox 1010 from BASF);
Figure BDA0003596213870000322
3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076 by BASF corporation);
Figure BDA0003596213870000323
bis (4- (2-phenylprop-2-yl) phenyl) amine (Naugard 445(NG445) commercially available from chemtura corporation);
Figure BDA0003596213870000324
bis (4- (tert-butyl) phenyl) amine (Stearer Star from Chemical Products);
Figure BDA0003596213870000331
bis (4-methoxyphenyl) amine (thermolflex);
Figure BDA0003596213870000332
bis (4-ethylphenyl) amine;
Figure BDA0003596213870000333
bis (4-isopropylphenyl) amine
Figure BDA0003596213870000334
Bis (4- (2,4, 4-trimethylpent-2-yl) phenyl) amine (Irganox 5057 from BASF corporation);
Figure BDA0003596213870000335
bis (4- (1-phenylethyl) phenyl) amine (Wingstay 29);
Figure BDA0003596213870000336
bis (4- (2,4, 4-trimethylpentyl) phenyl) amine (Irganox L57 from BASF);
Figure BDA0003596213870000341
1-benzyloctahydropyrrolo [1,2-a ] pyrimidine (CGI-90 from BASF);
Figure BDA0003596213870000342
tetrakis (2,3,4,5, 6-pentafluorophenyl) borate (1-) [4- (1-methylethyl) phenyl ] (4-methylphenyl) -iodonium (Blue Star Silicones, Rhodorsil PI 2074)
Figure BDA0003596213870000343
1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX from Lambson PLC);
Figure BDA0003596213870000344
10H-phenothiazine (phenothiazine Kanto Corporation)
Figure BDA0003596213870000345
1, 4-bis [ (vinyloxy) methyl ] -cyclohexane (cyclohexanedivinyl ether (CHDVE))
Figure BDA0003596213870000351
Wherein R and R' are independently (C)1-C4) Alkyl, and GE ═ glycidyl ether (BY-16-115);
Figure BDA0003596213870000352
silicone-modified epoxy Compounds from Toray-Dow Corning SiliconeCo., Ltd. BY16-115
Is commercially available.
Figure BDA0003596213870000353
(HP-7200); and
Figure BDA0003596213870000354
LowinoxCPL。
other exemplary epoxy resins or crosslinking additives also include araldite mto163 and araldite cy179 (manufactured by ciba geigy); and EHPE-3150 and Epolite GT300 (manufactured by Daicel chemical).
It should also be noted that any of these compounds can be used alone or as a mixture thereof in any combination thereof to obtain the desired benefits depending on the intended use, only when needed. Also, one or more of the above compounds can be used in any amount in the photosensitive composition of the present invention to obtain the intended result. These amounts are generally considered to be in the range of 0.5 to 20 parts by mass per 100 parts by mass (pphr) of the polymer (resin). In some embodiments, these amounts are in the range of 1 to 10 pphr.
The photosensitive composition according to the present invention may further contain other ingredients useful for the purpose of improving the properties of the composition and the obtained film or polymer layer. For example, as described below, the sensitivity of the composition to the desired wavelength of exposure radiation may result in improved desired properties. Examples of these optional ingredients include one or more compounds/various additives such as a surfactant, a silane coupling agent, a leveling agent, a phenol resin, an antioxidant, a flame retardant, a plasticizer, and a curing accelerator, but are not limited thereto.
The photosensitive composition according to an embodiment of the present invention is first coated on a desired substrate to form a thin film. Such substrates include any suitable substrate itself, or semiconductor substrates, such as those used in electrical, electronic or optoelectronic devices, ceramic substrates, glass substrates, and the like. For the application, any suitable coating method can be utilized, such as spin coating, spray coating, blade coating, meniscus coating, inkjet coating, and slot coating.
Next, the coated substrate is heated to facilitate removal of the residual casting solvent, for example, at a temperature of 70 ℃ to 140 ℃ for about 1 to 30 minutes, but other suitable temperatures and times can be used. After heating, the film is typically imagewise exposed to actinic radiation of a suitable wavelength, typically selected in accordance with the photoactive compound and/or photosensitizer incorporated into the polymer composition described in this specification. However, generally, such suitable wavelengths are 200 to 700 nm. It should be understood that the phrase "imagewise exposing" refers to exposing through a masking element to provide a final pattern of exposed and unexposed portions of the film.
After imagewise exposure of a film formed from a photosensitive composition or formulation according to an embodiment of the present invention, a development step is performed. In the case of the positive tone polymer formulations of the present invention, this development step removes only the exposed portions of the film, thus leaving a positive image of the masking layer in the film. In the case of the negative tone polymer formulations of the present invention, this development step removes only the unexposed portions of the film, thus leaving a negative image of the masking layer in the film. In the case of some embodiments, a post-exposure bake can be performed prior to the above-described development step.
Suitable developers particularly suited for positive tone formulations include aqueous inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia, and aqueous organic bases such as 0.26N tetramethylammonium hydroxide (TMAH), ethylamine, triethylamine, and triethanolamine. Where an organic base is used, an organic solvent that is substantially completely miscible with water is typically used to provide sufficient solubility for the organic base. Aqueous TMAH is a developing solution known in the semiconductor industry. Suitable developers can also include organic solvents such as Propylene Glycol Methyl Ether Acetate (PGMEA), 2-heptanone, cyclohexanone, toluene, xylene, ethylbenzene, mesitylene, and butyl acetate.
Thus, some embodiments of the formulations of the present invention provide self-imageable films that, after imagewise exposure, develop the obtained image with an aqueous base solution, while other embodiments develop the obtained image with an organic solvent. Regardless of the type of developer used, after image development, excess developer solution is removed by washing the substrate, with a typical rinse being water or a suitable alcohol and mixtures thereof.
After the above rinsing, the substrate is dried, and the imaged film is finally cured. In other words, the image is fixed. In the case where the remaining layers are not exposed during imagewise exposure, image fixing is typically accomplished by initiating a reaction in the remaining portions of the film. This reaction is typically a crosslinking reaction that can be initiated by heating and/or non-imagewise exposing or blanket exposing the remaining material. Such exposure and heating can be performed in separate steps, or in combination when a particular application suitable for imaging the film is found. The blanket exposure is typically performed using the same energy source as used in the imaging exposure, but any suitable energy source can be used. The heating is usually carried out at a desired temperature, for example, at a temperature higher than 110 ℃ for 40 minutes to1 hour or more. In the case where the remaining layers are exposed during the imagewise exposure, this is usually done by a heating step which is adjusted in such a way that any reaction initiated by the exposure is terminated. However, as described above, blanket exposure and heating may be additionally performed. However, it should be understood that the final curing step is also selected based on the type of device being formed, and thus the final fixing may not be a final cure when the remaining layers are used as an adhesive layer or structure.
Embodiments of the alkali-soluble photosensitive resin composition of the present invention are utilized to form a layer having properties such as high heat resistance, excellent water absorption, high transparency, and low dielectric constant, thereby fabricating a device. Also, such layers generally have an excellent coefficient of elasticity after curing, typically 0.1kg/mm2～200kg/mm2。
As described above, exemplary applications of the photosensitive composition according to the present invention include a die attach adhesive, a wafer bonding adhesive, an insulating film (interlayer dielectric layer), a protective film (passivation layer), a mechanical buffer film (stress buffer layer), or a planarization film for various semiconductor devices and printed circuit substrates. Specific applications of these embodiments include die attach adhesives for forming single or multilayer semiconductor devices, dielectric films formed on semiconductor devices; a buffer film formed on the passivation film; an interlayer insulating film formed on a circuit formed on the semiconductor device.
Thus, embodiments according to the present invention provide positive tone photosensitive polymer compositions that exhibit enhanced properties in one or more mechanical properties (e.g., elongation at break that remains low stress after aging) and have at least equivalent chemical resistance compared to alternative materials. In addition, these embodiments generally provide excellent electrical insulation, adhesion to a substrate, and the like. Accordingly, a semiconductor device, a device package, and a display device incorporating embodiments of the present invention can be provided.
It is considered that the photosensitive composition of the present invention is useful for forming an adhesive layer for bonding semiconductor chips to each other in chip stacking applications and the like. For example, the adhesive layer used for these purposes is formed from a cured product of the photosensitive adhesive composition of the present invention. Although the adhesive layer has a single-layer structure, it has not only sufficient adhesion to the substrate, but also no significant stress due to the curing step is found. Therefore, an unnecessary thick layer of the thin film including the chip as the laminate can be avoided. It was found that the laminate formed according to the present invention has reliability in alleviating stress concentration due to a difference in thermal expansion or the like. As a result, a semiconductor having a low height and high reliability can be obtained. That is, a device with a low aspect ratio and a thin thickness can be obtained. These semiconductor devices are particularly advantageous for electronic equipment having a very small internal volume and carried as mobile equipment, for example. Further advantageously, by implementing the present invention, various electronic devices characterized by miniaturization, thinning, and weight reduction that have not been achieved so far can be formed, and even if these devices are subjected to a severe operation of swinging or dropping, the functions of the semiconductor device are not easily impaired.
The cured product of the photosensitive adhesive composition of the present invention, that is, the adhesive layer or film, usually exhibits an indentation modulus of 2 to 3.5GPa at 25 ℃. The cured product of the photosensitive adhesive composition of the invention shows an indentation modulus of 70-120% of the indentation modulus of an uncured product at 25 ℃, namely before a curing step. In addition, the photosensitive adhesive composition of the present invention exhibits excellent adhesion to a suitable substrate such as a semiconductor chip, and is generally capable of obtaining an adhesion of 20 to 200 newtons (N) at 25 ℃ before curing, after etching and ashing steps.
Therefore, it is considered that the photosensitive adhesive composition of the present invention exhibits an indentation modulus comparable to that of an uncured sample at room temperature after curing, and does not cause significant stress concentration between semiconductor chips, but contributes to the formation of an adhesive layer having sufficient adhesiveness. Further, since the indentation modulus in the state before curing is within a prescribed range of the indentation modulus after curing, and for example, the photosensitive adhesive composition before curing is not significantly deformed or overflowed, it is possible to improve the alignment accuracy when laminating semiconductor chips. Further, since the variation of the indentation modulus before and after curing is relatively small, the shrinkage associated with photosensitivity can be reduced, and the interfacial stress between the semiconductor chips caused by curing shrinkage can be reduced. This also contributes to the reliability of the die stack.
On the other hand, the photosensitive adhesive composition of the present invention is advantageous in that it has sufficient adhesiveness to a semiconductor chip required for wafer bonding in a state before curing after the etching step and the ashing step. Therefore, the adhesive layer for bonding the semiconductor chips to each other firmly fixes the semiconductor chips to each other, and contributes to improvement of reliability of the die stacked body.
Thus, the photosensitive adhesive composition of the present invention can realize an adhesive layer having sufficient adhesiveness and stress relaxation properties. That is, since the adhesive layer has a single layer of the protective function (or buffer coat function) of the buffer coat film and the adhesive function (or wafer bonding function) of the die-bonding film, the die stack can be formed without lowering the reliability, and the wafer stack can be made thinner than the conventional 2-layer wafer stack. Further, since the die stack is thin, the volume of the mold portion can be reduced and the bonding line can be shortened, and these factors contribute to weight reduction and cost reduction.
Therefore, in some embodiments, as described above, the indentation modulus of a cured product of the photosensitive adhesive composition of the present invention is usually 2 to 3GPa at 25 ℃, and in other embodiments, the indentation modulus is 2.2 to 3.2GPa, and in still other embodiments, the indentation modulus is 2.4 to 3.0 GPa. When the indentation modulus of the cured product is less than the lower limit, the adhesiveness of the adhesive layer is lowered, and therefore the interface between the layer and the semiconductor chip is peeled off, and when the filler is contained in the mold portion, the filler penetrates through the adhesive layer and adversely affects the semiconductor chip. On the other hand, if the indentation modulus of the cured product is greater than the above upper limit, the flexibility of the adhesive layer is reduced, and therefore, stress relaxation is reduced, and for example, local concentration of residual stress caused by stacking of semiconductor chips and thermal stress caused by a difference in thermal expansion between the semiconductor chips and the adhesive layer cannot be relaxed. As a result, cracks are generated in the semiconductor chip, or the semiconductor chip and the adhesive layer are peeled off from each other. These problems are easily overcome by using the photosensitive adhesive composition of the present invention.
And the indentation modulus of the cured product was measured at 25 ℃ with a nanoindenter.
The melt viscosity of the photosensitive adhesive composition of the present invention before curing is usually about 20 to 500 pas (Pa · s) in the range of 100 to 200 ℃. Since such a composition has excellent wettability to the semiconductor chip 20 (fig. 2), it is difficult to generate voids in the adhesive layer. Therefore, since a homogeneous adhesive layer with little variation in physical properties can be formed, the adhesive layer hardly causes local concentration of stress when the semiconductor chips are bonded together by the adhesive layer. Therefore, the occurrence of cracks on the semiconductor chip can be suppressed, and the occurrence of peeling between the adhesive layer and the semiconductor chip can be suppressed.
The melt viscosity of the cured photosensitive adhesive composition of the present invention can be measured by a rheometer. Accordingly, in some embodiments of the present invention, the melt viscosity before curing is about 25 to 400Pa · s, and in other embodiments, the melt viscosity before curing is about 30 to 300Pa · s.
Further, although the photosensitive adhesive composition of the present invention has a certain adhesiveness in a state before curing, the adhesiveness can be reduced by irradiating UV radiation thereto. Therefore, the photosensitive adhesive composition of the present invention can control the adhesiveness according to UV radiation.
Specifically, as described above, the photosensitive adhesive composition of the present invention has a tack at 25 ℃ of usually more than 3.0N/25mm in the state before curing and after etching and ashing steps as described above, as compared with a back-grinding tape capable of being peeled off by UV radiation. Since the photosensitive adhesive composition of the present invention can have sufficient viscosity to the back grinding film even after a specific treatment such as etching treatment or ashing treatment for accelerating the degradation of the organic material is performed, the semiconductor wafer can be firmly fixed even when the semiconductor wafer formed from the photosensitive adhesive composition of the present invention is subjected to dicing treatment, and thus the dicing accuracy can be improved.
Therefore, in some embodiments of the present invention, the tack (i.e., bond strength) is 3.5 to 10.0N/25 mm.
On the other hand, the tackiness at 50 ℃ of the photosensitive adhesive composition of the present invention before curing and after UV irradiation is usually 0.5N/25mm with respect to a back-grinding tape peelable with UV irradiation. Since the photosensitive adhesive composition of the present invention has low adhesiveness to a back-grinding tape upon UV irradiation, when a chip is gripped after a dicing step, the dicing tape and a coating film are easily separated, and thus potential defects such as chip breakage are prevented.
Further, by reducing the tackiness (i.e., tackiness), for example, the photosensitive adhesive composition of the invention can be suppressed from adhering to the cutting blade in the cutting step and adhering to the collet in the mounting step. As a result, the occurrence of cutting or grasping errors can be suppressed.
Accordingly, in some embodiments of the invention, the above tack is 0.05N/25mm to 0.4N/25 mm.
Further, the above UV irradiation step is carried out with light having a wavelength of 365nm in a cumulative quantity of light of 600mJ/cm2The exposure dose of (a) is subjected to the step of irradiating. In some embodiments, the light sourceThe exposure dose is about 100 to 500mJ/cm2Within the range of (1). In other embodiments, the exposure dose of the light source is about 150-400 mJ/cm2Within the range of (1). In still other embodiments, the exposure dose of the light source is about 200-250 mJ/cm2Within the range of (1).
It is considered that a circular through hole having a very high resolution can be formed by using the photosensitive composition of the present invention. The resolution of the through holes can be in the range of 1-100 μm. In some embodiments, the resolution of the vias may be in the range of 3-30 μm. In still other embodiments, the resolution of the through holes may be in the range of 5-15 μm.
Further, the back-grind UV release tape used in the above embodiment is generally made of acrylic resin. However, any tape that can bring about the above results can also be used.
Thus, as described above, in some embodiments of the present invention, the photosensitive composition is soluble in an alkaline developer.
Furthermore, as described above, in some embodiments of the present invention, the electronic and/or semiconductor device according to the present invention comprises a laminated semiconductor device, wherein the above-described laminated body is composed of the photosensitive composition according to the present invention.
In some embodiments of the invention, a semiconductor device comprises a redistribution layer (RDL) structure further comprising a photosensitive composition according to the invention.
Further, as described above, in some embodiments of the present invention, the semiconductor device including a chip stack structure further includes the photosensitive composition according to the present invention.
As described above, in further embodiments of the present invention, a semiconductor device comprising a Complementary Metal Oxide Semiconductor (CMOS) image sensor dam structure further comprises a photosensitive composition according to the present invention.
Also, as described above, in some embodiments of the present invention, a film is formed from the photosensitive composition according to the present invention. As noted above, such films generally exhibit excellent chemical, mechanical, and elastic properties that have broad utility in electronic, optoelectronic, and microelectromechanical applications with excellent dielectric properties.
Accordingly, in some embodiments of the present invention, there is provided a microelectronic or optoelectronic device comprising one or more of a redistribution layer (RDL) structure, a chip stack structure, a CMOS image sensor dam structure, wherein the above structure further comprises a photosensitive composition according to the present invention.
Further, in some embodiments of the present invention, there is provided a method of forming a thin film for manufacturing a microelectronic device or an optoelectronic device, comprising:
a step of coating a suitable substrate with the composition according to the present invention to form a thin film;
a step of patterning the film with a mask by exposure to appropriate radiation;
a step of developing the film after exposure to form a light pattern; and
and curing the film by heating to a suitable temperature.
The photosensitive composition of the present invention can be applied to a substrate by any of the application steps described in the present specification and/or application steps such as spin coating known to those skilled in the art.
Also, development according to the method of the present invention can be performed by using any known development technique such as an aqueous developer.
In some embodiments of the invention, the developer used in accordance with the methods of the invention is an aqueous solution of tetramethylammonium hydroxide (TMAH).
Also, in some embodiments of the present invention, after the substrate is first hard-baked, it is cured at a temperature of 130 to 160 ℃ for 20 to 60 minutes.
Finally, in other embodiments of the present invention, the curing is carried out at a temperature of 170 ℃ to 200 ℃ with a heating ramp of 5 ℃ for 1 to 5 hours.
Examples
The polymers used to form the photosensitive composition of the present invention are generally known in the literature and are prepared according to known procedures. See, for example, U.S. patent No. 9,696,623B2, the relevant portions of which are incorporated herein by reference.
Example 1
Generally, any of the polymers described in the present specification can be used. For example, the terpolymer of polynorbornene derivatives described in the present specification is dissolved in an appropriate solvent such as Propylene Glycol Methyl Ether Acetate (PGMEA), and mixed with a specific amount of the additive shown in table 1 in parts per 100 parts of resin (pphr) in an amber HDPE bottle of an appropriate size. The mixture was shaken for 18 hours, resulting in a homogeneous solution. Particulate contamination was removed by filtering the polymer solution through a 0.45 μm pore Polytetrafluoroethylene (PTFE) disc filter under a pressure of 35psi, collecting the filtered polymer solution in a low particle HDPE amber bottle and storing the solution at 5 ℃.
TABLE 1
Ingredients (pphr) Example 1 Comparative example 1
Terpolymer and process for preparing the same 100 100
Photoactive compounds 14 15.5
Trifunctional epoxy compounds 7 20
Tetrafunctional epoxy compounds 14 0
Adhesion promoter kit 13.5 13.5
Antioxidant kit 3 11.5
Multifunctional phenolic compound kit 17 23
The composition thus formed was left at room temperature and applied to a plurality of 125mm diameter silicon wafers (thickness: 625 μm) by spin coating at 200rpm for 10 seconds initially and at 500rpm for 30 seconds thereafter. The thus-formed substrate was placed on a hot plate at 120 ℃ for 4 minutes, thereby obtaining a polymer film about 2 micrometers (μm) thick. Passing through 125-500 mJ/cm2A range of exposure energies were imagewise exposed to each polymer film. Each film was then developed using a spin-on immersion development method in which each film was immersed twice in 0.26N TMAH for about 5 seconds. After the development step, each wafer was rinsed by spraying deionized water for 5 seconds, and then dried by spinning at 3000rpm for 15 seconds.
FIG. 1 shows lithographic images obtained with different exposure energies using compositions of the present invention. Specifically, FIGS. 1A to 1D show a stepper and a mask aligner, each at 125mJ/cm2、175mJ/cm2、225mJ/cm2And 300mJ/cm2Is used to capture a lithographic image at the threshold exposure dose.
Comparative example 1
Essentially the same composition as in example 1 was prepared, but without the tetrafunctional epoxy compound set and with some of the other additives shown in table 1 used in the comparative tests described in examples 2 and 3.
Example 2
Wafer shear strength measurement
The composition described in example 1 was spin-coated on a silicon wafer and baked at 120 ℃ for 4 minutes, whereby a film having a thickness of 10 μm was obtained. The film was hard baked at 150 ℃ for 40 minutes. The wafer was then singulated into 10mmx20mm chips. Next, the chips were placed on a hot plate at 150 ℃ while pressing each of 4mmx4mm silicon chips against the surface of the coated singulated chips with a force of 1kg-f for 1 second. The bonded chips were transferred to a nitrogen oven and the composition of example 1 was cured at 180 ℃ for 2 hours. After curing, the chip assembly was moved to a heating station (260 ℃) and a wafer of 4mmx4mm was cut from 10mmx20mm chips containing the composition of example 1. The wafer shear force was measured and recorded.
Likewise, a sample was prepared in substantially the same manner as described above, except that the composition of comparative example 1 was used.
Fig. 2 shows the results obtained from wafer shear measurements. From this data, it can be seen that the composition of example 1 is significantly superior to comparative example 1.
Example 3
The composition described in example 1 was spin-coated onto a suitable substrate and baked at 120 ℃ for 4 minutes. The coating is then imagewise exposed to suitable actinic radiation using a mercury vapor lamp (200-450 nm). The exposed substrate is then developed with a tetramethylammonium hydroxide (TMAH) developer to expose the unexposed regions. The substrate is then heated to a temperature in the range of about 150 c to 240 c for up to 2 hours to fully cure the composition of the present invention. The cured sample is then exposed to an acidic etchant to remove any oxidized surfaces. The etchant temperature is maintained in a temperature range from room temperature to 50 c for about 5 minutes to 15 minutes. After the etching step, the polymer sample was observed with an optical microscope to see whether peeling or over-etching occurred in the etching step. Various compositions prepared according to the present invention showed less peeling compared to example 1 and comparative example 1.
The present invention has been described in terms of some of the above-described embodiments, but is not limited thereto, and it should be understood that the present invention encompasses the general scope of the above description. Various modifications and embodiments can be implemented without departing from the spirit and scope of the invention.

Claims (25)

1. A photosensitive composition, comprising:
a) a polymer having:
a first type of recurring unit of formula (IA) derived from a monomer of formula (I):
Figure FDA0003596213860000011
a second type of recurring unit of formula (IIA) derived from a monomer of formula (II):
Figure FDA0003596213860000012
and
a third type of recurring unit of formula (IIIA) derived from a monomer of formula (III):
Figure FDA0003596213860000013
wherein:
Figure FDA0003596213860000014
indicates a position bonded to another repeating unit;
a is an integer of 0 to 3;
b is an integer of 1-4;
c is an integer of 1-4;
R1selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propylPropyl and n-butyl;
R18is selected from- (CH)2)s-、-(CH2)t-OCH2-or- (CH)2)t-(OCH2CH2)u-OCH2-, wherein
s is an integer of 0 to 6,
t is an integer of 0 to 4,
u is an integer of 0 to 3,
R19is- (CH)2)v-CO2R20Wherein v is an integer of 0 to 4, and
R20is hydrogen or C1-C4An alkyl group;
b) a photoactive compound comprising a diazoquinone moiety of the general formula (a):
Figure FDA0003596213860000021
c) a multifunctional crosslinker selected from the group comprising:
a compound of the general formula (IV):
Figure FDA0003596213860000022
and
a compound of the general formula (V):
Figure FDA0003596213860000023
wherein:
n is an integer of 5-8;
a is selected from the group consisting of C, CH- (CR)2)d-CH and substituted or unsubstituted aryl, wherein d is an integer from 0 to 4 and R is selected from the group comprising hydrogen, methyl, ethyl, n-propyl, isopropyl and n-butyl;
b is selected from the group consisting of substituted or unsubstituted (C)2-C6) Alkylene and substituted or unsubstituted arylA group of (1);
wherein said substituents are selected from the group consisting of halogen, methyl, ethyl, straight or branched chain (C)3-C6) Alkyl, (C)3-C8) Cycloalkyl, (C)6-C10) Aryl group, (C)7-C12) Aralkyl, methoxy, ethoxy, straight or branched (C)3-C6) Alkoxy group, (C)3-C8) Cycloalkoxy, (C)6-C10) Aryloxy group and (C)7-C12) A group of aralkyloxy groups;
d) a phenolic compound selected from the group comprising:
Figure FDA0003596213860000031
Figure FDA0003596213860000032
and
Figure FDA0003596213860000033
e) a compound of the general formula (VI):
Figure FDA0003596213860000034
wherein d and e are integers of 1 to 4;
f and g are integers of 0 to 4;
R2and R3Are the same or different and are each independently selected from hydrogen, methyl, ethyl, straight or branched C3-C6Alkyl radical, C3-C8Cycloalkyl radical, C6-C10Aryl and C7-C12Aralkyl group; or
R2And R3Together with the carbon atom to which they are attached form a 5-to 8-membered substituted or unsubstituted carbocyclic ring, wherein the substituents are selected from C1-C8An alkyl group;
R4and R5Are identical or different and are each independently selected from hydrogen, methyl, ethyl, linear or branched (C)3-C6) Alkyl, (C)3-C8) Cycloalkyl group, (C)6-C10) Aryl and (C)7-C12) An aralkyl group.
2. The photosensitive composition according to claim 1, wherein,
the first repeat unit of the polymer is derived from a monomer selected from the group consisting of:
trioxononenyl norbornene (NBTON);
tetraoxadodecyl Norbornene (NBTODD);
5- (3-methoxybutoxy) methyl-2-norbornene (NB-3-MBM); and
5- (3-methoxypropanyloxy) methyl-2-norbornene (NB-3-MPM).
3. The photosensitive composition according to claim 2, wherein,
the second repeat unit of the polymer is derived from a monomer selected from the group consisting of:
4- (bicyclo [2.2.1]]Hept-5-en-2-yl) -1,1, 1-trifluoro-2- (trifluoromethyl) butan-2-ol (HFACH)2NB)；
Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB); and
5- (bicyclo [2.2.1]]Hept-5-en-2-yl) -1,1, 1-trifluoro-2- (trifluoromethyl) pent-2-ol (HFACH)2CH2NB)。
4. The photosensitive composition according to claim 3,
the third repeat unit of the polymer is derived from a monomer selected from the group consisting of:
3- (bicyclo [2.2.1] hept-5-en-2-yl) acetic acid (NBMeCOOH);
ethyl 3- (bicyclo [2.2.1] hept-2-en-2-yl) propionate (EPEsNB);
bicyclo [2.2.1] hept-5-ene-2-carboxylic Acid (Acid NB); and
norbornenylpropionic acid (nbetoh).
5. The photosensitive composition according to claim 1, wherein,
the polymer is a terpolymer derived from 3 monomers selected from the group comprising:
trioxononenyl norbornene (NBTON);
tetraoxadodecyl Norbornene (NBTODD);
5- (3-methoxybutoxy) methyl-2-norbornene (NB-3-MBM);
5- (3-methoxypropanyloxy) methyl-2-norbornene (NB-3-MPM);
4- (bicyclo [2.2.1]]Hept-5-en-2-yl) -1,1, 1-trifluoro-2- (trifluoromethyl) butan-2-ol (HFACH)2NB)；
Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);
5- (bicyclo [2.2.1]]Hept-5-en-2-yl) -1,1, 1-trifluoro-2- (trifluoromethyl) pent-2-ol (HFACH)2CH2NB)；
3- (bicyclo [2.2.1] hept-5-en-2-yl) acetic acid (NBMeCOOH);
ethyl 3- (bicyclo [2.2.1] hept-2-en-2-yl) propionate (EPEsNB);
bicyclo [2.2.1] hept-5-ene-2-carboxylic Acid (Acid NB); and
norbornenylpropionic acid (nbetoh).
6. The photosensitive composition according to claim 1, wherein,
the diazoquinone moiety is represented by general formula (C), (D) or (E):
Figure FDA0003596213860000051
7. the photosensitive composition according to claim 1, wherein,
the photoactive compound is selected from one or more of the following:
Figure FDA0003596213860000061
Figure FDA0003596213860000062
and
Figure FDA0003596213860000063
wherein at least one Q is a group of formula (C) or (D):
Figure FDA0003596213860000071
the remainder of Q is hydrogen.
8. The photosensitive composition according to claim 1, wherein,
the multifunctional crosslinking agent is selected from the group comprising:
Figure FDA0003596213860000072
2,2' - (((2, 2-bis ((oxiran-2-ylmethoxy) methyl) propane-1, 3-diyl) bis (oxy)) bis (methylene)) bis (oxiran);
Figure FDA0003596213860000073
2,2' - (((2- (1, 3-bis (oxiran-2-ylmethoxy) propan-2-yl) propan-1, 3-diyl) bis (oxy)) bis (methylene)) bis (oxiran);
Figure FDA0003596213860000074
1,2,4, 5-tetrakis ((oxiran-2-ylmethoxy) methyl) benzene; and
Figure FDA0003596213860000081
2,2' - (((2- (1, 3-bis (oxido-2-ylmethoxy) propan-2-yl) -2- ((oxido-2-ylmethoxy) methyl) propan-1, 3-diyl) bis (oxy)) bis (methylene)) bis (oxiranes).
9. The photosensitive composition according to claim 1, wherein,
the compound of formula (VI) is selected from the group comprising:
2,2' -methylenediphenol;
4,4' -methylenediphenol;
2,2' - (ethane-1, 1-diyl) diol;
4,4' - (ethane-1, 1-diyl) diphenol;
2,2' - (propane-1, 1-diyl) diol;
4,4' - (propane-1, 1-diyl) diol;
2,2' - (propane-2, 2-diyl) diol;
4,4' - (propane-2, 2-diyl) diol;
2,2' - (4-methylpentane-2, 2-diyl) diphenol;
4,4' - (4-methylpentane-2, 2-diyl) diphenol;
2,2' - (5-methylheptane-3, 3-diyl) diol;
4,4' - (5-methylheptane-3, 3-diyl) diol;
4,4' - (propane-2, 2-diyl) bis (2-cyclohexylphenol);
4,4' - (2-methylpropane-1, 1-diyl) bis (2-cyclohexyl-5-methylphenol);
5,5 "- (cyclohexane-1, 1-diyl) bis (([1,1' -biphenyl ] -2-ol));
4,4' - (cyclohexane-1, 1-diyl) bis (2-cyclohexylphenol);
4,4' - (4-methylcyclohexane-1, 1-diyl) diol;
2-cyclohexyl-4- (2- (4-hydroxyphenyl) propan-2-yl) -5-methylphenol;
6,6' -methylenebis (2- (tert-butyl) -4-methylphenol);
6,6' - (2-methylpropane-1, 1-diyl) bis (2, 4-dimethylphenol);
4,4' - (2-methylpropane-1, 1-diyl) bis (2- (tert-butyl) -5-methylphenol);
and mixtures thereof in any combination.
10. The photosensitive composition according to claim 1, wherein,
the phenolic compound is selected from the group comprising:
Figure FDA0003596213860000091
Figure FDA0003596213860000092
and
Figure FDA0003596213860000093
11. the photosensitive composition according to claim 1, wherein,
the phenolic compound is:
Figure FDA0003596213860000094
12. the photosensitive composition according to claim 1, wherein,
the phenolic compound of general formula (VI) is selected from the group comprising:
2,2' - (4-methylpentane-2, 2-diyl) diphenol;
4,4' - (4-methylpentane-2, 2-diyl) diol;
2,2' - (5-methylheptane-3, 3-diyl) diol;
4,4' - (5-methylheptane-3, 3-diyl) diol;
and mixtures thereof in any combination.
13. The photosensitive composition according to claim 1, further comprising one or more compounds selected from the group consisting of:
Figure FDA0003596213860000101
triethoxy (3- (oxiran-2-ylmethoxy) propyl) silane;
Figure FDA0003596213860000102
3,3,10, 10-tetramethoxy-2, 11-dioxa-3, 10-disilodecane;
Figure FDA0003596213860000103
4,4,13, 13-tetraethoxy-3, 14-dioxa-8, 9-dithia-4, 13-disilahexadecane;
Figure FDA0003596213860000104
2,2' - ((2-hydroxy-5-methyl-1, 3-phenylene) bis (methylene)) bis (4-methylphenol);
Figure FDA0003596213860000111
6,6' -methylenebis (2- (2-hydroxy-5-methylbenzyl) -4-methylphenol);
Figure FDA0003596213860000112
bis (4- (2-phenylprop-2-yl) phenyl) amine;
Figure FDA0003596213860000113
bis (4- (tert-butyl) phenyl) amine;
Figure FDA0003596213860000114
bis (4-methoxyphenyl) amine;
Figure FDA0003596213860000115
bis (4-ethylphenyl) amine;
and mixtures thereof in any combination.
14. The photosensitive composition according to claim 1, further comprising one or more compounds selected from the group consisting of a phenolic resin, a leveling agent, an antioxidant, a flame retardant, a plasticizer, a silane coupling agent, and a curing accelerator.
15. The photosensitive composition according to claim 1, which is soluble in an alkaline developer.
16. A semiconductor or optoelectronic device comprising a stacked semiconductor element or adhesive element, wherein the element is composed of the photosensitive composition according to claim 1.
17. A semiconductor device including a chip stack structure, wherein,
the chip stack structure further comprises the photosensitive composition of claim 1.
18. A film comprising the composition of claim 1.
19. A microelectronic or optoelectronic device comprising one or more of a redistribution layer (RDL) structure, a chip stack structure, a CMOS image sensor dam structure, wherein the structure further comprises the composition of claim 1.
20. A method of forming a thin film for use in fabricating a microelectronic or optoelectronic device, comprising:
a step of coating a suitable substrate with the composition of claim 1 to form a thin film;
a step of patterning the film with a mask by exposure to appropriate radiation;
a step of developing the film after exposure to form a light pattern; and
and curing the film by heating to a suitable temperature.
21. The method of claim 20, wherein,
the coating step is performed by spin coating.
22. The method of claim 20, wherein,
the developing step is performed by an aqueous developer.
23. The method of claim 22, wherein,
the developer is a tetramethylammonium hydroxide (TMAH) aqueous solution.
24. The method of claim 20, wherein,
first, the substrate is hard-baked and then cured at a temperature of 130 to 160 ℃ for 20 to 60 minutes.
25. The method of claim 20, wherein,
the curing is carried out at a temperature of 170-200 ℃ for 1-5 hours with an incremental heating slope of 5 ℃.
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