TWI848011B - Photosensitive compositions and applications thereof - Google Patents

Abstract

The present invention relates to photosensitive compositions containing polynorbornene (PNB) polymers and certain additives that are useful for forming microelectronic and/or optoelectronic devices and assemblies thereof, and more specifically to compositions encompassing PNBs and certain multifunctional crosslinking agents, and two or more phenolic compounds which are resistant to thermo-oxidative chain degradation and exhibit improved mechanical properties.

Description

Photosensitive composition and its application

Embodiments of the present invention generally relate to a polynorbornene (PNB) composition comprising various additives for forming microelectronic and/or optoelectronic devices and components thereof, and more specifically to a composition comprising a PNB having at least one norbornene-type repeating unit comprising a terminal functionalized polyether, wherein the composition exhibits improved thermal, mechanical and optoelectronic properties.

Organic polymer materials are increasingly used in a variety of applications in the microelectronics and optoelectronics industries. For example, uses of such organic polymer materials include interlayer dielectric layers, redistribution layers, stress buffer layers, leveling or planarization layers, alpha particle blocking layers, and passivation layers for microelectronics and optoelectronics devices. Since such organic polymer materials are photosensitivity and self-imaging, they have the 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 are capable of directly bonding devices and device components to form various structures. Such devices include microelectromechanical systems (MEMS) and micro-opto-electromechanical systems (MOEMS).

唑(PBO)及苯并環丁烯(BCB)組成物由於通常具有良好的熱穩定性和機械強度而已成為前述各種應用的選用材料，但每一種上述材料均在硬化期間由前驅物形成，該前驅物會進行反應來改質聚合物的主鏈(PI及PBO)或形成主鏈(BCB)，因此通常在硬化期間需要以特定處理條件來去除在硬化期間形成的副產物和/或排除能夠防止硬化之氧氣 或水蒸氣。又，該種材料的硬化通常需要超過250℃(有些材料高達400℃)的處理溫度，導致過多或不必要的處理成本。因此，該種材料有可能不適於一些應用，例如再分配及層間介電層、以及遮蓋影像感測陣列之透明遮蓋物的直接黏接。 Although polyimide (PI), polybenzo

Poly(vinylidene oxadiazole) (PBO) and benzocyclobutene (BCB) compositions have become the materials of choice for various applications mentioned above due to their generally good thermal stability and mechanical strength, but each of the above materials is formed from a precursor during the curing period, which reacts to modify the polymer backbone (PI and PBO) or form the backbone (BCB), and therefore generally requires specific processing conditions during the curing period to remove byproducts formed during the curing period and/or to exclude oxygen or water vapor that can prevent curing. In addition, the curing of such materials generally requires processing temperatures in excess of 250°C (some materials as high as 400°C), resulting in excessive or unnecessary processing costs. Therefore, such materials may not be suitable for some applications, such as redistribution and interlayer dielectric layers, and direct bonding of transparent covers covering image sensing arrays.

Therefore, it is considered desirable to provide a material that can be used to form the aforementioned structures and exhibits thermal stability and mechanical strength equivalent to known PI, PBO and BCB compositions, wherein the material has a fully formed polymer backbone that is capable of hardening at temperatures below 200°C. In addition, such an advantageous material 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. In addition, it is advantageous that the material is self-imageable. Again, several currently available compositions may not be suitable for some applications because they do not have the required dissolution rate (DR) properties including resolution and photospeed as further described in detail below.

Although some of the above problems have been successfully overcome by polynorbornene-based photosensitive compositions described in U.S. Patents Nos. 9,341,949 and 9,696,623, there is still a need for suitable flexible materials with the necessary adhesive strength and mechanical strength, especially the chip shear strength used in the manufacture of various micro-photoelectronic devices such as display devices.

Therefore, there is still a need to develop a self-imageable photosensitive polymer composition that has the desired thermal properties, solubility, orthogonality to various solvents used at different stages in the device manufacturing process, adhesion, and most importantly, integration with all relevant process steps.

Below, the embodiments of the present invention are described with reference to the following drawings and/or images. When drawings are provided, they are simplified portions of the embodiments of the present invention and are only used for illustrative purposes.

Figures 1A to 1D show the photolithographic images formed by the composition of the present invention under various exposure doses.

FIG2 shows the wafer shear strength of the composition of the present invention compared to the comparative composition.

According to the embodiments of the present invention, there is a self-imageable composition comprising a norbornene-type polymer and a film, layer, structure, device or component that can be formed using the composition. Some embodiments include a self-imageable composition that can provide a positive tone image after imagewise exposure of a film formed from the composition, and then developing the images using an alkaline aqueous developer solution.

In addition, the embodiments described in this specification are generally capable of providing a film having a desired thickness in the range of about 2 to 5 micrometers (μm) or more, wherein the image in the film shows a 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 dielectric layers, redistribution layers, stress buffer layers, leveling or planarizing layers, alpha particle blocking layers used in microelectronic and optoelectronic devices and components formed therefrom, and for forming wafer stacks and bonding for fixing transparent covers on image sensing arrays.

The terms used in this specification have the following meanings: Unless otherwise specified, all numbers, values and/or expressions used in this specification regarding the amount of ingredients, reaction conditions, polymer compositions and formulations, etc. are modified by the term "about" in any case, because such numbers are essentially approximate values that reflect the various measurement uncertainties encountered when obtaining such values. In addition, unless otherwise specified, when numerical ranges are disclosed in this specification, such ranges are continuous and include every value from the minimum value to the maximum value of the range. In addition, unless otherwise specified, such ranges refer to integers, including every integer from the minimum value to the maximum value. In addition, when multiple ranges are provided to describe a property or feature, such ranges can be combined to describe such properties or features.

As used in this specification, the articles "a/an" and "the" include plural referents unless expressly limited to one referent.

It should be understood that the phrase "microelectronic device" used in this specification includes "micro-photoelectronic device" and "optoelectronic device". Therefore, references to microelectronic devices or microelectronic device components include optoelectronic devices and micro-optoelectronic devices and their components. Similarly, micro-electromechanical systems (MEMS) include micro-opto-electromechanical systems (MOEMS).

It should be understood that the term "redistribution layer (RDL)" refers to an insulating material for routing electrical signals with the required reliable properties. The term RDL may also be used interchangeably to describe a required buffer coating, such as a stress relief or buffer layer between solder balls and fragile low-K structures.

The term "polymer" used in this specification should be understood as a molecule containing a main chain of more than one different type of repeating units (the smallest constituent unit of a polymer). In addition to the polymer itself, the polymer also includes residues from initiators, catalysts, and other components produced with the formation of such polymers, wherein such residues are generally considered not to be covalently bonded to them, but can be covalently bonded to the front or back end of the polymer chain in the same way as some catalyst-induced polymerization. In addition, although such residues and other components are usually removed in post-polymerization purification treatment, they are usually mixed or blended with the polymer, so a small amount of residues are usually left when transferred between containers or between solvents or dispersion media.

The term "polymer composition" used in this specification refers to at least one synthetic polymer and materials added after the polymerization to provide or improve specific properties. Exemplary materials that can be added include solvents, photoactive compounds (PACs), dissolution rate inhibitors, dissolution rate enhancers, dissolution promoters, crosslinking moieties, reactive diluents, antioxidants, adhesion promoters, and plasticizers, but are not limited thereto.

The term "modulus" as used in this specification, unless otherwise specified, is to be understood as the ratio of stress to strain, representing the Young's modulus or tensile modulus measured in the linear elastic region of the stress-strain curve. Modulus values are usually measured according to ASTM method DI708-95. Films with low modulus are considered to have low internal stress.

The term "photosensitive" refers to a characteristic of a material or material composition, such as a polymer or polymer composition according to an embodiment of the present invention, which itself forms a patterned layer or structure. In other words, the "photosensitive layer" does not require the use of another material layer formed thereon, such as a photoresist layer, to form the aforementioned patterned layer or structure. It will be further understood that polymer compositions having such characteristics are generally used in patterning schemes to form patterned films/layers or structures. It should be noted that such schemes include "image-wise exposure" of the photosensitive material or layer formed therefrom. The image-wise exposure employed refers to exposing selected portions of the layer to actinic radiation, while unselected portions are protected from such actinic radiation exposure.

The term "self-imageable composition" as used in this specification is to be understood as a material which is photosensitive and is therefore capable of providing a patterned layer and/or structure upon direct imagewise exposure of a film formed from the composition, the image then being developed on the film using a suitable developer.

As used in this specification, "hydrocarbyl" refers to a free radical or group containing only carbon atoms and hydrogen atoms, non-limiting examples of which are alkyl, cycloalkyl, aryl, aralkyl, alkaryl and alkenyl. The term "halohydrocarbyl" refers to a alkyl group in which at least one hydrogen atom is replaced by a halogen atom. The term "perhalocarbyl" refers to a alkyl group in which all hydrogen atoms are replaced by halogens. The term "heterohydrocarbyl" refers to any of the aforementioned alkyl, halogenated alkyl and perhalogenated alkyl groups, in which at least one carbon atom of the carbon chain is replaced by an N, O, S, Si or P atom.

”表示與另一重複單元或另一原子或分子或基團或一部分發生鍵結之位置，依據情況與所示基團的結構發生鍵結之位置。 The symbols used in this manual are "

” indicates the position at which a bond occurs to another repeat unit or to another atom or molecule or group or part, as the case may be, to the structure of the group indicated.

The expression "alkyl" used in this specification refers to a saturated, straight-chain or branched hydrocarbon substituent having a specified number of carbon atoms. Specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, tertiary butyl, etc. Derivative expressions such as "alkoxy", "thioalkyl", "alkoxyalkyl", "hydroxyalkyl", "alkylcarbonyl", "alkoxycarbonylalkyl", "alkoxycarbonyl", "diphenylalkyl", "phenylalkyl", "phenylcarboxyalkyl" and "phenoxyalkyl" should be interpreted accordingly.

The expression "cycloalkyl" used in this specification includes all known cyclic aliphatic free radicals. Representative examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., but are not limited thereto. Derivative terms such as "cycloalkoxy", "cycloalkylalkyl", "cycloalkylaryl" and "cycloalkylcarbonyl" should be interpreted accordingly.

The expression "alkenyl" used in this specification refers to an acyclic, straight or branched hydrocarbon chain having a specified number of carbon atoms and at least a carbon-carbon double bond, and includes vinyl and straight or branched propenyl, butenyl, pentenyl and hexenyl. Similarly, the expression "alkynyl" refers to an acyclic, straight or branched hydrocarbon chain having a specified number of carbon atoms and at least one carbon-carbon triple bond, and includes ethynyl and straight or branched butynyl, pentynyl and hexynyl.

The expression "acyl" used in this specification shall have the same meaning as "alkanoyl", which can also be represented by the structure "R-CO-", wherein R is an "alkyl" described in this specification with a specified number of carbon atoms. In addition, "alkylcarbonyl" shall have the same meaning as the acyl described in this specification. Specifically, "(C ₁ -C ₄ ) acyl" shall mean formyl, acetyl (acetyl or ethanoyl), propionyl, n-butyryl, etc. Derivative expressions such as "acyloxy" and "acyloxyalkyl" shall be interpreted accordingly.

The expression "perfluoroalkyl" used in this specification refers to all hydrogen atoms in the aforementioned alkyl group replaced by fluorine atoms. Illustrative examples include trifluoromethyl and pentafluoroethyl, linear or branched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl. The derived expression "perfluoroalkoxy" should be interpreted accordingly.

The expression "aryl" used in this specification refers to substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or substituted naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. "Substituted phenyl" or "substituted naphthyl" also includes any possible substituents described in this specification or known in the art. The derived expression "arylsulfonyl" should be interpreted accordingly.

The expression "arylalkyl" or "aralkyl" is used interchangeably in the present specification. Specifically, "(C ₆ -C ₁₀ )aryl(C ₁ -C ₄ )alkyl" or "(C ₇ -C ₁₄ )aralkyl" means that the (C ₆ -C ₁₀ )aryl group shown in the present specification is further bonded to the (C ₁ -C ₄ )alkyl group described in the present specification. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

唑基(oxazolyl)、噻唑基、異噻唑基等。代表性6員環雜芳基包括吡啶基、噠

基(pyridazinyl)、嘧啶基、吡

基(pyrazinyl)、三

基(triazinyl)等基。雙環雜芳基的代表性例子包括苯并呋喃基、苯并噻吩基、吲哚基、喹啉基、異喹啉基、噌啉基(cinnolyl)、苯并咪唑基、吲唑基、吡啶并呋喃基、吡啶并噻吩基等基。 The term "heteroaryl" used in this specification includes all known heteroatom-containing aromatic groups. Representative 5-membered heteroaryl groups include furanyl, thienyl (thiophenyl), pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl,

Representative 6-membered heteroaryl groups include pyridyl,

pyridazinyl, pyrimidine, pyridazinyl

Pyrazinyl, tri

Representative examples of the bicyclic heteroaryl group include benzofuranyl, benzothiophenyl, indolyl, quinolyl, isoquinolyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothiphenyl and the like.

唑基等。代表性6員雜環基包括哌啶基、哌

基、嗎啉基(morpholinyl)、硫代嗎啉基等。各種其他雜環基包括氮丙啶基(aziridinyl)、氮雜環庚烷基(azepanyl)、二氮雜環庚烷基(diazepanyl)、二氮雜雙環[2.2.1]庚-2-基、三氮雜環辛烷基(triazocanyl)等，但並不限於此。 The term "heterocyclic" used in this specification includes all known cyclic groups containing reduced heteroatoms. Representative 5-membered heterocyclic groups include tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydro

Representative 6-membered heterocyclic groups include piperidinyl,

The various other heterocyclic groups include aziridinyl, azepanyl, diazepanyl, diazepanyl, diazepanyl [2.2.1] hept-2-yl, triazocanyl, etc., but are not limited thereto.

"Halogen" or "halogen (halo)" refers to chlorine, fluorine, bromine and iodine.

In a broad sense, the term "substituted" may include all permissible substituents of organic compounds. In some specific embodiments disclosed in the present specification, the term "substituted" refers to substitution with one or more substituents independently selected from the group consisting of (C _1- C ₆ ) alkyl, (C _2- C ₆ ) alkenyl, (C ₁ C ₆ ) perfluoroalkyl, phenyl, hydroxyl, -CO ₂ H, ester, amide, (C ₁ -C ₆ ) alkoxy, (C ₁ C ₆ ) thioalkyl, (C ₁ -C ₆ ) perfluoroalkoxy, NH ₂ , Cl, Br, I, F, NH lower alkyl, and -N(lower alkyl) ₂ . However, any other suitable substituents known to those skilled in the art may also be applicable to these embodiments.

The term organic field effect transistor (OFET) used in this specification should be understood to include the subclass 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, references to insulating materials or layers include dielectric materials or layers, and vice versa. Furthermore, the term "organic electronic device" as used in this specification should be understood to include the term "organic semiconductor device" and several specific embodiments of such devices, such as organic field effect transistors (OFETs).

As used in this specification, the terms "orthogonal" and "orthogonality" are understood to mean chemical orthogonality. For example, an orthogonal solvent is a solvent that allows a layer of material dissolved therein to be deposited on a previously deposited layer without dissolving or swelling the previously deposited layer.

The terms "polycycloolefin", "poly(cyclo)olefin" and "polynorbornene-type" are used interchangeably in this specification to refer to a polymer formed from an addition polymerizable monomer, a repeating unit in the resulting polymer, or a composition comprising such a polymer, wherein the repeating units of the resulting polymer include at least one norbornene-type moiety. The simplest norbornene-type polymerizable monomer included in the embodiments of the present invention is norbornene itself, i.e., bicyclo[2.2.1]hept-2-ene as shown below.

However, the terms norbornene monomer, norbornene repeating unit or norbornene polymer (PNB) used in this specification are not limited to only the part containing norbornene itself, but also include substituted norbornene or substituted or unsubstituted higher cyclic derivatives derived therefrom.

Some additives are known to significantly improve the performance of the composition when used in combination with the composition of the present invention when formed into thick or thin films, which can be used in various applications including but not limited to mechanical, electronic or electromechanical devices, including chip stacking applications, as redistribution layers (RDL) and complementary metal oxide semiconductor (CMOS) image sensors and various other devices including MEMS and MOEMS.

Therefore, according to the implementation of the present invention, a photosensitive composition is provided, which comprises: a) a polymer having: a first type of repeating units of the general formula (IA) derived from a monomer of the general formula (I):

衍生自通式(III)的單體之通式(IIIA)的第三類型的重複單元：

A second type of repeating unit of formula (IIA) derived from a monomer of formula (II):

A third type of repeating unit of formula (IIIA) derived from a monomer of formula (III):

表示與另一重複單元鍵結之位置；a為0~3的整數；b為1~4的整數；c為1~4的整數；R₁選自包括氫、甲基、乙基、正丙基、異丙基及正丁基的群組，其中一個以上的亞甲基亦即CH₂基可以任意被選自包括(C₁-C₄)烷基、苯基及苯基(C₁-C₄)烷基的群組中的基團獨立地取代；R₁₈選自-(CH₂)_s-、-(CH₂)_t-OCH₂-或-(CH₂)_t-(OCH₂CH₂) _u-OCH₂-，其中s為0~6的整數；t為0~4的整數；u為0~3的整數；R₁₉係-(CH₂)_v-CO₂R₂₀，其中v為0~4的整數，且R₂₀係氫或C₁-C₄烷基；b)光活性化合物，包含通式(A)的重氮醌部分：

c)多官能交聯劑，選自包括如下之群組：通式(IV)的化合物：

通式(V)的化合物：

in:

represents the position of bonding with another repeating unit; a is an integer of 0 to 3; b is an integer of 1 to 4; c is an integer of 1 to 4; R ₁ is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl and n-butyl, wherein one or more methylene groups, i.e., CH ₂ groups, may be arbitrarily substituted with groups selected from the group consisting of (C ₁ -C ₄ ) alkyl, phenyl and phenyl(C ₁ -C ₄ ) alkyl; R ₁₈ is selected from -(CH ₂ ) _s -, -(CH ₂ ) _t -OCH ₂ - or -(CH ₂ ) _t -(OCH ₂ CH ₂ ) _u -OCH ₂ -, wherein s is an integer of 0 to 6; t is an integer of 0 to 4; and u is an integer of 0 to 3; R ₁₉ is -(CH ₂ ) _v -CO ₂ R ₂₀ , wherein v is an integer of 0 to 4, and R ₂₀ is hydrogen or C ₁ -C ₄ alkyl; b) a photoactive compound comprising a diazoquinone moiety of the general formula (A):

c) a multifunctional crosslinking agent selected from the group consisting of: a compound of formula (IV):

Compounds of general formula (V):

e)通式(VI)的化合物：

wherein: n is an integer of 5 to 8; A is selected from the group consisting of C, CH-(CR ₂ ) _d -CH and a substituted or unsubstituted aryl group, wherein d is an integer of 0 to 4 and R is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl and n-butyl; B is selected from the group consisting of substituted or unsubstituted (C ₂ -C ₆ )alkylene and substituted or unsubstituted aryl groups; wherein the substituent is selected from the group consisting of halogen, methyl, ethyl, straight or branched (C ₃ -C ₆ )alkyl, (C ₃ -C ₈ )cycloalkyl, (C ₆ -C ₁₀ )aryl, (C ₇ -C ₁₂ )aralkyl, methoxy, ethoxy, straight or branched (C ₃ -C ₆ )alkoxy, (C ₃ -C ₈ )cycloalkoxy, (C 6 -C 10 )aryl, (C 7 -C 12 )aralkyl, ₆ -C ₁₀ )aryloxy and (C ₇ -C ₁₂ )aralkyloxy; d) a phenolic compound selected from the group consisting of:

e) Compounds of the general formula (VI):

wherein d and e are integers of 1 to 4; f and g are integers of 0 to 4; _R2 and _R3 are the same or different and are each independently selected from hydrogen, methyl, ethyl, linear or branched _C3 - _C6 alkyl, _C3 - _C8 cycloalkyl, _C6 - _C10 aryl and _C7 - _C12 aralkyl; or _R2 and _R3 together with the carbon atoms to which they are bound form a 5-8 membered substituted or unsubstituted carbocyclic ring, wherein the substituent is selected from _C1 - _C8 alkyl; _R4 and _R5 are the same or different and are each independently selected from hydrogen, methyl, ethyl, linear or branched ( _C3 - _C6 ) alkyl, ( _C3 - _C8 ) cycloalkyl, ( _C6 - _C10 ) aryl and ( _C7 - _C12 ) aralkyl.

In some embodiments, the polymers of the present invention comprise repeating units of formula (IIIA), wherein _R20 is typically hydrogen. However, in some embodiments, the polymers comprise a mixture of repeating units of formula (IIIA), wherein a portion of the repeating units of formula (IIIA) have _R20 as hydrogen, and another portion of the repeating units of formula (IIIA) have _R20 as ( _C1 - _C4 ) alkyl. Therefore, those skilled in the art will readily appreciate that such variations are all part of the present invention.

Non-limiting examples of monomers that can be used to form the first repeating unit of the present invention include the following:

5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene, also known as trioxanononylnorbornene (NBTON);

1-(Bicyclo[2.2.1]hept-5-en-2-yl)-2,5,8,11-tetraoxadodecyl, also known as tetraoxadodecylnorbornene (NBTODD);

5-(3-methoxybutoxy)methyl-2-norbornene (NB-3-MBM);

5-(3-methoxypropanoxy)methyl-2-norbornene (NB-3-MPM);

5-(2-(2-ethoxyethoxy)ethyl)bicyclo[2.2.1]hept-2-ene; and

5-(2-(2-(2-propoxyethoxy)ethoxy)ethoxy)bicyclo[2.2.1]hept-2-ene; Non-limiting examples of monomers that can be used to form the second repeating unit of the present invention include the following:

Norbornyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

4-(Bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)butan-2-ol (HFACH ₂ NB); and

5-(Bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)pentan-2-ol (HFACH ₂ CH ₂ NB).

Non-limiting examples of monomers that can be used to form the second repeating unit of the present invention include the following:

Ethyl 3-(bicyclo[2.2.1]hept-2-en-2-yl) propionate (EPEsNB);

3-(Bicyclo[2.2.1]hept-5-en-2-yl)acetic acid (NBMeCOOH);

Norbornene propionic acid (NBEtCOOH); and

Bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (acid 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 within the range of the monomers of formula (I) to (III) listed above. In addition, any amount of the monomers of formula (I) to (III) can be used to form a polymer that brings the expected benefits and expected purposes as described below. Therefore, all possible monomer ratios are 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 containing any three monomers described in this specification.

Typically, polymers according to embodiments of the present invention contain one or more of the above-mentioned first, second and third different types of repeating units, and as will be seen below, the other repeating units contained in the polymer embodiment are selected in a manner to impart properties to the polymer embodiment that are conducive to the use of the embodiment, so that the polymer embodiment is suitable for various specific applications.

For example, polymer embodiments generally require at least one repeating unit intended to provide imageability. Thus, the different types of repeating units represented by formula (IIIA) include carboxylic acid R ₁₉ with side groups. However, any other functional group that provides an acidic side group can be used instead. The carboxylic acid side group can generally be used to react with appropriately selected additives or other repeating units that can fix the positive tone image by post-development thermal crosslinking. Thus, similar side groups including but not limited to phenolic groups, sulfonic groups and other functional groups can also play a role in embodiments of the present invention. It should also be noted that it is readily understood by those skilled in the art that such polymer compositions containing acidic side groups can be prepared by post-polymerization using appropriate monomers. For example, polymers containing NBEtCOOH monomer repeating units can generally be prepared by first forming the polymer with EPEsNB and then hydrolyzing the ester functional groups of the resulting polymer using any method known in the art. Therefore, a certain residual amount of ester monomer repeating units may always be present in the polymers used in this specification. That is, when using polymers containing NBEtCOOH and other repeating units, the polymers may still contain some monomer repeating units derived from EPEsNB, i.e., starting monomers.

It should also be noted that one or more different types of monomers of formula (I) to (III) can be used in any molar ratio to form the polymer of the present invention. That is, one or more monomers of formula (I) can be used simultaneously with one or more monomers of formula (II) and one or more monomers of formula (III) to form the polymer of the present invention. Thus, the polymer of the present invention typically incorporates about 1 mol % to about 98 mol % of the repeating unit of formula (IA). The remaining repeating units are derived from a combination of one or more repeating units of formula (IIA) and (IIIA). Thus, in some embodiments, the terpolymer comprises any combination of monomer repeating units of formula (IA), (IIA) and (IIIA), wherein the molar ratio of the repeating units may 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, etc. In other embodiments, the examples of the molar ratio of the monomers (I): (II): (III) used to form the polymer may be in the range of 1:1:98~98:1:1~1:98:1, respectively, wherein the molar ratio of the repeating units of formula (IA): (IIA): (IIIA) is 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 generally contain monomer repeating units having acidic side groups (generally of the general formula (IIIA)) advantageously provide specific benefits to the photosensitive compositions of the present invention. Thus, in some embodiments of the present invention, the polymer used in the composition of the present invention contains about 10-80 mol% of monomer repeating units containing acidic side groups, and in other embodiments, 20-70 mol%. In other embodiments, the molar % of monomer repeating units of the general formula (IA) in the polymer can be about 0-80 mol%, 10-80 mol%, and in other embodiments, about 20-70 mol%. In other embodiments, the molar % of monomer repeating units of the general formula (IIA) in the polymer can be about 0-80 mol%, 10-80 mol%, and in other embodiments, about 20-70 mol%.

It should also be noted that it is not necessary to include all three of the above monomers to form a polymer to bring about the desired results described in this specification. It is believed that homopolymers comprising any repeating unit of formula (IA), (IIA) or (IIIA) can also function in the present invention. In addition, copolymers having any two repeating units of formula (IA), (IIA) or (IIIA) can also function as polymer resins in the compositions of the present invention. More specifically, it is believed that copolymers of HFANB and NBEtCO ₂ H can be used in the photosensitive compositions of the present invention. Again, as mentioned above, terpolymers are used in embodiments of the present invention.

The weight average molecular weight ( _Mw ) of the polymer used in the photosensitive composition according to the present invention is generally at least about 5,000. In other embodiments, the _Mw of the polymer used in the present invention is at least about 7,000. In other embodiments, the _Mw of the polymer is at least about 500,000. In addition, in one embodiment of the present invention, the weight average molecular weight of the polymer used in this specification is 5,000-500,000 or 7,000-200,000 or 8,000-100,000. The weight average molecular weight ( _Mw ) and number average molecular weight ( _Mn ) are generally defined by gel permeation chromatography (GPC) using polystyrene calibration standards. However, any known method can also be used to define _Mw and _Mn . The polydispersity index (PDI) ( _Mw / _Mn ) of a polymer can also be defined.

In another aspect of the invention, the photosensitive composition of the invention comprises a photoactive compound, typically having a photoactive diazoquinone moiety. Such photoactive compounds (PACs) are known to undergo photoinduced rearrangement when exposed to actinic (or electromagnetic) radiation of an appropriate wavelength, such as 254, 365, 405 or 436 nm, and by using an appropriate light source, the wavelength of the radiation can be varied depending on the nature of the PAC used. For example, the PAC used in some embodiments of the invention comprises one or more diazoquinone moieties represented by the general formula (C), (D) or (E), respectively:

其中至少一個Q為通式(C)或(D)的基團，且任意剩餘的Q為 氫。該等光活性化合物的例子的市售品包括Toyo Gosei Co.,Ltd.的TrisP-3M6C-2(4)-201。 Typically, structures of formula (C), (D) and/or (E) are incorporated into a photosensitive composition as an esterification product of a sulfonyl chloride (or other reactive moiety) and a phenolic compound, such as one of structures b-1 to b-6 shown below, which are generally referred to as photoactive compounds or PACs as described above. Therefore, any combination of any one or more of these PACs is combined with a polymer to form a positive tone composition of an embodiment of the present invention. In each of formulas (b-1) to (b-6), Q represents any structure of formula (C), (D) or (E). Advantageously, when a portion of a film or layer of the photosensitive composition is exposed to appropriate actinic or electromagnetic radiation, the esterification products produce carboxylic acids that enhance the solubility of the exposed portions in aqueous alkaline solutions compared to any unexposed portions of the films. Typically, the photosensitive materials are blended into the composition in an amount of 5 to 50 pphr of polymer, wherein the specific ratio of the photosensitive material to the polymer is a function of the dissolution rate of the exposed portion relative to the unexposed portion and the amount of radiation required to achieve the expected difference in dissolution rate. Advantageous photosensitive materials that can be used in the embodiments of the present invention are shown in the following general formulas b-1 to b-6; other useful photosensitive materials are shown in U.S. Patent No. 7,524,594 B2, Items 14-20, the relevant portions of which are incorporated into this specification by reference:

At least one Q is a group of the general formula (C) or (D), and any remaining Q is hydrogen. Examples of commercially available 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 this specification can be used in the photosensitive composition of the present invention. Generally, the equivalent amount is in the range of 1 to 50 parts by weight per 100 parts by weight (pphr) of the polymer (i.e., resin) described in this specification. In other embodiments, the equivalent amount can be in the range of 5 to 30 pphr.

Advantageously, it is believed that the use of at least one suitable multifunctional crosslinking agent of general formula (IV) or (V) as described in this specification in the photosensitive composition of the present invention can bring beneficial effects to the composition of the present invention. Such benefits include, but are not limited to, improvements in mechanical and thermal properties.

Any amount of crosslinking agent of general formula (IV) or (V) that brings the expected benefit can be used in the composition of the present invention. In some embodiments, the amount of one or more compounds of general formula (IV) or (V) used in the composition of the present invention is in the range of 8 to 30 parts by weight per 100 parts by weight (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. However, it should be noted that, especially when using more than one compound of general formula (IV) or (V), compounds of general formula (IV) or (V) greater than 30 pphr may also be used

Non-limiting examples of functional crosslinking agents of formula (IV) or (V) that can be used in the present invention include the following:

2,2'-(((2,2-bis((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxirane), commercially available as PEGE from Alfa Aesar;

2,2'-(((2-(1,3-bis(oxiran-2-ylmethoxy)propan-2-yl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxiran);

1,1,2,2-Tetrakis(4-((oxiran-2-ylmethoxy)methyl)phenyl)ethane;

1,2,4,5-Tetrakis((oxiran-2-ylmethoxy)methyl)benzene; and

2,2'-(((2-(1,3-bis(oxiran-2-ylmethoxy)prop-2-yl)-2-((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxiran).

Other suitable crosslinking agents include the following:

Wherein, n=1-3 (OXBP), for example, when n=1, 4,4'-bis(((3-ethyloxycyclobutane-3-yl)methoxy)methyl)-1,1'-biphenyl;

Bis(4-(oxiran-2-ylmethoxy)phenyl)methane;

Phenol formaldehyde polymer epoxypropane, where n=1~10 (EPON862);

Tris(oxypropylene) ether of glycerol, commercially available as Heloxy 84 or GE-36 from Momentive Specialty Chemicals Inc.;

Heloxy107.

It is believed that the use of one or more phenolic compounds of the general formula a-1 to a-6 will further provide favorable benefits to the composition of the present invention. Some of these phenolic compounds are commercially available, for example, from Toyo Gosei Co., Ltd. as Tris P-3M6C-2 Ballast. In addition, any amount of one or more phenolic compounds of the general formula a-1 to a-6 that bring the desired results described in this specification can be used in the photosensitive composition of the present invention. Generally, the equivalent amount is in the range of 1 to 25 parts by weight per 100 parts by weight (pphr) of the polymer (i.e., resin) described in this specification. In other embodiments, the equivalent amount may be in the range of 3 to 20 pphr, and in still other embodiments, the equivalent amount may be in the range of 5 to 15 pphr.

As mentioned above, more than one compound of the general formula (VI) can also be used in the composition of the present invention. Non-limiting examples of compounds of the general formula (VI) can be listed as follows: 2,2'-methylenediphenol (also known as 2,2'-bis(hydroxyphenyl)methane or o,o'-BPF); 4,4'-methylenediphenol; 2,2'-(ethane-1,1-diyl)diphenol; 4,4'-(ethane-1,1-diyl)diphenol; 2,2'-(propane-1,1-diyl)diphenol; 4,4'-(propane-1,1-diyl)diphenol; 2,2'-( Propane-2,2-diyl)diphenol; 4,4'-(propane-2,2-diyl)diphenol; 2,2'-(4-methylpentane-2,2-diyl)diphenol; 4,4'-(4-methylpentane-2,2-diyl)diphenol; 2,2'-(5-methylheptane-3,3-diyl)diphenol; 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)diphenol; 2-cyclohexyl-4-(2-(4-hydroxyphenyl)prop-2-yl)-5-methylphenol; 6,6'- Methylenebis(2-(tert-butyl)-4-cresol); 6,6'-(2-methylpropane-1,1-diyl)bis(2,4-xylenol); 4,4'-(2-methylpropane-1,1-diyl)bis(2-(tert-butyl)-5-cresol); 4-(4-hydroxybenzyl)benzene-1,2,3-triol (also known as 1,2,3-trihydroxy-4-[(4'-hydroxyphenyl)methyl]benzene; and any mixtures thereof.

Furthermore, any amount of one or more compounds of the general formula (VI) that bring about the desired results described in the specification can be used in the photosensitive composition of the present invention. Usually, the equivalent amount is in the range of 5 to 30 parts by weight per 100 parts by weight (pphr) of the polymer (i.e., resin) described in the specification. In other embodiments, the equivalent amount may be in the range of 7 to 20 pphr, and in still other embodiments, the equivalent amount may be in the range of 9 to 15 pphr.

唑啉-2-基等

唑啉基、N-羥甲基胺基羰基等羥甲基或N-甲氧基甲基胺基羰基等烷氧基甲基，但並不限於此。通常，上述之與聚合物的酸性側基的鍵結為藉由加熱至適當溫度而引發之交聯反應，通常在高於110℃的溫度下加熱適當時間。因此，在本發明的一些實施形態中，本發明的感光性組成物包含選自以下之一種以上的環氧化合物，但並不限於此：

The photosensitive composition of the present invention also includes an additive capable of bonding with the acidic side groups of the polymer resin. The material includes an additive, the additive being mixed with one or more epoxy groups of epoxypropyl, epoxycyclohexyl, and cyclobutylene; 2-

Oxazoline-2-yl, etc.

The photosensitive composition of the present invention comprises at least one epoxy compound selected from the following:

2,2'-(((2-ethyl-2-((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxirane), commercially available as Denacol EX321 (Nagase);

(2R,3R,4R,5S)-1,3,5,6-Tetra(oxiran-2-ylmethoxy)hexane-2,4-diol (also known as tetra-O-(oxiranylmethyl)-D-glucitol) (Denacol EX-614 from Nagase); and

1,2-Bis(oxiran-2-ylmethoxy)ethane.

唑啉環之聚合物，例如2-甲基-2-

唑啉、2-乙基-2-

唑啉、1,3-雙(2-

唑啉-2-基)苯、1,4-雙(2-

唑啉-2-基)苯、2,2’-雙(2-

唑啉)、2,6-雙(4-異丙基-2-

唑啉-2-基)吡啶、2,6-雙(4-苯基-2-

唑啉-2-基)吡啶、2,2’-異亞丙基雙(4-苯基-2-

唑啉)、(S,S)-(-)-2,2’-異亞丙基雙(4-第三丁基-2-

唑啉)、聚(2-丙烯基-2-

唑啉)等；N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺、糠醇、苄醇、柳醇、1,2-苯二甲醇、1,3-苯二甲醇、1,4-苯二甲醇及可溶酚醛型酚樹脂或該等的混合物等。通常認為該種材料在使用5pphr聚合物~40pphr聚合物時為有效。然而，應理解，更多或更少的添加量亦證明有效，因為該等功效中的至少一部分取決於所使用聚合物的性質及包含交聯性側基之重複單元的莫耳%。 Other exemplary crosslinkable or crosslinkable materials that can be used as additives to form the photosensitive composition of the present invention include bisphenol A epoxy resin, bisphenol F epoxy resin, epoxy resin containing silicone, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycidyloxypropyl trimethoxysilane, polymethyl (glycidyloxypropyl) cyclohexane, etc.;

Azoline ring polymers, such as 2-methyl-2-

Oxazoline, 2-ethyl-2-

Oxazoline, 1,3-bis(2-

oxazolin-2-yl)benzene, 1,4-bis(2-

oxazolin-2-yl)benzene, 2,2'-bis(2-

oxazoline), 2,6-bis(4-isopropyl-2-

Oxazoline-2-yl)pyridine, 2,6-bis(4-phenyl-2-

oxazolin-2-yl)pyridine, 2,2'-isopropylidenebis(4-phenyl-2-

oxazoline), (S,S)-(-)-2,2'-isopropylidenebis(4-tert-butyl-2-

oxazoline), poly(2-propenyl-2-

oxazoline); N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, furfuryl alcohol, benzyl alcohol, salicyclic alcohol, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol and soluble phenolic resin or mixtures thereof. It is generally believed that such materials are effective when 5 pphr to 40 pphr of polymer is used. However, it should be understood that more or less addition amounts are also proven to be effective, because at least part of these effects depend on the nature of the polymer used and the molar % of repeating units containing crosslinking side groups.

In another aspect of the present invention, the photosensitive composition comprises a compound or a mixture of compounds that improves the properties of the composition, including, but not limited to, improved photospeed and solubility properties and various other uses. Advantageously, it is believed that the compound of formula (VII) can be used as an additive according to the practice of the present invention.

wherein x and y are integers of 0 to 4. R ₂₁ and R ₂₂ are the same or different and are each independently selected from hydrogen, halogen, methyl, ethyl, linear or branched C ₃ -C ₁₈ alkyl, C ₁ -C ₁₈ perfluoroalkyl, methoxy, ethoxy, linear or branched C ₃ -C ₁₈ alkoxy, C ₃ -C ₁₆ cycloalkyl, C ₆ -C ₁₆ bicycloalkyl, C ₈ -C ₁₆ tricycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₈ aralkyl, -(CH ₂ ) _w CO ₂ R ₂₃ , -(CH ₂ ) _z OR ₂₄ . _Ar1 and _Ar2 are the same or different and are independently selected from _C6 - _C10 aryl, _C7 - _C18 aralkyl, wherein the aryl or aralkyl can be further substituted by substituents known to those skilled in the art. Z is selected from a bond, O, S, P, -NR-, -C(=O)-, -C(=O)-O-, -C(=O)-NR-, -SO-, -SO2-, _{-SO2NH -} alkyl or any carbocyclic crosslinking group including cycloalkyl, heterocycloalkyl, aryl, aralkyl, etc. wherein any cycloalkyl, bicycloalkyl or tricycloalkyl may contain one or more heteroatoms selected from O, S, N, P and Si. wherein w is an integer of 0 to 8, R ₂₃ is hydrogen, methyl, ethyl, straight or branched C ₃ -C ₁₈ alkyl. wherein z is an integer of 0 to 8, R ₂₄ is hydrogen, methyl, ethyl, straight or branched C ₃ -C ₁₈ alkyl. wherein R is hydrogen, methyl, ethyl, straight or branched C ₃ -C ₁₈ alkyl, C ₁ -C ₁₈ perfluoroalkyl, C ₃ -C ₁₆ cycloalkyl, C ₆ -C ₁₆ bicycloalkyl, C ₈ -C ₁₆ tricycloalkyl.

It is believed that various other phenolic compounds can also be used in the compositions of the present invention. Non-limiting examples of such compounds can be selected from the group consisting of: compounds of formula (VIII):

wherein h is an integer of 0 to 4; i is 1 or 2; R ₆ is independently hydrogen, methyl, ethyl, linear or branched C ₃ -C ₁₆ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₂ aralkyl or -CO ₂ H; the compound of general formula (IX):

wherein j and k are integers of 1 to 4; l and m are integers of 0 to 4; _R7 and _R8 are the same or different and are independently selected from hydrogen, methyl, ethyl, linear or branched _C3 - _C6 alkyl, _C3 - _C8 cycloalkyl, _C6 - _C10 aryl and _C7 - _C12 aralkyl; and compounds of general formula (X):

wherein n and o are integers of 1 to 4; p and q are integers of 0 to 4; R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are the same or different and are independently selected from hydrogen, methyl, ethyl, linear or branched C ₃ -C ₆ alkyl; or when R ₁₃ is -(CH ₂ ) _r -, one of R ₉ or R ₁₀ and one of R ₁₁ or R ₁₂ together with the carbon atom to which they are bound form a 5-8 membered substituted or unsubstituted carbocyclic ring, wherein the substituent is selected from C ₁ -C ₆ alkyl; R ₁₃ is -(CH ₂ ) _r - or phenylene, wherein r is 1 to 2; and R ₁₄ and R ₁₅ are the same or different and are independently selected from hydrogen, methyl, ethyl, linear or branched C ₃ -C ₆ alkyl, C ₃ -C C ₈ cycloalkyl, C ₆ -C ₁₀ aryl and C ₇ -C ₁₂ aralkyl.

Non-limiting examples of additives included in the compound of general formula (VIII) include: 2-cyclohexylphenol; 4-cyclohexylphenol; 2-cyclohexyl-5-cresol; 2,4-di-di-butylphenol; 2,6-di-tert-butyl-4-cresol; 2,4-di-tert-butylphenol; 4-dodecylphenol; 4-ethylresorcinol; 2-propylresorcinol; 4-butylresorcinol; 4-hexylresorcinol (also known as 4-hexylbenzene-1,3-diol); and any combination thereof.

Non-limiting examples of additives contained in the compound of general formula (IX) include: [1,1'-biphenyl]-2,2',4,4'-tetrol; 2'-methyl-[1,1'-biphenyl]-2,3,4,4'-tetrol; [1,1'-biphenyl]-2,2',4,4',6-pentanol; [1,1'-biphenyl]-2,2',3,4,4'-pentanol; and any combination thereof.

Non-limiting examples of additives included in the compound of general formula (X) include: 4,4',4"-(butane-1,1,3-triyl)tris(2-(tert-butyl)-5-methylphenol); 4,4'-(4-isopropyl-1-methylcyclohexane-1,3-diyl)diphenol; 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 any combination thereof.

Various other compounds that can be used in the composition of the present invention can be listed as follows:

-2,5-二酮(亦稱為肌胺酸酐)；1-乙基-4-甲基哌

-2,5-二酮；1,4-二乙基哌

-2,5-二酮；1-甲基-4-丙基哌

-2,5-二酮；1-乙基-4-丙基哌

-2,5-二酮；1-乙基-4-異丙基哌

-2,5-二酮；及任意組合該等的混合物。 1,4-Dimethylpiperidin

-2,5-dione (also known as creatinine anhydride); 1-ethyl-4-methylpiperidin

-2,5-dione; 1,4-diethylpiperidin

-2,5-dione; 1-methyl-4-propylpiperidin

-2,5-dione; 1-ethyl-4-propylpiperidin

-2,5-dione; 1-ethyl-4-isopropylpiperidin

-2,5-dione; and any combination thereof.

In other embodiments, the following compounds can also be used in the composition 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)phthalate; and any combination thereof.

In general, the various compounds and additives listed in this specification improve the overall performance of the photosensitive composition of the present invention, thereby providing a clear photopattern structure with various uses, including chip stacking applications, redistribution layers, and dam structures for forming CMOS image sensors. Advantageously, it is known 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 show specific dissolution enhancing activity, but can also play a promoting role as a crosslinking agent as described above. Therefore, the additives used in this specification do not limit the activity of the compounds to only one of the properties, but can also promote other functions of the photosensitive composition of the present invention.

It should also be noted that any additive represented by the above-mentioned structural formula (VI) to (X) can be used alone, that is, as any single compound and/or a combination of more than one compound in any combination thereof. That is, for example, in some embodiments, one or more compounds of the general formula (VI) can be used in combination with other compounds of the general formula (VII) to (X), such as a compound of the general formula (VI) combined with a compound of the general formula (VII) or a compound of the general formula (IX) or a compound of the general formula (X). In addition, the amount of additive that can be used depends on the expected result of the photosensitive composition of the present invention. Therefore, any amount that brings the expected result can be used in the present invention. Generally, the amount of additive that can be used can be in the range of 0.5 to 20 pphr, and in some embodiments, the amount can be in the range of 1 to 12 pphr.

It is known that various other compounds represented by structural formula (XIa)-(XIh) can also be used as one or more additives alone or in combination with any of the compounds of general formula (VI)-(X) listed above for forming the photosensitive composition of the present invention. It should also be noted that the additives, i.e. the compounds represented by structural formula (XIa)-(XIh), can be used alone or as a mixture of any combination thereof in any desired amount.

Aurintricarboxylic acid (XIa);

5,5'-Methylenedisalicylic acid (XIb);

5,5'-Thiodihydroxysalicylic acid (XIc);

3,3,3',3'-Tetramethyl-1,1'-spirobiindan-5,5',6,6',7,7'-hexanol (XId);

p-Toluenesulfonyl-p-toluidine (XIe);

Reduced phenolphthalein (XIf);

Biphenyl dicarboxylic acid (XIg); and

]-4a'(2'H)-基)苯-1,2,3-三醇，通常亦稱為五倍子酚-FZ(XIh)。 4-(5',6'-dihydroxy-1',3',4',9a'-tetrahydrospiro[cyclohexane-1,9'-

]-4a'(2'H)-yl)benzene-1,2,3-triol, also commonly known as gallol-FZ (XIh).

In another aspect of the present invention, various other additives suitable for use with the composition of the present invention include the following, but are not limited to:

D-sorbitol;

Absolute stereochemistry, rotation (+)

(+)-N,N,N',N'-Tetramethyl-L-tartaric acid diamide;

Lactide;

Diphenolic acid;

2,3,4-Trihydroxybenzoic acid;

2,4,6-Trihydroxybenzoic acid (hydrate);

4,5-Dihydroxymethyl-2-phenylimidazole.

The photosensitive composition of the present invention further comprises compounds which are particularly useful as adhesion promoters, antioxidants, crosslinking agents, coupling agents or hardeners. Non-limiting examples of such compounds are selected from the group consisting of the following, and commercially available materials are designated by such trade names.

Triethoxy(3-(oxiran-2-ylmethoxy)propyl)silane, also commonly known as 3-glycidoxypropyltriethoxysilane (3-GTS or (KBE-403 of Shin-Etsu Chemical Co., Ltd.));

Trimethoxy(3-(oxiran-2-ylmethoxy)propyl)silane, also commonly known as 3-glycidoxypropyltrimethoxysilane (KBM-403 from Shin-Etsu Chemical Co., Ltd.); C ₆ H ₅ (CH ₃ O) ₃ Si

Phenyltrimethoxysilane

C ₆ H ₅ (C ₂ H ₅ O) ₃ Si

Phenyltriethoxysilane (KBE-103, commercially available from Gelest, Inc. or Shin-Etsu Chemical Co., Ltd.)

3,3,10,10-Tetramethoxy-2,11-dioxa-3,10-disiladodecane (SIB-1832 from Gelest, Inc.);

Undec-10-en-1-ylsilane (SIU9048.0);

3-(Dimethoxy(methyl)silyl)propane-1-thiol (SIM6474.0);

2,2'-((3-(Triethoxysilyl)propyl)aminediyl)bis(ethan-1-ol) (SIB1140.0);

N,N'-bis[(3-triethoxysilylpropyl)aminocarbonyl]polyethylene oxide (SIB-1824.84 from Gelest, Inc.);

4,4,13,13-Tetraethoxy-3,14-dioxa-8,9-disulfa-4,13-disilahexadecane;

Triethoxy(3-thiocyanatopropyl)silane(SIT7908.0)

3,3,12,12-Tetramethoxy-2,13-dioxa-7,8-disulfa-3,12-disilotetradecane (Si-75 or Si-266 from Evonik Industries AG);

2,2'-((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene))bis(4-cresol) (TCI Japan's antioxidant AO-80);

4,4'-((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene))bis(2,6-xylenol)(Bis26X-PC)

6,6'-methylenebis(2-(2-hydroxy-5-methylbenzyl)-4-cresol)(4-PC);

Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (Irganox 1010 from BASF);

3,5-Bis(1,1-dimethylethyl)-4-hydroxy-octadecylphenylpropanoate (Irganox 1076 from BASF);

Bis(4-(2-phenylpropan-2-yl)phenyl)amine (Naugard 445 (NG445) commercially available from Chemtura Corporation);

Bis(4-(tert-butyl)phenyl)amine (Stearer Star from Chemical Products);

Bis(4-methoxyphenyl)amine (Thermoflex);

Bis(4-ethylphenyl)amine;

Bis(4-isopropylphenyl)amine

Bis(4-(2,4,4-trimethylpentan-2-yl)phenyl)amine (Irganox 5057 from BASF);

Bis(4-(1-phenylethyl)phenyl)amine (Wingstay29);

Bis(4-(2,4,4-trimethylpentyl)phenyl)amine (Irganox L 57 from BASF);

1-Benzyloctahydropyrrolo[1,2-a]pyrimidine (CGI-90 from BASF);

Tetrakis(2,3,4,5,6-pentafluorophenyl)borate (1-)[4-(1-methylethyl)phenyl](4-methylphenyl)-iodonium (Rhodorsil PI 2074 from Blue Star Silicones)

-9-酮(Lambson PLC的CPTX)；

1-Chloro-4-propoxy- 9H -sulfur

-9-Keto (CPTX from Lambson PLC);

(Kanto Corporation的吩噻

) 10H-Phenothianilide

(Phenothiazine from Kanto Corporation

)

1,4-Bis[(vinyloxy)methyl]-cyclohexane (cyclohexane divinyl ether (CHDVE))

Wherein R and R' are independently (C ₁ -C ₄ ) alkyl, and GE = epoxypropyl ether (BY-16-115);

Silicone-modified epoxy compound, commercially available as BY16-115 from Toray-Dow Corning Silicone Co., Ltd.

(HP-7200); and

Lowinox CPL.

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 the compounds can be used alone or as a mixture of any combination thereof to obtain the desired benefit, depending on the desired use. In addition, any amount of one or more of the above compounds can be used in the photosensitive composition of the present invention to obtain the desired results. It is generally believed that the equivalent amount is in the range of 0.5 to 20 parts by weight per 100 parts by weight (pphr) of the polymer (resin). In some embodiments, the equivalent amount is in the range of 1 to 10 pphr.

The photosensitive composition according to the present invention may also contain other components that can be used to improve the properties of the composition and the resulting film or polymer layer. For example, as described below, the sensitivity of the composition to the desired exposure radiation wavelength can bring about improved expected properties. Examples of such arbitrary components include one or more compounds/various additives, such as surfactants, silane coupling agents, leveling agents, phenolic resins, antioxidants, flame retardants, plasticizers, and hardening accelerators, but are not limited thereto.

First, the photosensitive composition according to the embodiment of the present invention is coated on the desired substrate to form a film. Such substrates include any suitable substrate itself, or, for example, semiconductor substrates, ceramic substrates, glass substrates, etc. used in electrical, electronic or optoelectronic devices. For the application, any suitable coating method can be used, such as spin coating, spray coating, scraper coating, meniscus coating, inkjet coating and slit coating.

The coated substrate is then heated to facilitate removal of residual casting solvent, for example at a temperature of 70°C to 140°C for about 1 to 30 minutes, but other suitable temperatures and times can also be used. After heating, the film is typically imagewise exposed to a suitable wavelength of actinic radiation, typically selected based on the photoactive compounds and/or photosensitizers incorporated into the polymer composition described in this specification. However, typically such suitable wavelengths are 200 to 700 nm. It should be understood that the phrase "imagewise exposure" refers to exposure through a masking factor to provide a pattern of exposed and unexposed portions of the resulting film.

After the film formed by the photosensitive composition or formulation according to the embodiment of the present invention is image-exposed, a developing step is performed. In the case of the positive-tone polymer formulation of the present invention, the developing step only removes the exposed portion of the film, thereby leaving a positive image of the shielding layer on the film. In the case of the negative-tone polymer formulation of the present invention, the developing step only removes the unexposed portion of the film, thereby leaving a negative image of the shielding layer on the film. In some embodiments, post-exposure baking can be performed before the above-mentioned developing step.

Suitable developers, particularly for positive tone formulations, may include aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and aqueous solutions of 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 generally used to provide solubility for the organic base. Aqueous solutions of TMAH are well known developer solutions in the semiconductor industry. Suitable developers may 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 formulation of the present invention provide a self-imageable film that develops the obtained image using an aqueous alkaline solution after imagewise exposure, while other embodiments develop the obtained image using an organic solvent. Independent of the type of developer used, after the image is developed, the excess developer solution is removed by washing the substrate, typically with water or a suitable alcohol and mixtures thereof.

After the above-mentioned rinsing, the substrate is dried and the imaging film is finally hardened. In other words, the image is fixed. In the case where the residual layer is not exposed during the imaging exposure, the fixing is usually achieved by initiating a reaction in the remaining part of the film. This reaction is usually a cross-linking reaction that can be initiated by heating and/or non-imaging exposure or full exposure of the residual material. This exposure and heating can be implemented in different steps, or in combination as is known to be suitable for the specific use of the imaging film. The full exposure is usually carried out using the same energy as used in the imaging exposure, but any suitable energy can be used. Heating is usually carried out at the required temperature, for example at a temperature above 110°C for 40 minutes to 1 hour or more. In the case where the residual layer is exposed during the imagewise exposure, this is usually completed by a heating step adjusted to terminate any reactions initiated by the exposure. However, as described above, it is also possible to additionally carry out a full exposure and heating. However, it should be understood that the final curing step is also selected depending on the type of device being formed, so when the residual layer is used as an adhesive layer or structure, the final fixation may not be the final curing.

The alkali-soluble photosensitive resin composition of the present invention is used to form a layer having high heat resistance, excellent water absorption, high transparency and low dielectric constant to manufacture devices. In addition, the layer usually has an excellent elastic coefficient after curing, typically 0.1kg/ ^mm2 ~200kg/ ^mm2 .

As described above, exemplary applications of the photosensitive composition according to the present invention include chip connection adhesives, wafer bonding adhesives, insulating films (interlayer dielectric layers), protective films (passivation layers), mechanical buffer films (stress buffer layers) or planarization films for various semiconductor devices and printed circuit substrates. Specific applications of these embodiments include chip connection adhesives for forming single-layer or multi-layer semiconductor devices, dielectric films formed on semiconductor devices; buffer films formed on passivation films; interlayer insulating films formed on circuits formed on semiconductor devices.

Therefore, according to the embodiments of the present invention, a positive tone photosensitive polymer composition is provided, which exhibits enhanced properties in one or more mechanical properties (e.g., elongation at break with low stress after aging) and has at least equal chemical resistance compared to alternative materials. In addition, such embodiments generally provide excellent electrical insulation, adhesion to substrates, etc. Therefore, semiconductor devices, device packages, and display devices incorporating embodiments of the present invention can be provided.

Advantageously, the photosensitive composition of the present invention is considered to be 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 such purposes is formed by a cured product of the photosensitive adhesive composition of the present invention. Although the adhesive layer is a single-layer structure, it not only has sufficient adhesion to the substrate, but also no significant stress is found to be generated by the curing step. Therefore, it is possible to avoid an unnecessary thick layer of a film containing a chip as a laminate. It is found that the laminate formed according to the present invention has reliability in alleviating stress concentration caused by thermal expansion difference and 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. Such semiconductor devices are particularly advantageous for electronic devices with very small internal volumes and, for example, carried as mobile devices. More advantageously, by implementing the present invention, various electronic devices characterized by miniaturization, thinness, and lightness that have not been achieved so far can be formed, and even if such devices are subjected to severe operations such as shaking or dropping, the functions of the semiconductor devices are not easily damaged.

The cured product of the photosensitive adhesive composition of the present invention, i.e., the adhesive layer or film, generally exhibits an indentation modulus of 2 to 3.5 GPa at 25°C. The cured product of the photosensitive adhesive composition of the present invention exhibits an indentation modulus of 70 to 120% of the indentation modulus of the uncured product at 25°C, i.e., before the 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 generally can obtain an adhesion of 20 to 200 Newtons (N) at 25°C before curing, etching, and ashing steps.

Therefore, it is believed that the photosensitive adhesive composition of the present invention exhibits an indentation modulus equivalent to that of an uncured sample at room temperature after curing, and not only does it not cause significant stress concentration between semiconductor chips, but it also helps to form an adhesive layer with sufficient adhesion. In addition, since the indentation modulus in the state before curing is within the specified range of the indentation modulus after curing, and the photosensitive adhesive composition before curing does not significantly deform or overflow, for example, it is possible to improve the alignment accuracy when laminating semiconductor chips. Furthermore, since the change in the indentation modulus before and after curing is relatively small, it is possible to reduce the shrinkage related to photosensitivity, and it is possible to reduce the interface stress between semiconductor chips caused by the curing shrinkage. This also helps improve the reliability of chip stacking.

On the other hand, advantageously, the photosensitive adhesive composition of the present invention has sufficient adhesion to the semiconductor chip required for chip bonding before hardening and after the etching step and the ashing step. Therefore, the adhesive layer used to bond the semiconductor chips to each other firmly fixes the semiconductor chips to each other and helps to improve the reliability of the chip stack.

Thus, the photosensitive adhesive composition according to the present invention can realize an adhesive layer with sufficient adhesion and stress relief. That is, since the adhesive layer has the protective function of the buffer coating film (or buffer coating function) and the adhesive function of the chip adhesive film (or chip bonding function) in a single layer, it is possible to form a chip stack without reducing reliability, and make the chip stack thinner than the existing two-layer chip stack. In addition, since the chip stack is thinner, the volume of the mold part can be reduced and the bonding line can be shortened, so these factors contribute to weight reduction and cost reduction.

Therefore, in some embodiments, as described above, the indentation modulus of the cured product of the photosensitive adhesive composition of the present invention is generally 2 to 3 GPa at 25° C., and in other embodiments, the indentation modulus is 2.2 to 3.2 GPa, and in still other embodiments, the indentation modulus is 2.4 to 3.0 GPa. In addition, when the indentation modulus of the cured product is less than the above lower limit, the adhesiveness of the adhesive layer is reduced, so that the interface between the layer and the semiconductor chip is peeled off, and when the mold portion contains a filler, the filler passes through the adhesive layer and has an adverse effect on the semiconductor chip. At the same time, when the indentation modulus of the hardened product is greater than the above upper limit, the flexibility of the adhesive layer will decrease, so the stress will be relieved, for example, the residual stress generated by the lamination of the semiconductor chip and the local concentration of thermal stress caused by the thermal expansion difference between the semiconductor chip and the adhesive layer cannot be relieved. As a result, cracks are generated on the semiconductor chip, or the semiconductor chip and the adhesive layer are peeled off from each other. These problems can be easily overcome by using the photosensitive adhesive composition of the present invention.

In addition, the indentation modulus of the hardened product is measured at 25°C using an indentation machine.

In addition, the melt viscosity of the photosensitive adhesive composition of the present invention is generally about 20 to 500 Pascal seconds (Pa.s) in the range of 100 to 200°C before curing. Since this composition has excellent wettability to the semiconductor chip 20 (Figure 2), it becomes less likely to generate voids in the adhesive layer. Therefore, since a homogeneous adhesive layer with less uneven physical properties can be formed, when the semiconductor chips are bonded together by the adhesive layer, the adhesive layer rarely causes local concentration of stress. Therefore, cracks on the semiconductor chip can be suppressed, and peeling between the adhesive layer and the semiconductor chip can be suppressed.

The melt viscosity of the hardened photosensitive adhesive composition of the present invention can be measured by a rheometer. Therefore, in some embodiments of the present invention, the melt viscosity before hardening is about 25~400Pa.s, and in other embodiments, the melt viscosity before hardening is about 30~300Pa.s.

In addition, although the photosensitive adhesive composition of the present invention has a certain degree of adhesiveness in the pre-curing state, the adhesiveness can be reduced by irradiating it with UV radiation. 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 viscosity of generally greater than 3.0N/25mm at 25°C relative to a back grinding tape that can be peeled off by UV radiation before hardening and after etching and ashing steps. Since the photosensitive adhesive composition of the present invention still has sufficient adhesion to the back grinding film after undergoing specific treatments such as etching treatment and ashing treatment that accelerate the degradation of organic materials, the semiconductor wafer formed by the photosensitive adhesive composition of the present invention can still be firmly fixed when the semiconductor wafer is cut, thereby improving the cutting accuracy.

Therefore, in some embodiments of the present invention, the above-mentioned viscosity (i.e., bonding strength) is 3.5~10.0N/25mm.

On the other hand, the photosensitive adhesive composition of the present invention, before curing and after UV irradiation, has a viscosity of 0.5N/25mm at 50°C relative to the back grinding tape that can be peeled by UV irradiation. Since the photosensitive adhesive composition of the present invention has less adhesion to the back grinding tape when UV irradiated, it is easy to separate the dicing tape and the coating film when the chip is clamped after the dicing step, thereby preventing potential defects such as chip damage.

In addition, by reducing the viscosity (i.e., adhesiveness), for example, it is possible to suppress the photosensitive adhesive composition of the present invention from adhering to the cutting blade in the cutting step and adhering to the clamp in the mounting step. As a result, it is possible to suppress the occurrence of cutting or clamping errors.

Therefore, in some embodiments of the present invention, the above viscosity is 0.05N/25mm~0.4N/25mm.

In addition, the UV irradiation step is a step of irradiating with light of 365 nm wavelength with an exposure dose of 600 mJ/cm ² in cumulative light amount. In some embodiments, the exposure dose of the light source is in the range of about 100-500 mJ/cm ^2. In other embodiments, the exposure dose of the light source is in the range of about 150-400 mJ/cm ^2. In still other embodiments, the exposure dose of the light source is in the range of about 200-250 mJ/cm ² .

It is believed that by using the photosensitive composition of the present invention, a circular through hole with very high resolution can be formed. The resolution of the through hole can be in the range of 1 to 100 μm. In some embodiments, the resolution of the through hole can be in the range of 3 to 30 μm. In other embodiments, the resolution of the through hole can be in the range of 5 to 15 μm.

Furthermore, the back-grinding UV peeling tape used in the above embodiments is typically made of acrylic resin. However, any tape that can produce the above results can be used.

Therefore, as described above, in some embodiments of the present invention, the photosensitive composition is soluble in an alkaline developer.

In addition, as described above, in some embodiments of the present invention, the electronic and/or semiconductor device according to the present invention includes a multilayer semiconductor device, wherein the multilayer body contains the photosensitive composition according to the present invention.

In some embodiments of the present invention, the semiconductor device includes a redistribution layer (RDL) structure further including a photosensitive composition according to the present invention.

In addition, as described above, in some embodiments of the present invention, the semiconductor device includes a chip stacking structure further including a photosensitive composition according to the present invention.

As described above, in some other embodiments of the present invention, the semiconductor device includes a complementary metal oxide semiconductor (CMOS) image sensor dam structure further including a photosensitive composition according to the present invention.

Furthermore, as described above, in some embodiments of the present invention, a film is formed from the photosensitive composition according to the present invention. As described above, such a film generally exhibits excellent chemical, mechanical, and elastic properties, which are widely used in electronic, optoelectronic, and micro-electromechanical applications with excellent dielectric properties.

Therefore, in some embodiments of the present invention, a microelectronic device or optoelectronic device is provided, which includes one or more redistribution layer (RDL) structures, chip stacking structures, and CMOS image sensor dam structures, wherein the aforementioned structures further include a photosensitive composition according to the present invention.

In addition, in some embodiments of the present invention, a method for forming a film for manufacturing a microelectronic device or an optoelectronic device is provided, which includes: a step of coating a suitable substrate with a composition according to the present invention to form a film; a step of patterning the film with a mask by exposing it to suitable radiation; a step of developing the film after exposure to form a photo pattern; and a step of hardening the film by heating it to a suitable temperature.

The photosensitive composition of the present invention can be coated on a substrate by any coating step described in this specification and/or coating steps such as spin coating known to those skilled in the art.

Furthermore, the development according to the method of the present invention can be performed by any known developing technique such as using an aqueous developer.

In some embodiments of the present invention, the developer used in the method of the present invention is an aqueous solution of tetramethylammonium hydroxide (TMAH).

Furthermore, in some embodiments of the present invention, before the hardening step, the substrate is first hard-baked at a temperature of 130°C to 160°C for 20 minutes to 60 minutes.

Finally, in some other embodiments of the present invention, the hardening is performed at a temperature of 170°C to 200°C with a heating ramp of 5°C increments for 1 to 5 hours.

[Implementation example]

Generally, the polymers used to form the photosensitive composition of the present invention are known in the literature and are prepared according to known procedures. For example, refer to U.S. Patent No. 9,696,623 B2, the relevant parts of which are introduced into this specification by reference.

Implementation Example 1

Generally, any polymer described in this specification can be used. For example, the terpolymer of polynorbornene derivatives described in this specification is dissolved in a suitable solvent such as propylene glycol methyl ether acetate (PGMEA) and mixed with a specific amount of the additives shown in Table 1 expressed as parts per 100 parts of resin (pphr) in an amber HDPE bottle of appropriate size. The mixture is shaken for 18 hours to produce a homogeneous solution. Particle contamination is removed by filtering the polymer solution with a 0.45μm pore polytetrafluoroethylene (PTFE) disc filter at a pressure of 35psi, and the filtered polymer solution is collected in a low-particle HDPE amber bottle and stored at 5°C.

The composition thus formed was placed at room temperature and applied to a plurality of 125 mm diameter silicon wafers (thickness: 625 μm) by spin coating, initially at 200 rpm for 10 seconds and then at 500 rpm for 30 seconds. The substrate thus formed was placed on a heating plate at 120°C for 4 minutes, thereby obtaining a polymer film of approximately 2 micrometers (μm) thick. Each polymer film was image-exposed with an exposure energy ranging from 125 to 500 mJ/cm ^2. Then, each film was developed by immersion development by immersing it twice in 0.26 N TMAH for 5 seconds using a spin coating method. After the development step, each wafer was rinsed by spraying deionized water for 5 seconds and then spin dried at 3000 rpm for 15 seconds.

Figure 1 shows the lithographic images obtained with different exposure energies using the compositions of the present invention. Specifically, Figures 1A to 1D show lithographic images taken with a stepper and a mask alignment exposure machine at threshold exposure doses of 125mJ/ ^cm2 , 175mJ/ ^cm2 , 225mJ/ ^cm2 , and 300mJ/ ^cm2, respectively.

Comparison Example 1

A composition substantially the same as Example 1 was prepared, but without the tetrafunctional epoxy compound kit and including some of the other additives shown in Table 1 for use in the comparative experiments described in Examples 2 and 3.

Example 2

Chip shear strength measurement

The composition described in Example 1 was spin-coated on a silicon wafer and baked at 120°C for 4 minutes to obtain a 10μm thick film. The film was hard-baked at 150°C for 40 minutes. The wafer was then singulated into 10mmx20mm chips. Next, the chips were placed on a heating plate at 150°C, and each 4mmx4mm silicon chip was pressed against the surface of the coated singulated chip with a force of 1kg-f for 1 second. The bonded chips were moved into a nitrogen oven and the composition of Example 1 was hardened at 180°C for 2 hours. After hardening, the chip assembly was moved to a heating table (260°C), and a 4mmx4mm chip was cut out from the 10mmx20mm chip containing the composition of Example 1. Wafer shear forces were measured and recorded.

Similarly, except for using the composition of Comparative Example 1, the sample was prepared in basically the same manner as the above method.

Figure 2 shows the results obtained from the wafer shear measurement. From the data, it can be seen that the composition of Example 1 is significantly better than that of Comparative Example 1.

Implementation Example 3

The composition described in Example 1 is spin coated on a suitable substrate and baked at 120°C 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 using a tetramethylammonium hydroxide (TMAH) developer to reveal unexposed areas. 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 hardened sample is then exposed to an acidic etchant to remove any oxidized surface. The etchant temperature is maintained in a temperature range from room temperature to 50°C for 5 minutes to 15 minutes. After the etching step, the polymer sample was observed with an optical microscope to observe whether peeling or over-etching occurred during the etching step. When comparing Example 1 with Comparative Example 1, the various compositions prepared according to the present invention showed less peeling.

The present invention is illustrated by some of the above-mentioned embodiments, but is not limited thereto. It should be understood that the present invention includes the general scope described above. Various modifications and implementation forms can be realized without departing from the spirit and scope of the present invention.

Claims (20)

A photosensitive composition comprising: a) a polymer having: a first type of repeating units of formula (IA) derived from a monomer of formula (I):

A second type of repeating unit of formula (IIA) derived from a monomer of formula (II):

A third type of repeating unit of formula (IIIA) derived from a monomer of formula (III):

in:

represents the position of bonding with another repeating unit; a is an integer of 0 to 3; b is an integer of 1 to 4; c is an integer of 1 to 4; R ₁ is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl and n-butyl; R ₁₈ is selected from -(CH ₂ ) _s -, -(CH ₂ ) _t -OCH ₂ - or -(CH ₂ ) _t -(OCH ₂ CH ₂ ) _u -OCH ₂ -, wherein s is an integer of 0 to 6, t is an integer of 0 to 4, and u is an integer of 0 to 3, R ₁₉ is -(CH ₂ ) _v -CO ₂ R ₂₀ , wherein v is an integer of 0 to 4, and R ₂₀ is hydrogen or C ₁ -C ₄ alkyl; b) a photoactive compound comprising a diazoquinone moiety of the general formula (A):

c) a multifunctional crosslinking agent selected from the group consisting of:

2,2'-(((2,2-bis((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxiran);

2,2'-(((2-(1,3-bis(oxiran-2-ylmethoxy)propan-2-yl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxiran);

1,1,2,2-Tetrakis(4-((oxiran-2-ylmethoxy)methyl)phenyl)ethane;

1,2,4,5-Tetrakis((oxiran-2-ylmethoxy)methyl)benzene; and

2,2'-(((2-(1,3-bis(oxiran-2-ylmethoxy)prop-2-yl)-2-((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxiran); d) a phenolic compound selected from the group consisting of:

e) Compounds of the general formula (VI):

wherein d and e are integers of 1 to 4; f and g are integers of 0 to 4; _R2 and _R3 are the same or different and are each independently selected from hydrogen, methyl, ethyl, linear or branched _C3 - _C6 alkyl, _C3 - _C8 cycloalkyl, _C6 - _C10 aryl and _C7 - _C12 aralkyl; or _R2 and _R3 , together with the carbon atom to which they are bonded, form a 5-8 membered substituted or unsubstituted carbocyclic ring, wherein the substituent is selected from _C1 - _C8 alkyl; and _R4 and _R5 are the same or different and are each independently selected from hydrogen, methyl, ethyl, linear or branched ( _C3 - _C6 ) alkyl, ( _C3 - _C8 ) cycloalkyl, ( _C6 - _C10 ) aryl and ( _C7 - _C12 ) aralkyl. The photosensitive composition as described in item 1 of the patent application, wherein the first repeating unit of the polymer is derived from a monomer selected from the group consisting of: trioxa nonyl norbornene (NBTON); tetraoxa dodecyl norbornene (NBTODD); 5-(3-methoxybutoxy)methyl-2-norbornene (NB-3-MBM); and 5-(3-methoxypropaneoxy)methyl-2-norbornene (NB-3-MPM). The photosensitive composition as claimed in claim 2, wherein the second repeating 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 ₂ NB); norbornyl-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)pentan-2-ol (HFACH ₂ CH ₂ NB). The photosensitive composition as described in claim 3, wherein the third repeating 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 norbornene propionic acid (NBEtCOOH). The photosensitive composition as described in item 1 of the patent application, wherein the diazoquinone part is represented by the general formula (C), (D) or (E):

The photosensitive composition as described in item 1 of the patent application, wherein the photoactive compound is selected from one or more of the following:

Wherein at least one Q is a group of general formula (C) or (D):

, and the remaining Q is hydrogen. The photosensitive composition as described in claim 1, wherein the multifunctional crosslinking agent is selected from the group consisting of:

2,2'-(((2,2-bis((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxiran); and

2,2'-(((2-(1,3-bis(oxiran-2-ylmethoxy)propan-2-yl)-2-((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxiran). The photosensitive composition as described in item 1 of the patent application, wherein the compound of general formula (VI) is selected from the group consisting of: 2,2'-methylenediphenol; 4,4'-methylenediphenol; 2,2'-(ethane-1,1-diyl)diphenol; 4,4'-(ethane-1,1-diyl)diphenol; 2,2'-(propane-1,1-diyl)diphenol; 4,4'-(propane-1,1-diyl)diphenol Phenol; 2,2'-(propane-2,2-diyl)diphenol; 4,4'-(propane-2,2-diyl)diphenol; 2,2'-(4-methylpentane-2,2-diyl)diphenol; 4,4'-(4-methylpentane-2,2-diyl)diphenol; 2,2'-(5-methylheptane-3,3-diyl)diphenol; 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)diphenol; 2-cyclohexyl-4-(2-(4-hydroxyphenyl)prop-2-yl)-5-methylphenol; 6,6'-methylenebis(2-(tert-butyl)-4-methylphenol); 6,6'-(2-methylpropane-1,1-diyl)bis(2,4-xylenol); 4,4'-(2-methylpropane-1,1-diyl)bis(2-(tert-butyl)-5-methylphenol); and any combination thereof. The photosensitive composition as described in claim 1, wherein the phenolic compound is selected from the group consisting of:

The photosensitive composition as described in item 1 of the patent application, wherein the compound of general formula (VI) is selected from the group including: 2,2'-(4-methylpentane-2,2-diyl)diphenol; 4,4'-(4-methylpentane-2,2-diyl)diphenol; 2,2'-(5-methylheptane-3,3-diyl)diphenol; 4,4'-(5-methylheptane-3,3-diyl)diphenol; and any combination of these mixtures. The photosensitive composition as described in claim 1 further comprises one or more compounds selected from the group consisting of:

Triethoxy(3-(oxiran-2-ylmethoxy)propyl)silane;

3,3,10,10-Tetramethoxy-2,11-dioxa-3,10-disiladodecane;

4,4,13,13-Tetraethoxy-3,14-dioxa-8,9-disulfa-4,13-disilahexadecane;

2,2'-((2-Hydroxy-5-methyl-1,3-phenylene)bis(methylene))bis(4-cresol);

6,6'-Methylenebis(2-(2-hydroxy-5-methylbenzyl)-4-cresol);

Bis(4-(2-phenylpropan-2-yl)phenyl)amine;

Bis(4-(tert-butyl)phenyl)amine;

Bis(4-methoxyphenyl)amine;

Bis(4-ethylphenyl)amine; and any combination thereof. The photosensitive composition described in Item 1 of the patent application is soluble in an alkaline developer. A semiconductor device or optoelectronic device comprising a laminated semiconductor element or a bonded element, wherein the element is composed of the photosensitive composition described in item 1 of the patent application scope. A semiconductor device comprising a chip stacking structure, wherein the chip stacking structure further comprises the photosensitive composition described in item 1 of the patent application scope. A membrane comprising the composition described in item 1 of the patent application. A microelectronic device or optoelectronic device comprising one or more redistribution layer (RDL) structures, chip stacking structures, and CMOS image sensor dam structures, which further comprise the composition described in item 1 of the patent application scope. A method for forming a film for manufacturing microelectronic devices or optoelectronic devices, the method comprising: The step of coating a suitable substrate with the composition described in item 1 of the patent application scope to form a film; the step of patterning the film with a mask by exposing it to suitable radiation; the step of developing the film after exposure to form a light pattern; and the step of hardening the film by heating it to a suitable temperature. The method as described in claim 17, wherein the developing step is performed by an aqueous developer. As described in item 17 of the patent application, before the hardening, the substrate is first hard-baked at a temperature of 130°C to 160°C for 20 minutes to 60 minutes. The method as described in claim 17, wherein the hardening is performed at a temperature of 170°C to 200°C with a heating ramp of 5°C increments for 1 to 5 hours.