TWI765291B - Method for detecting copper corrosion - Google Patents

Abstract

A multilayer substrate for copper corrosion detection and a method for detecting copper corrosion are provided. The method includes the following steps: providing a multilayer substrate, wherein the multilayer substrate includes a copper layer; forming a gap in the multilayer substrate, wherein a depth of the gap reaches the copper layer; forming a photosensitive resin composition on the multilayer substrate, wherein the photosensitive resin composition covers the gap and is in contact with the copper layer; providing a mask layer on the multilayer substrate, and performing an exposure process; removing the mask layer and performing a development process; performing a post-baking process on the multilayer substrate; and observing the degree of copper corrosion of the gap.

Description

Methods for the detection of copper corrosion

The present disclosure relates to a multilayer substrate for copper corrosion detection and a copper corrosion detection method, and in particular, to a detection method for evaluating the degree of copper corrosion by a photosensitive resin composition.

In recent years, the array wiring in the panel manufacturing process has gradually replaced the traditional aluminum wiring process with the copper wire process. Due to the good conductivity of copper metal, the wiring line width can be reduced to meet the requirements of more complex and higher resolution. The panel wiring design can also improve the light penetration rate of the panel.

As mentioned above, in response to the requirement of using copper wires in the panel manufacturing process, developing a method for effectively detecting corrosion of copper wires and improving the reliability of the detection method are still one of the current research topics in the industry. In addition, developing the formulation of photosensitive resin composition that is less likely to cause copper wire disconnection or corrosion defects is also one of the research topics in the industry.

Due to the difference between copper and aluminum in nature, process compatibility issues arise. Unexpected chemical reactions may occur during this time, which may lead to corrosion or disconnection of copper wires on the array substrate, which may lead to reliability problems of subsequent products. The aforementioned problems often occur in panel products using color filter on array (COA) designs.

According to some embodiments of the present disclosure, a multilayer substrate for copper corrosion detection is provided, which includes a base layer and a copper layer, and the copper layer is disposed on the base layer.

According to some embodiments of the present disclosure, a method for detecting copper corrosion is provided, including the following steps: providing a multilayer substrate, wherein the multilayer substrate includes a copper layer; forming a crack in the multilayer substrate, wherein the depth of the crack reaches the copper layer; forming a photosensitive resin composition On the multilayer substrate, the photosensitive resin composition covers the cracks and contacts the copper layer; provides a mask layer on the multilayer substrate, and performs the exposure process; ; and observe the degree of copper corrosion of the crack.

In order to make the features or advantages of the present disclosure more obvious and easy to understand, some embodiments are exemplified below, and are described in detail as follows in conjunction with the accompanying drawings.

The method for detecting copper corrosion according to the embodiment of the present disclosure will be described in detail below. It should be appreciated that the following description provides many different embodiments or examples for implementing various aspects of some embodiments of the present disclosure. The specific elements and arrangements described below are merely to briefly and clearly describe some embodiments of the present disclosure. Of course, these are only examples and not limitations of the present disclosure. Furthermore, similar and/or corresponding reference numerals may be used in different embodiments to designate similar and/or corresponding elements in order to clearly describe the present disclosure. However, the use of these similar and/or corresponding reference numbers is merely for the purpose of simply and clearly describing some embodiments of the present disclosure, and does not imply any correlation between the different embodiments and/or structures discussed.

The embodiments of the present disclosure can be understood together with the drawings, and the drawings of the present disclosure are also regarded as a part of the disclosure description. It should be understood that the drawings in this disclosure are not in accordance with the Drawing to scale, elements may, in fact, be arbitrarily enlarged or reduced in size in order to clearly represent the features of the present disclosure.

Furthermore, relative terms such as "lower" or "bottom" or "higher" or "top" may be used in the examples to describe the relative relationship of one element of the drawings to another element. It will be understood that if the device in the figures were turned upside down, elements described on the "lower" side would become elements on the "upper" side. Furthermore, when it is mentioned that a first material layer is located on or above a second material layer, the case where the first material layer and the second material layer are in direct contact is included. Alternatively, one or more other material layers may be spaced apart, in which case the first material layer and the second material layer may not be in direct contact.

In the text, the terms "about" and "substantially" usually mean within 10%, or within 5%, or within 3%, or within 2%, or within 1%, of a given value or range. or within 0.5%. The quantity given here is an approximate quantity, that is, the meanings of "about" and "substantially" can still be implied if "about" and "substantially" are not specifically stated. Furthermore, the phrase "a range between a first value and a second value" means that the range includes the first value, the second value, and other values in between.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It is understood that these terms, such as those defined in commonly used dictionaries, should be interpreted as having meanings consistent with the relevant art and the background or context of the present disclosure, and should not be interpreted in an idealized or overly formal manner, Unless otherwise defined in the embodiments of the present disclosure.

According to some embodiments of the present disclosure, a method for detecting copper corrosion is provided, including a method for evaluating the degree of corrosion of copper wires by a photosensitive resin composition by using a patterned multilayer substrate. In detail, the method includes using a specific multi-layer substrate structure and performing a photolithography process with a photosensitive resin composition, so as to efficiently and simply determine whether the copper wire is corroded. The provided detection method for copper corrosion has good reliability. According to some embodiments of the present disclosure, the photosensitive resin composition of the specific composition provided has low reactivity with the copper wires, thus effectively reducing the risk of corrosion or disconnection of the copper wires.

Please refer to FIGS. 1A to 1E. FIGS. 1A to 1E are schematic cross-sectional views of the multilayer substrate 100 during the process of implementing the copper corrosion detection method according to some embodiments of the present disclosure. It should be appreciated that, according to some embodiments, additional operational steps may be provided before, during, and/or after the copper corrosion detection method is performed. According to some embodiments, some of the described operational steps may be replaced or omitted. According to some embodiments, the order of the operational steps is interchangeable.

First, as shown in FIG. 1A, a multilayer substrate 100 is provided. According to some embodiments, the multilayer substrate 100 includes a base layer 102 and a copper layer 104 , and the copper layer 104 may be disposed on the base layer 102 . According to some embodiments, the multilayer substrate 100 may further include a protective layer 106 , and the protective layer 106 may be disposed on the copper layer 104 .

According to some embodiments, the material of the base layer 102 may include glass, quartz, sapphire, ceramic, other suitable base materials, or a combination of the foregoing, but is not limited thereto. According to some embodiments, the material of the glass substrate may include silicon (Si), silicon carbide (SiC), gallium nitride (GaN), silicon dioxide (SiO ₂ ), other suitable materials, or a combination of the foregoing, but not limited to this.

According to some embodiments, the copper layer 104 has _a thickness T ₁ that may range between 500 nm and 1000 nm, or between 600 nm and 900 nm, eg, 700 nm, or 800 nm.

According to some embodiments, the copper layer 104 may be formed on the base layer 102 by a chemical vapor deposition process, a physical vapor deposition process, an electroplating process, an electroless plating process, other suitable processes, or a combination of the foregoing. The physical vapor deposition process may include, for example, a sputtering process, an evaporation process, a pulsed laser deposition process, and the like.

Furthermore, according to some embodiments, the protective layer 106 has a thickness T ₂ that can range from 100 nm to ₂₀₀ nm, or 100 nm to 150 nm, eg, 110 nm, 120 nm, 130 nm, or 140 nm.

According to some embodiments, the material of the protective layer 106 may include silicon nitride (SiN), transparent conductive oxide (TCO), or a combination thereof. For example, the transparent conductive oxide may include indium tin oxide (ITO), antimony zinc oxide (AZO), tin oxide (SnO), zinc oxide (ZnO), Indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), indium tin zinc oxide (ITZO), antimony tin oxide (ATO), other suitable of transparent conductive materials, or a combination of the foregoing.

It is worth noting that, according to some embodiments, the protective layer 106 is substantially transparent or light transmissive, so that the degree of corrosion of the copper layer 104 underlying the protective layer 106 can be observed through the protective layer 106 .

According to some embodiments, the protective layer 106 may be formed on the copper layer 104 by a chemical vapor deposition process, a coating process, a printing process, other suitable processes, or a combination of the foregoing. For example, the chemical vapor deposition process may include low pressure chemical vapor deposition (LPCVD), low temperature chemical vapor deposition (LTCVD), rapid temperature rise chemical vapor deposition (RTCVD), plasma assisted chemical vapor deposition (PECVD) ) or atomic layer deposition (ALD), etc.

Next, as shown in FIG. 1B , a gap GP is formed in the multilayer substrate 100 , and the depth of the gap GP reaches the copper layer 104 . In detail, according to some embodiments, the gap GP may completely penetrate the protective layer 106 and the copper layer 104 and expose the top surface 102 t of the base layer 102 . According to other embodiments, the gap GP may completely penetrate the protective layer 106 but only partially form in the copper layer 104 , that is, the gap GP does not expose the top surface 102 t of the base layer 102 .

According to some embodiments, the gap GP has _a width Wi, which may range from 30 μm to ₁₀₀ μm, or 40 μm to 90 μm, eg, 50 μm, 60 μm, 70 μm, or 80 μm. It is worth noting that if the width W ₁ of the gap GP is too small (for example, less than 30 μm), the observation difficulty of the copper corrosion phenomenon may be increased.

According to some embodiments, the gap GP may be formed in the multilayer substrate 100 by a dicing process. For example, the dicing process may include a knife dicing process, a laser dicing dicing process, other suitable dicing processes, or a combination of the foregoing.

Next, as shown in FIG. 1C , a photosensitive resin composition 108 is formed on the multilayer substrate 100 , and the photosensitive resin composition 108 covers the gap GP and is in contact with the copper layer 104 . According to some embodiments, the photosensitive resin composition 108 covers the protective layer 106 and extends in the gap GP, and contacts the sidewalls of the protective layer 106 and the copper layer 104 exposed by the gap GP.

According to some embodiments, the photosensitive resin composition 108 may include a colorant (A), a resin (B), a photopolymerizable monomer (C), a photoinitiator (D), and a solvent (E). According to some embodiments, colorant (A) may include pigment (A-1) and dye (A-2). Herein, the colorant (A), pigment (A-1), dye (A-2), resin (B), photopolymerizable monomer (C), photoinitiator (D) and solvent (E) ) and other ingredients, which can independently contain one or more colorants (A), pigments (A-1), dyes (A-2), resins (B), photopolymerizable monomers (C), photoinitiators In the case of components such as agent (D) and solvent (E).

According to some embodiments, the pigment (A-1) of the colorant (A) may comprise C.I. 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. red pigments; C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83 , 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, Orange pigments of 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 , 80 and other blue pigments; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. violet pigments; C.I. Pigment Green 7, 36, 58, etc. green pigments; C.I. Pigment Brown 23, 25, etc. Brown pigments; black pigments such as C.I. Pigment Black 1, 7, etc. According to some embodiments, the red pigment (A-1) may be C.I. Pigment Red 254 (R245). Alternatively, other known pigments can be used as the pigment (A-1). The aforementioned pigments may be used alone or in combination of two or more.

According to some embodiments, the dye (A-2) of the colorant (A) may comprise oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, or sulfonamides of acid dyes Derivatives, etc. Alternatively, other known dyes may be used as the dye (A-2). Moreover, depending on the chemical structure, for example, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, Naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye ), styrene dye (styryl dye), coumarin dye (coumarin dye), quinoline dye (quinoline dye) and nitro dye (nitro dye) and the like. According to some embodiments, the aforementioned dye (A-2) is preferably an organic solvent-soluble dye. According to some embodiments, the dye (A-2) may be a xanthene dye and an azo dye. In addition, the aforementioned dyes may be used alone, or two or more of them may be mixed and used.

According to some embodiments, resin (B) may be an alkali-soluble resin. For example, the alkali-soluble resin may comprise a carboxylic acid group-containing unsaturated monomer, a copolymer of a carboxylic acid group-containing unsaturated monomer and a vinyl unsaturated monomer, or a combination thereof. For example, according to some embodiments, the aforementioned carboxylic acid-based unsaturated monomers may be selected from acrylic acid (AA) compounds, methacrylic compounds, or a combination thereof. According to some embodiments, the aforementioned ethylenically unsaturated monomer may be selected from methyl acrylate, methyl methacrylate, benzyl acrylate, phenyl methacrylate ( benzyl methacrylate), ethyl acrylate (ethyl acrylate), ethyl methacrylate (ethyl methacrylate), 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate), 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate) ), hydroxypropyl acrylate, hydroxypropyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, ethylene glycol dimethyl acrylate ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, pentaerythritol triacrylate, ethoxylate ethoxylated pentaerythritol tetraacrylate, ethoxylated trimethylpropane triacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dipentaerythritol Dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate), dihydrodicyclopentadienyl acrylate (DCPA), epoxy dicyclopentenyl acrylate (EDCPA), methacrylic acid (methacrylic acid), N - Phenyl maleimide (N-benzyl maleimide), tricyclodecyl methacrylate (tricyclodecyl methacrylate), vinyltoluene (vi nyl toluene), N-cyclohexylmaleimide (N-cyclohexylmaleimide), 2-ethylhexyl acrylate (2-ethylhexyl acrylate), glycidyl methacrylate (glycidyl methacrylate), methacrylic acid ring cyclohexyl methacrylate, tert-butyl methacrylate, or a combination of the foregoing. According to some embodiments, resin (B) may be a resin in combination with monomer EDCPA and monomer AA. According to some embodiments, resin (B) may be SH5052A.

Furthermore, the photopolymerizable monomer (C) may be a monomer that can be polymerized by active radicals and/or acids generated by the photoinitiator (D). For example, according to some embodiments, the photopolymerizable monomer (C) may include, but is not limited to, an ethylenically unsaturated bond having polymerizability, such as a (meth)acrylate compound. Here, the compound described with parentheses represents the presence or absence of the characters in the parentheses, such as the aforementioned (meth)acrylate compound, the case where the acrylate compound and the methacrylate compound are included. For example, the photopolymerizable monomer (C) may include, but is not limited to, at least one selected from the group consisting of: nonylphenyl carbitol acrylate, 2-hydroxy-3- acrylate Phenoxypropyl ester, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and other polymerizable compounds with one ethylenically unsaturated bond; di(meth)acrylic acid 1 ,6-hexanediol, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(meth)acrylate Polymerizable compounds having two ethylenically unsaturated bonds, such as acryloxyethyl) ether and 3-methylpentanediol di(meth)acrylate; and trimethylolpropane tri(meth)acrylate ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, Tripentaerythritol hepta(meth)acrylate, pentaerythritol ten(meth)acrylate, pentaerythritol nona(meth)acrylate, tris(2-(meth)acrylooxyethyl)isocyanate, tetrakis(meth)acrylate base) ethylene glycol modified pentaerythritol acrylate, ethylene glycol hexa(meth)acrylate modified dipentaerythritol, propylene glycol tetra(meth)acrylate modified pentaerythritol, propylene glycol hexa(meth)acrylate modified dipentaerythritol , tetra (meth) acrylic acid caprolactone modified pentaerythritol, hexa (meth) acrylic acid caprolactone modified dipentaerythritol and other polymerizable compounds with three ethylenically unsaturated bonds. According to some embodiments, the photopolymerizable monomer (C) may be dipentaerythritol hexaacrylate (DPHA).

Furthermore, the photoinitiator (D) may be a compound capable of generating active radicals, acids, etc. by the action of light or heat, thereby starting polymerization. For example, according to some embodiments, the photoinitiator (D) may include an O-acyloxime compound, an alkyl phenyl ketone compound, a bisimidazole compound, a triazine compound, an acylphosphine oxide (acyl phosphine oxide), benzoin compound, benzophenone compound, quinone compound, 10-butyl-2-chloroacridone, benzyl, methyl phenylformate, titanium cyclopentadiene (titanocene) compound, or a combination of the foregoing. According to some embodiments, the photoinitiator (D) may be 2,4,6-trimethylbenzyldiphenylphosphine oxide (I-819), PBG-345 (Tronly), PBG-365 (Tronly) ), PBG-380 (Tronly), or PBG-327 (Tronly).

In particular, according to some embodiments of the present disclosure, by implementing the copper corrosion detection method, it is further found that the photosensitive resin composition 108 with a specific photoinitiator composition has low reactivity with the copper wire, so that the corrosion of the copper wire can be effectively reduced or risk of disconnection.

Specifically, according to some embodiments, the photoinitiator included in the photosensitive resin composition 108 is not an oxime-based photoinitiator (ie, does not contain an oxime structure), and the solid content of the photoinitiator is not greater than 8wt % (≤8wt%), the copper corrosion degree of the observed crack GP was judged to be in compliance with the standard, that is, there was no copper corrosion phenomenon or the copper corrosion degree was quite slight. According to other embodiments, the photoinitiator included in the photosensitive resin composition 108 is an oxime-based photoinitiator (ie, contains an oxime structure) and does not contain a nitro group (-NO ₂ ) or a sulfur group (-S) structure, and the solid content of the photoinitiator is not more than 5wt% (≤5wt%), the copper corrosion degree of the observed crack GP is judged to meet the standard, that is, there is no copper corrosion phenomenon or the copper corrosion degree is quite slight. According to other embodiments, the photoinitiator included in the photosensitive resin composition 108 is an oxime-based photoinitiator and includes a nitro group (-NO ₂ ) or a sulfur group (-S) structure, and the solid state of the photoinitiator is Part is not more than 2.5wt% (≤2.5wt%), the copper corrosion degree of the observed crack GP is judged to meet the standard, that is, there is no copper corrosion phenomenon or the copper corrosion degree is quite slight. The detailed implementation of the embodiments of the present disclosure will be described below.

According to some embodiments, the solvent (E) may include, but is not limited to, ester solvents (herein meaning solvents containing -COO- in the molecule but not -O-), ether solvents (herein meaning in the molecules containing - O-but not -COO-solvent), ether ester solvent (here means a solvent containing -COO- and -O- in the molecule), ketone solvent (here means containing -CO- in the molecule but Solvents not containing -COO-), alcohol solvents (here means solvents containing OH in the molecule but not -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl Chia and others. According to some embodiments, solvent (E) may be diacetone alcohol (DAA), propylene glycol methyl ether (PGME), or propylene glycol methyl ether acetate (PGMEA).

According to some embodiments, the colorant (A) is 200 to 270 parts by weight, or 220 to 250 parts by weight, and the photopolymerizable monomer (C) is 210 parts by weight relative to 100 parts by weight of the resin (B). to 260 parts by weight, or 230 to 240 parts by weight, the photoinitiator (D) is 5 to 80 parts by weight, or 10 to 60 parts by weight, and the solvent (E) is 3200 to 4000 parts by weight parts, or 3400 to 3900 parts by weight.

According to some embodiments, the photosensitive resin composition 108 may further include dispersants, binders, or other additives, such as leveling agents, polymerization initiation aids, fillers, adhesion promoters, antioxidants, light stabilizers, Other additives such as chain transfer agents, but not limited thereto. According to some embodiments, the additive may comprise a fluorolipophilic organic oligomer, such as F554 (DIC).

According to some embodiments, the photosensitive resin composition 108 may be formed on the protective layer 106 by a chemical vapor deposition process, a coating process, a printing process, other suitable processes, or a combination thereof. According to some embodiments, the photosensitive resin composition 108 may be processed by a spin coater, a slot spin coater, a slot coater (also known as a die coater, a curtain coater) (curtain flow coater), or spinless coater (spinless coater), or a coating device such as an ink jet machine to perform the coating process.

According to some embodiments, after the step of forming the photosensitive resin composition 108 on the multilayer substrate 100 , a drying process may be further performed on the photosensitive resin composition 108 . Specifically, the drying process may include vacuum drying, natural drying, ventilation drying, reduced pressure drying, heating drying (also referred to as pre-baking), or a combination of the foregoing. According to some embodiments, vacuum drying may be performed followed by heat drying. According to some embodiments, the pressure range of vacuum drying may be between 40pa-90pa, or between 50pa-80pa. According to some embodiments, the temperature range of heating and drying may be between 30°C and 120°C, or between 40°C and 100°C, and the heating time may be between 10 seconds and 60 minutes, or between 30°C and 30°C. seconds to 30 minutes.

Afterwards, as shown in FIG. 1D , a mask layer 110 is provided on the multilayer substrate 100 to perform an exposure process. According to some embodiments, the mask layer 110 includes a light-transmitting region 110a and a non-light-transmitting region 110b, the non-light-transmitting region 110b is disposed above the gap GP, and the width W ₂ of the non-light-transmitting region 110b is greater than the width W ₁ of the gap GP, That is, the non-light-transmitting area 110 can completely cover the gap GP. According to some embodiments, in the normal direction of the base layer 102, the non-transmissive region 110b overlaps the gap GP, and overlaps the copper layer 104 and the protective layer 106 adjacent to a portion of the gap GP.

According to some embodiments, there is a distance D ₁ between the edge of the gap GP and the edge of the non-transmissive region 110b, and the distance D ₁ may range from 100 μm to 500 μm, or from 200 μm to 400 μm, for example , 250 μm, 300 μm, or 350 μm. In detail, the aforementioned distance D ₁ refers to the minimum distance between the edge of the gap GP and the edge of the non-transmissive region 110 b in a direction parallel to the top surface of the base layer 102 .

It is worth noting that one of the reasons for the corrosion of the copper layer 104 may be caused by the reaction between the solvent used in the photosensitive resin composition 108 and the copper during exposure. Therefore, if the distance D1 is too small or too large (for example, less than ₁₀₀ μm or greater than 500 μm), which may increase the difficulty of observing copper corrosion.

According to some embodiments, the width W ₂ of the non-transmissive region 110b of the mask layer 110 may be between 130 μm and 600 μm, or between 200 μm and 500 μm, eg, 300 μm, or 400 μm. Furthermore, the light-transmitting region 110a of the mask layer 110 has a width W ₃ , and the width W ₃ may be greater than 500 μm.

It should be understood that the embodiments in the drawings are taken as an example using the photosensitive resin composition 108 of negative photoresist, but according to other embodiments, the photosensitive resin composition 108 of positive photoresist can be used, such as As a result, the positions of the light-transmitting area 110a and the non-light-transmitting area 110b of the mask layer 110 will be opposite to those in the drawings, that is, the light-transmitting area 110a can be disposed above the gap GP, and the width of the light-transmitting area 110a W ₃ is greater than the width W ₁ of the gap GP.

Referring to FIG. 1E, then, the mask layer 110 can be removed and a developing process can be performed. In detail, according to some embodiments, after exposure using the mask layer 110 , the patterned photosensitive resin composition 108 can be obtained by removing the unexposed portion through a developing process. As shown in FIG. 1D and FIG. 1E, light (as indicated by arrows in the figure) can penetrate the light-transmitting region 110a of the mask layer 110 but cannot penetrate the non-light-transmitting region 110b, corresponding to the non-light-transmitting region The portion 108X of the photosensitive resin composition 108 of 110b will be removed in the subsequent development process, while the portion 108' of the photosensitive resin composition 108 corresponding to the light-transmitting area 110a will not be removed in the subsequent development process. remove.

According to some embodiments, in the exposure step, light sources such as mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps can be used, and light with a wavelength range of 250 nm to 450 nm can be used. According to some embodiments, a mask alignment exposure machine, stepper, etc. device may be used to uniformly illuminate the entire exposure surface with parallel light, and/or to precisely align the mask and substrate.

Furthermore, in the developing step, a developer such as an organic solvent or an aqueous solution of an alkaline compound can be used to dissolve a predetermined portion (eg, an unexposed portion) for removal, thereby obtaining a pattern.

Notably, according to some embodiments, the use of an aqueous solution of an alkaline compound as a developer is particularly helpful in obtaining well-shaped graphics. According to some embodiments, the concentration range of the developer may be, for example, between 0.001 mass % and 0.100 mass %, eg, between 0.040 mass % and 0.050 mass %. According to some embodiments, the developer used in the developing process may include an aqueous potassium hydroxide (KOH) solution.

According to some embodiments, the developer may be provided on the multilayer substrate 100 by a paddle stirring method, a dipping method, a spraying method, or the like. According to some embodiments, a cleaning step may be performed on the multilayer substrate 100 after the development process.

Furthermore, according to some embodiments, after the development process, a post-bake process may be performed on the multilayer substrate 100 . According to some embodiments, the drying process may include heat drying. According to some embodiments, the temperature range for heating may be between 150°C and 300°C, or between 200°C and 250°C, eg, 210°C, 220°C, 230°C, or 240°C. According to some embodiments, the heating time may be between 5 minutes and 60 minutes, or between 10 minutes and 50 minutes, for example, 20 minutes, 30 minutes, or 40 minutes

It is worth noting that the post-baking process will cause the copper layer 104 and the protective layer 106 adjacent to the gap GP to expand and protrude, which is more conducive to the subsequent observation of the copper corrosion degree of the gap GP.

Next, after the post-baking process, the copper corrosion degree of the crack GP was observed. Please refer to FIG. 2A and FIG. 2B. FIG. 2A shows the multilayer substrate 100 (and the photosensitive resin composition 108 formed thereon) after the copper corrosion detection method is performed according to some embodiments of the present disclosure. 108 ′), and FIG. 2B shows a top-view structure diagram corresponding to the multilayer substrate 100 in FIG. 2A . It should be understood that, for the sake of clarity, the protective layer 106 on the uneven color region 104r of the copper layer 104 is not shown in FIG. 2B .

As shown in FIGS. 2A and 2B , according to some embodiments, after performing the foregoing steps of the copper corrosion detection method (as shown in FIGS. 1A to 1E ), color is generated around the gap GP in the multilayer substrate 100 Uneven region 104r. According to some embodiments, the uneven color area 104r generally presents a gradient smear shape of light red, light orange, light yellow, and white, and is light red, light orange, light yellow, light red, light orange, light yellow, White (see Figure 4, for example, which shows the actual image taken with an optical microscope). According to some embodiments, the degree of copper corrosion of the gap GP may be observed using an optical microscope.

According to some embodiments, the specific method for determining the degree of copper corrosion includes measuring the width W ₄ of the uneven color region 104r around the crack GP, if the width W ₄ of the uneven color region 104r minus the width W ₁ of the crack GP is greater than or equal to 30 μm (W _{4 -W 1} ≥ ₃₀ μm), it is determined that the standard does not meet the standard, that is, the degree of copper corrosion is serious _; -W ₁ <30 μm), it is judged that the standard is met, that is, there is no copper corrosion phenomenon or the copper corrosion degree is quite slight.

It should be noted that the width W4 of the uneven color area _104r refers to the maximum width of the uneven color area 104r in the direction perpendicular to the extending direction of the gap GP, and this value can be measured three times (different positions). The average value obtained after. In addition, it should be understood that, according to different embodiments, it may be adjusted according to the requirements of the product to determine whether the degree of copper corrosion meets the specified critical value.

Furthermore, please refer to FIG. 3A and FIG. 3B. FIG. 3A shows the composition of the multilayer substrate 100 (and the photosensitive resin formed thereon) after the copper corrosion detection method described above is performed according to other embodiments of the present disclosure. Fig. 3B shows a schematic top view structure corresponding to the multilayer substrate 100 in Fig. 3A.

As shown in FIGS. 3A and 3B , according to some embodiments, after performing the aforementioned steps of the copper corrosion detection method (as shown in FIGS. 1A to 1E ), there is no gap around the gap GP in the multilayer substrate 100 . An uneven color region 104r is generated, that is, in this embodiment, no copper corrosion occurs (for example, please refer to FIG. 5, which shows an actual image obtained by an optical microscope).

Based on the foregoing, according to some embodiments of the present disclosure, a method for detecting copper corrosion is provided, including a method for evaluating the corrosion degree of a photosensitive resin composition on copper wires by using a patterned multilayer substrate, which includes using a specific multilayer substrate structure with a photosensitive resin. The composition is subjected to a photolithography process, whereby whether the copper wire is corroded can be judged efficiently and simply, and the provided method for detecting copper corrosion has good reliability. In addition, according to some embodiments of the present disclosure, the photosensitive resin composition with a specific composition has low reactivity with the copper wires, so the risk of corrosion or disconnection of the copper wires can be effectively reduced.

In order to make the above-mentioned and other objects, features, and advantages of the present disclosure more clearly understood, several embodiments, comparative examples, and test examples are given below for detailed description, but they are not intended to limit the content of the present disclosure. Examples 1~9/ Comparative Examples 1~6

First, a patterned multi-layer substrate is prepared. The steps are as follows: metal copper with a thickness of 500 nm to 1000 nm is plated on the surface of the plain glass, and then a silicon nitride layer with a thickness of 100 nm to 150 nm is plated on the metal copper plating layer. Then, the silicon nitride layer and the metal copper layer are scribed together with a blade to form a straight crack, and the width of the crack is between 20 μm and 50 μm.

Then, the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 6 were prepared according to the contents shown in Table 1 and Table 2 below. In detail, the photosensitive resin compositions with different material ratios shown in Table 1 and Table 2 are mixed uniformly, and then the photosensitive resin composition is coated on the aforementioned pattern of 5cm*5cm by means of spin coating. On the multi-layer substrate, the wet film test piece is completed.

Next, put the wet film test piece into the vacuum dryer, cover it with a sealing cover, and then vacuumize, set the bottom pressure of the suction to 66 Pa and maintain it for 20 seconds. After completion, break the vacuum and restore the atmospheric pressure. The vacuum dryer was taken out and placed on a heating plate with a temperature of 90° C. for 38 seconds, and then cooled at room temperature to complete the pre-drying step.

Put the completed wet film test piece into the exposure machine for exposure, set the accumulated light amount to 40 mJ/cm ² , and set the distance between the mask and the wet film test piece to be 265 μm, and perform exposure after the setting is completed. The widths of the light-transmitting area and the non-light-transmitting area of the selected photomask are respectively 1000 μm and 1000 μm, and the non-light-transmitting area covers the crack.

Put the wet film test piece after exposure into the developing machine, use KOH aqueous solution with a concentration of 0.044% as the developer, the development time is set to 60 seconds, the development pressure is set to 0.06MPa, and the height of the developer nozzle is 17 cm away from the wet film test piece. . After completion of development, deionized water was used to perform the cleaning step. The cleaning time and pressure were set to 40 seconds and 0.1 Mpa, respectively, and the height of the cleaning nozzle was 17 cm from the wet film test piece. Both the developer and the deionized water for cleaning were maintained at a temperature range of 23±1° C. using a heating and cooling device.

The wet film test piece was put into an oven with a temperature of 230°C for post-baking step, and after baking for 20 minutes, it was taken out and cooled to complete the production of the test piece (multilayer substrate with the photosensitive resin composition thereon).

Next, use an optical microscope (manufacturer, model: _OLYMPUS DSX500_) to observe whether there is copper corrosion at the crack, and the specific method for judging the degree of copper corrosion is as described above.

Table 1 Element(%) Make and Model Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Example 6 Example 7 Comparative Example 2 pigment R254 34.1 34.1 34.1 34.1 34.1 34.1 34.1 34.1 34.1 Resins, Dispersants and Binders SH5052A 26.1 25.4 24.5 26.1 25.4 24.5 26.1 25.4 24.5 monomer DPHA (Nihon Kayaku) 36.2 34.4 32.4 36.2 34.4 32.4 36.2 34.4 32.4 Non-oxime-based photoinitiators I-819 2.5 5.0 8.0 -- -- -- -- -- -- Oxime-based photoinitiators, without -NO ₂ or -S PBG-345 (Tronly) -- -- -- 2.5 5.0 8.0 -- -- -- Oxime-based photoinitiators, without -NO ₂ or -S PBG-365 (Tronly) -- -- -- -- -- -- 2.5 5.0 8.0 Oxime photoinitiator, containing -NO ₂ PBG-380 (Tronly) -- -- -- -- -- -- -- -- -- Oxime photoinitiator, containing S PBG-327 (Tronly) -- -- -- -- -- -- -- -- -- additive BBM-S (Sumitomo Chemical) 1.0 1.0 0.9 1.0 1.0 0.9 1.0 1.0 0.9 additive F554 (DIC) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 sum(%) 100 100 100 100 100 100 100 100 100 Copper corrosion degree (μm) (width of uneven color area W ₄ - crack width W ₁ ) (○=0~30μm, △=31~50μm, ╳≧51μm) ○ ○ ○ ○ ○ △ ○ ○ △ 0.0 0.0 0.0 12.6 23.9 34.5 18.2 25.5 32.5

Table 2 Element(%) Make and Model Example 8 Comparative Example 3 Comparative Example 4 Example 9 Comparative Example 5 Comparative Example 6 pigment R254 34.1 34.1 34.1 34.1 34.1 34.1 Resins, Dispersants and Binders SH5052A 26.1 25.4 24.5 26.1 25.4 24.5 monomer DPHA (Nihon Kayaku) 36.2 34.4 32.4 36.2 34.4 32.4 Non-oxime-based photoinitiators I-819 -- -- -- -- -- -- Oxime-based photoinitiators, without -NO ₂ or -S PBG-345 (Tronly) -- -- -- -- -- -- Oxime-based photoinitiators, without -NO ₂ or -S PBG-365 (Tronly) -- -- -- -- -- -- Oxime photoinitiator, containing -NO ₂ PBG-380 (Tronly) 2.5 5.0 8.0 -- -- -- Oxime photoinitiator, containing S PBG-327 (Tronly) -- -- -- 2.5 5.0 8.0 additive BBM-S (Sumitomo Chemical) 1.0 1.0 0.9 1.0 1.0 0.9 additive F554 (DIC) 0.1 0.1 0.1 0.1 0.1 0.1 sum(%) 100.0 100.0 100.0 100.0 100.0 100.0 Copper corrosion degree (μm) (width of uneven color area W ₄ - crack width W ₁ ) (○=0~30μm, △=31~50μm, ╳≧51μm) ○ △ ╳ ○ △ ╳ 20.5 36.4 51.5 17.8 31.3 41.0

The percentage of each component in Table 1 and Table 2 is expressed in solid content (%), wherein pigment R254 is the pigment (A-1) of the aforementioned colorant (A), SH5052A is the aforementioned resin (B), and DPHA is the aforementioned Photopolymerizable monomers (C), I-819, PBG-345, PBG-365, PBG-380, PBG-327 are the aforementioned photoinitiators (D), and DAA, PGME, PGMEA are the aforementioned solvents (E ).

According to the results in Table 1 and Table 2, when the photoinitiator contained in the photosensitive resin composition is a non-oxime-based photoinitiator, and the solid content of the photoinitiator is not more than 8 wt % (Examples 1 to 3 ), the copper corrosion degree of the observed crack GP is 0 μm, which meets the standard. When the photoinitiator contained in the photosensitive resin composition is an oxime-based photoinitiator and does not contain a nitro group (-NO ₂ ) or a sulfur group (-S) structure, and the solid content of the photoinitiator is not more than 5wt% (Examples 4 to 7), the copper corrosion degree of the observed crack GP is between 12.6 μm and 25.5 μm, which meets the standard. Furthermore, when the photoinitiator contained in the photosensitive resin composition is an oxime-based photoinitiator and contains a nitro group (-NO ₂ ) or a sulfur group (-S) structure, and the solid content of the photoinitiator is not greater than At 2.5 wt% (Examples 8-9), the observed copper corrosion degree of the crack GP is between 17.8 μm and 27.2 μm, which meets the standard.

Although the embodiments of the present disclosure and their advantages have been disclosed above, it should be understood that those skilled in the art can make changes, substitutions and modifications without departing from the spirit and scope of the present disclosure. The features between the embodiments of the present disclosure can be arbitrarily mixed and matched as long as they do not violate the spirit of the invention or conflict with each other. In addition, the protection scope of the present disclosure is not limited to the process, machine, manufacture, material composition, device, method and steps in the specific embodiments described in the specification. It is understood that processes, machines, manufactures, compositions of matter, devices, methods and steps developed in the present or in the future can be used in accordance with the present disclosure as long as they can perform substantially the same functions or obtain substantially the same results in the embodiments described herein. Therefore, the protection scope of the present disclosure includes the above-mentioned processes, machines, manufactures, compositions of matter, devices, methods and steps. The scope of protection of this disclosure shall be determined by the scope of the appended patent application.

100: multilayer substrate 102: base layer 102t: top surface 104: copper layer 104r: uneven color area 106: protective layer 108: photosensitive resin composition 108': part 108X: part 110: mask layer 110a: light-transmitting area 110b: Non-light-transmitting area D ₁ : Distance GP: Gap T ₁ : Thickness T ₂ : Thickness W ₁ : Width W ₂ : Width W ₃ : Width W ₄ : Width

1A to 1E show schematic cross-sectional structures of the multilayer substrate in the process of implementing the copper corrosion detection method according to some embodiments of the present disclosure; and FIG. 2A shows the copper corrosion in some embodiments according to the present disclosure. Schematic diagram of the cross-sectional structure of the multi-layer substrate in the process of the detection method; FIG. 2B shows a schematic diagram of the top-view structure of the multi-layer substrate in the process of implementing the detection method for copper corrosion according to some embodiments of the present disclosure; FIG. 3A shows a schematic diagram of a cross-sectional structure of a multi-layer substrate in the process of implementing the copper corrosion detection method according to some embodiments of the present disclosure; FIG. 3B shows the copper corrosion detection method according to some embodiments of the present disclosure. During the process, a schematic top view of the multilayer substrate; FIG. 4 shows an image of the multilayer substrate obtained by an optical microscope in the process of implementing the copper corrosion detection method according to some embodiments of the present disclosure; FIG. In some embodiments of the present disclosure, in the process of implementing the copper corrosion detection method, the image of the multilayer substrate is obtained by an optical microscope.

100: Multilayer substrate

102: basal layer

104: Copper layer

106: Protective layer

108: Photosensitive resin composition

110: mask layer

110a: light transmission area

110b: non-transparent area

D ₁ : Distance

GP: rip

W ₁ : width

W ₂ : width

W ₃ : width

Claims (13)

A method for detecting copper corrosion, comprising: providing a multi-layer substrate, wherein the multi-layer substrate includes a copper layer; forming a crack in the multi-layer substrate, wherein a depth of the crack reaches the copper layer; forming a photosensitive resin composition on the multi-layer substrate, the photosensitive resin composition covers the crack and contacts the copper layer; provides a mask layer on the multi-layer substrate, and performs an exposure process; removes the mask layer and performs a development process ; perform a post-baking process on the multilayer substrate; and observe the copper corrosion degree of the crack. The method for detecting copper corrosion as claimed in claim 1, wherein the mask layer comprises a light-transmitting area and a non-light-transmitting area, the non-light-transmitting area is disposed above the crack, and the width of the non-light-transmitting area is larger than the crack width. The method for detecting copper corrosion according to claim 2, wherein the width of the crack is between 30 μm and 100 μm. The method for detecting copper corrosion according to claim 2, wherein a distance between an edge of the crack and an edge of the non-transmitting area is between 100 μm and 500 μm. The method for detecting copper corrosion according to claim 1, wherein the mask layer includes a light-transmitting area and a non-light-transmitting area, the light-transmitting area is disposed above the crack, and the width of the light-transmitting region is larger than the crack width. The method for detecting copper corrosion as claimed in claim 1, wherein the step of observing the copper corrosion degree of the crack comprises: measuring the width of a color uneven area around the crack, if the width of the color uneven area deducts the crack If the width is greater than or equal to 30 μm, it is judged as not meeting the standard, and if the width of the uneven color area minus the width of the crack is less than 30 μm, it is judged as meeting the standard. The method for detecting copper corrosion according to claim 1, wherein the multilayer substrate further comprises a protective layer, the protective layer is disposed on the copper layer, and the crack penetrates through the protective layer. The method for detecting copper corrosion as claimed in claim 1, wherein the multilayer substrate further comprises a base layer, wherein the crack exposes a top surface of the base layer. The method for detecting copper corrosion according to claim 1, wherein the photosensitive resin composition comprises at least one photoinitiator, the at least one photoinitiator is not an oxime-based photoinitiator, and the photoinitiator is The solid content of the initiator is not more than 8 wt %, and the copper corrosion degree of the crack is observed to be in compliance with the standard. The method for detecting copper corrosion according to claim 1, wherein the photosensitive resin composition includes at least one photoinitiator, and the at least one photoinitiator is an oxime-based photoinitiator and does not include nitro (-NO) ₂ ) or sulfur-based (-S) structure, and the solid content of the at least one photoinitiator is not more than 5wt%, wherein the copper corrosion degree of the crack is observed to be judged to meet the standard. The method for detecting copper corrosion as claimed in claim 1, wherein the photosensitive resin composition comprises at least one photoinitiator, and the at least one photoinitiator is an oxime light The initiator includes a nitro group or a sulfur-based structure, and the solid content of the at least one photoinitiator is not more than 2.5 wt %, wherein the copper corrosion degree of the crack is judged to meet the standard. The copper corrosion detection method according to claim 7, wherein the thickness of the copper layer is between 500 nm and 1000 nm; and/or the thickness of the protective layer is between 100 nm and 200 nm. The method for detecting copper corrosion according to claim 7 or 8, wherein the base layer is selected from glass, quartz, sapphire, ceramic or a combination thereof; and/or the protective layer is selected from silicon nitride, transparent conductive oxide or combination of the foregoing.

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