CN112881270A - Multilayer substrate for copper corrosion detection and method for detecting copper corrosion - Google Patents
Multilayer substrate for copper corrosion detection and method for detecting copper corrosion Download PDFInfo
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Abstract
The present disclosure provides a multi-layer substrate for copper corrosion detection and a method for detecting copper corrosion. The detection method of copper corrosion comprises the following steps: providing a multilayer substrate, wherein the multilayer substrate comprises a copper layer; forming a crack in the multilayer substrate, wherein the crack has a depth reaching 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 multi-layer substrate, and performing an exposure process; removing the mask layer and performing a developing process; performing a post-baking process on the multilayer substrate; and observing the copper corrosion degree of the crack.
Description
Technical Field
The present disclosure relates to a multi-layer substrate for copper corrosion detection and a method for detecting copper corrosion, and more particularly, to a method for evaluating the degree of copper corrosion of a photosensitive resin composition.
Background
In recent years, in the array (array) wiring in the panel process, a copper wire process is gradually used to replace the conventional aluminum wire process, and the conductivity of copper metal is good, so that the wiring line width can be reduced to satisfy the more complicated and higher-resolution panel wiring design, and the light transmittance of the panel can also be improved.
In view of the foregoing, it is still one of the subjects of research in the industry to develop a method for effectively detecting copper wire corrosion and improving the reliability of the detection method in response to the requirement of using copper wire in the panel process. In addition, the development of a photosensitive resin composition that is not prone to cause copper wire disconnection or corrosion defects has been one of the subjects of research.
Disclosure of Invention
The intrinsic difference between copper and aluminum causes process compatibility problems, for example, the material used in aluminum wire process may generate unexpected chemical reaction when applied to copper wire process, which may result in copper wire corrosion or wire breakage on the array substrate and reliability problems of subsequent products. The foregoing problems often occur with panel products that employ color filter on array (COA) designs.
According to some embodiments of the present disclosure, a multi-layer substrate for copper corrosion detection is provided, which includes a base layer and a copper layer disposed on the base layer.
According to some embodiments of the present disclosure, a method for detecting copper corrosion is provided, comprising: providing a multilayer substrate, wherein the multilayer substrate comprises a copper layer; forming a crack in the multilayer substrate, wherein the crack has a depth reaching 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 multi-layer substrate, and performing an exposure process; removing the mask layer and performing a developing process; performing a post-baking process on the multilayer substrate; and observing the copper corrosion degree of the crack.
In order to make the features and advantages of the present disclosure comprehensible, several embodiments accompanied with figures are described in detail below.
Drawings
FIGS. 1A-1E illustrate schematic cross-sectional views of a multi-layer substrate during a copper corrosion detection method according to some embodiments of the present disclosure;
FIG. 2A is a schematic cross-sectional view of a multi-layer substrate during a copper corrosion detection method according to some embodiments of the present disclosure;
FIG. 2B is a schematic top view of a multi-layer substrate during a copper corrosion detection method according to some embodiments of the present disclosure;
FIG. 3A is a schematic cross-sectional view of a multi-layer substrate during a copper corrosion detection method according to some embodiments of the present disclosure;
FIG. 3B is a schematic top view of a multi-layer substrate during a copper corrosion detection method according to some embodiments of the present disclosure;
FIG. 4 is an image of a multi-layer substrate taken with an optical microscope during a copper corrosion inspection process according to some embodiments of the present disclosure;
FIG. 5 is an image of a multi-layer substrate taken with an optical microscope during a copper corrosion inspection process according to some embodiments of the present disclosure.
[ notation ] to show
100 multilayer substrate
102 base layer
102t top surface
104 copper layer
104r color uneven area
106 protective layer
108 photosensitive resin composition
108' part
108X part
110 mask layer
110a light-transmitting region
110b non-light-transmitting region
D1Distance
GP fracture
T1Thickness of
T2Thickness of
W1Width (L)
W2Width (L)
W3Width (L)
W4Width (L)
Detailed Description
The method for detecting copper corrosion according to the embodiment of the present disclosure is described in detail below. It is to be understood that the following description provides many different embodiments, or examples, for implementing different aspects of some embodiments of the disclosure. The specific components and arrangements are described below to provide a simple and clear description of certain embodiments of the disclosure. These are, of course, merely examples and are not intended to be limiting. Moreover, similar and/or corresponding reference numerals may be used to identify similar and/or corresponding elements in different embodiments to clearly describe the present disclosure. However, the use of such similar and/or corresponding reference numerals is merely for simplicity and clarity in describing some embodiments of the present disclosure and does not represent any correlation between the various embodiments and/or structures discussed.
The embodiments of the present disclosure can be understood together with the accompanying drawings, which are incorporated in and constitute a part of this specification. It should be understood that the drawings of the present disclosure are not drawn to scale and that, in fact, the dimensions of the elements may be arbitrarily increased or reduced to clearly illustrate the features of the present disclosure.
Furthermore, relative terms, such as "lower" or "bottom" or "upper" or "top," may be used in embodiments to describe one element's relative relationship to another element of the figures. It will be understood that if the device of the drawings is turned over and upside down, elements described as being on the "lower" side will be elements on the "upper" side. Furthermore, when a first material layer is located on or above a second material layer, the first material layer and the second material layer are in direct contact. Alternatively, one or more layers of other materials may be present, in which case there may not be direct contact between the first and second layers of material.
As used herein, the term "about" or "substantially" generally means within 10%, or within 5%, or within 3%, or within 2%, or within 1%, or within 0.5% of a given value or range. The amounts given herein are approximate, that is, the meanings of "about" and "substantially" may be implied without specifically stating "about" or "substantially". Furthermore, the term "range from a first value to a second value" means that the range includes the first value, the second value, and other values therebetween.
Unless defined otherwise, 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 will be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
According to some embodiments of the present disclosure, a method for detecting copper corrosion is provided, which comprises evaluating the degree of corrosion of a photosensitive resin composition on a copper wire by using a patterned multi-layer substrate. In detail, the method comprises using a specific multi-layer substrate structure and performing a photolithography (photolithography) process with a photosensitive resin composition, thereby efficiently and easily determining whether the copper wire is corroded, and the provided method for detecting copper corrosion has good reliability. According to some embodiments of the present disclosure, the photosensitive resin composition with a specific composition has low reactivity with the copper wire, so that the risk of corrosion or wire breakage of the copper wire can be effectively reduced.
Referring to fig. 1A to 1E, fig. 1A to 1E show schematic cross-sectional structures of a multi-layered substrate 100 during a copper corrosion detection method according to some embodiments of the present disclosure. It is understood that additional processing steps may be provided before, during, and/or after the copper corrosion detection process is performed, according to some embodiments. 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, the copper layer 104 may be disposed on the base layer 102. According to some embodiments, the multi-layer substrate 100 may further include a protection layer 106, and the protection layer 106 may be disposed on the copper layer 104.
According to some embodiments, the material of the substrate layer 102 may include glass, quartz, sapphire, ceramic, other suitable substrate 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), and the like2) Other suitable materials, or combinations of the foregoing, but are not limited to such.
According to some embodiments, the copper layer 104 has a thickness T1Thickness T1May range between 500nm and 1000nm, or between 600nm and 900nm, e.g. 700nm, 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 thereof. The physical vapor deposition process may include, for example, a sputtering process, an evaporation process, a pulsed laser deposition process, etc.
Furthermore, according to some embodiments, the protective layer 106 has a thickness T2Thickness T2May range between 100nm and 200nm, or between 100nm and 150nm, for example 110nm, 120nm, 130nm, or 140 nm.
According to some embodiments, the material of the protection 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 transparent conductive materials, or a combination thereof.
It is noted that, according to some embodiments, the protection layer 106 is substantially transparent or light transmissive, and thus, the degree of corrosion of the underlying copper layer 104 may be observed through the protection layer 106.
According to some embodiments, the protection 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 thereof. For example, the chemical vapor deposition process may include a low pressure chemical vapor deposition process (LPCVD), a low temperature chemical vapor deposition process (LTCVD), a rapid thermal chemical vapor deposition process (RTCVD), a plasma enhanced chemical vapor deposition Process (PECVD), or an atomic layer deposition process (ALD).
Next, as shown in fig. 1B, a crack GP is formed in the multi-layer substrate 100, and the depth of the crack GP reaches the copper layer 104. In detail, according to some embodiments, the crack GP may completely penetrate the protection layer 106 and the copper layer 104 and expose the top surface 102t of the substrate layer 102. According to other embodiments, the crack GP may extend completely through the protection layer 106 but only partially formed in the copper layer 104, i.e., the crack GP does not expose the top surface 102t of the substrate layer 102.
According to some embodiments, the split GP has a width W1Width W1Can range between 30 μm to 100 μm, or 40 μm to 90 μm, for example, 50 μm, 60 μm, 70 μm, or 80 μm. It is noted that if the width W of the split GP1Too small (e.g., less than 30 μm) may increase the difficulty of observing the copper corrosion phenomenon.
According to some embodiments, the gap GP may be formed in the multi-layer substrate 100 by a cutting process. For example, the cutting process may include a knife cutting process, a laser cutting process, other suitable cutting processes, or a combination thereof.
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 contacts the copper layer 104. According to some embodiments, the photosensitive resin composition 108 covers the protection layer 106 and extends into the gap GP, and contacts the sidewall of the protection layer 106 and the sidewall of 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, the colorant (A) may comprise a pigment (A-1) and a dye (A-2). In the present specification, the terms "colorant (a), pigment (a-1)," dye (a-2), "resin (B)," photopolymerizable monomer (C), "photoinitiator (D)," and "solvent (E)" may be used to refer to a single or a plurality of components, including the colorant (a), pigment (a-1), "dye (a-2)," resin (B), "photopolymerizable monomer (C)," photoinitiator (D), "and" solvent (E), "independently.
According to some embodiments, the pigment (a-1) of colorant (a) may comprise a red pigment of c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; 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, etc.; orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, 80, etc. blue pigments; violet pigments of c.i. pigment violet 1, 19, 23, 29, 32, 36, 38, etc.; green pigments of c.i. pigment green 7, 36, 58, etc.; brown pigments of c.i. pigment brown 23, 25, etc.; c.i. pigment black 1, 7, and the like. According to some embodiments, the red pigment (a-1) may be c.i. pigment red 254 (R245). Alternatively, other known pigments may be used as the pigment (A-1). The aforementioned pigments may be used alone, or 2 or more kinds may be mixed and used.
According to some embodiments, the dye (a-2) of the colorant (a) may include a dye of an oil-soluble dye, an acid dye, a basic dye, a direct dye, a mordant dye, an amine salt of an acid dye, or a sulfonamide derivative of an acid dye, or the like. Alternatively, other known dyes may be used as the dye (A-2). Further, according to the chemical structure, there may be exemplified azo dyes, anthocyanine dyes (cyanine dyes), triphenylmethane dyes (triphenylmethane dyes), oxonone dyes (xanthone dyes), phthalocyanine dyes (phthalocyanine dyes), naphthoquinone dyes (naphthoquinone dyes), quinonimine dyes (quinoneine dyes), methine dyes (methine dyes), azomethine dyes (azomethine dyes), squarylium dyes (squarylium dyes), acridine dyes (acridine dyes), styrene dyes (styryl dyes), coumarin dyes (coumarine dyes), quinoline dyes (quinoline dyes), nitro dyes (nitrodye) 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 an oxonol dye (xanthene dye) and an azo dye (azo dye). Further, the aforementioned dyes may be used alone, or 2 or more kinds may be mixed and used.
According to some embodiments, the resin (B) may be an alkali-soluble resin. For example, the alkali-soluble resin can comprise a carboxylic acid group-containing unsaturated monomer, a copolymer of a carboxylic acid group-containing unsaturated monomer and a vinyl group-containing unsaturated monomer, or a combination of the foregoing. For example, according to some embodiments, the carboxylic acid based unsaturated monomer can be selected from Acrylic Acid (AA) based compounds, methacrylic acid based compounds, or combinations thereof. According to some embodiments, the aforementioned ethylenically unsaturated monomer may be selected from methyl acrylate (methyl acrylate), methyl methacrylate (methyl methacrylate), phenyl acrylate (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 acrylate), hydroxypropyl methacrylate (hydroxypropyl methacrylate), isobutyl acrylate (isobutylmethacrylate), isobutyl methacrylate (isobutylmethyl methacrylate), ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), 1, 4-butanediol diacrylate (1, 4-butanediol diacrylate), ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), and mixtures thereof, Pentaerythritol triacrylate (pentaerythrityl triacrylate), ethoxylated pentaerythritol tetraacrylate (ethoxylated pentaerythrityl tetraacrylate), dipentaerythritol pentaacrylate (dipentaerythrityl tetraacrylate), pentaerythritol tetraacrylate (pentaerythrityl tetraacrylate), dipentaerythritol hexaacrylate (dipentaerythrityl tetraacrylate), dicyclopentenyl methacrylate (DCPA), epoxydicyclopentenyl methacrylate (EDCA), epoxydicyclopentenyl methacrylate (EDCPA), methacrylic acid (methacrylate), N-phenylmaleimide (N-imide), tricyclodecenylmethyl acrylate (tricyclohexylmethacrylate), N-phenylmaleimide (N-glycidyl 2-ethylhexyl methacrylate), N-ethylhexylmethacrylate (2-ethylhexylmethacrylate), N-ethylhexylmethacrylate (dimethylhexylmethacrylate), N-ethylhexylmethacrylate (dimethylglycidyl methacrylate), N-ethylmethacrylate (dimethylglycidyl methacrylate), N-2-ethylmethacrylate (dimethylglycidyl methacrylate), N-ethylmethacrylate (dimethylmethacrylate), N-dimethylmethacrylate (dimethylmethacrylate), N-dimethylglycidyl methacrylate, and dimethylmethacrylate (dimethylmethacrylate), and dimethylmethacrylate (dimethylmethacrylate), and dimethylmethacrylate), wherein, Cyclohexyl methacrylate, tert-butyl methacrylate, or combinations of the foregoing. According to some embodiments, the resin (B) may be a resin in combination with monomer EDCPA and monomer AA. According to some embodiments, resin (B) may be SH 5052A.
Further, the photopolymerizable monomer (C) may be a monomer polymerizable by a living radical and/or an acid generated from 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. The compounds described herein with parentheses include the presence and absence of the parenthesized characters, such as the (meth) acrylate compounds described above, including the acrylate compounds and the methacrylate compounds. For example, the photopolymerizable monomer (C) may include, but is not limited to, at least one selected from the group consisting of: polymerizable compounds having one ethylenically unsaturated bond such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolone; polymerizable compounds having two ethylenically unsaturated bonds such as 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate; and polypentaerythritol having three ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc A synthetic compound. According to some embodiments, the photopolymerizable monomer (C) may be dipentaerythritol hexaacrylate (DPHA).
Further, the photoinitiator (D) may be a compound capable of generating an active radical, an acid, etc. by the action of light or heat, thereby initiating polymerization. For example, according to some embodiments, the photoinitiator (D) may include an O-acyloxime (O-acyloxime) compound, an alkylphenone compound, a bisimidazole compound, a triazine compound, an acylphosphine oxide (acyl phosphine oxide), a benzoin compound, a diphenylketone compound, a quinone-based compound, 10-butyl-2-chloroacridone, a benzyl group, a methyl phenylglyoxylate, a cyclopentadienyl titanium (titanocene) compound, or a combination of the foregoing. According to some embodiments, the photoinitiator (D) may be 2,4, 6-trimethylbenzoyldiphenylphosphine 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 performing the copper corrosion detection method, it is further found that the reactivity of the photosensitive resin composition 108 having a specific photoinitiator composition with the copper wire is low, and therefore, the risk of copper wire corrosion or wire breakage can be effectively reduced.
Specifically, according to some embodiments, the photosensitive resin composition 108 includes a photoinitiator that is not an oxime-based photoinitiator (i.e., the photoinitiator is not an oxime-based photoinitiator)Not containing oxime structures) and the photoinitiator has a solids content of not more than 8 wt.% (8 wt.%), the observed degree of copper corrosion of the splits GP is judged to be satisfactory, i.e. no copper corrosion phenomena or a rather slight degree of copper corrosion. According to other embodiments, the photosensitive resin composition 108 includes a photoinitiator that is an oxime-based photoinitiator (i.e., contains an oxime structure) and does not include a nitro group (-NO)2) Or a thio (-S) structure and the photoinitiator has a solids content of not more than 5 wt.% (≦ 5 wt.%), the observed degree of copper corrosion of the vent GP being judged as satisfactory, i.e. no copper corrosion phenomena or a rather slight degree of copper corrosion. According to other embodiments, the photosensitive resin composition 108 includes a photoinitiator that is an oxime-based photoinitiator and includes a nitro group (-NO)2) Or a thio (-S) structure and the photoinitiator has a solids content of not more than 2.5 wt.% (≦ 2.5 wt.%), the observed degree of copper corrosion of the breach GP being judged to be satisfactory, i.e. no copper corrosion phenomena or a rather slight degree of copper corrosion. The detailed description of the embodiments of the present disclosure will be provided below.
According to some embodiments, the solvent (E) may include, but is not limited to, ester solvents (herein, meaning solvents containing-COO-but not-O-in the molecule), ether solvents (herein, meaning solvents containing-O-but not-COO-in the molecule), ether ester solvents (herein, meaning solvents containing-COO-and-O-in the molecule), ketone solvents (herein, meaning solvents containing-CO-but not-COO-in the molecule), alcohol solvents (herein, meaning solvents containing OH but not-O-, -CO-, and-COO-in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like. According to some embodiments, the 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, the photopolymerizable monomer (C) is 210 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, or 3400 to 3900 parts by weight, relative to 100 parts by weight of the resin (B).
According to some embodiments, the photosensitive resin composition 108 may further include a dispersant, a binder, or other additives, such as a leveling agent, a polymerization initiation aid, a filler, an adhesion promoter, an antioxidant, a light stabilizer, a chain transfer agent, and the like, but is not limited thereto. According to some embodiments, the additive may comprise a fluorophilic organic oligomer, such as F554 (DIC).
According to some embodiments, the photosensitive resin composition 108 may be formed on the protection 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 applied by a spin coater, a slit coater (also called a die coater), a curtain flow coater, or a spinless coater), or an ink jet.
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, air drying, reduced pressure drying, heat drying (also referred to as pre-baking), or a combination thereof. According to some embodiments, vacuum drying may be followed by heat drying. According to some embodiments, the pressure range for vacuum drying may be between 40pa and 90pa, or between 50pa and 80 pa. According to some embodiments, the temperature for heat drying may range from 30 ℃ to 120 ℃, or from 40 ℃ to 100 ℃, and the time for heating may range from 10 seconds to 60 minutes, or from 30 seconds to 30 minutes.
Thereafter, as shown in FIG. 1D, a mask layer 110 is provided on the multi-layer substrate 100 and an exposure process is performed. According to some embodiments, the mask layer 110 includes a transparent region 110a and a non-transparent region 110b, the non-transparent region 110b is disposed above the gap GP, and the width W of the non-transparent region 110b2Width W greater than gap GP1That is, the opaque region 110 may completely cover the gap GP. According to some embodiments, in the substrate layer 102, the non-transparent region 110b overlaps the gap GP, and overlaps the copper layer 104 and the passivation layer 106 adjacent to a portion of the gap GP.
According to some embodiments, there is a distance D between an edge of the gap GP and an edge of the opaque region 110b1Distance D1Can 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 distance D1Refers to the minimum distance between the edge of the split GP and the edge of the non-light-transmitting region 110b in a direction parallel to the top surface of the substrate layer 102.
It is noted that one of the reasons for corrosion of the copper layer 104 may be caused by the reaction of the copper and the solvent used in the exposure of the photosensitive resin composition 108, and therefore, if the distance D is set1Too small or too large (e.g., less than 100 μm or greater than 500 μm) may increase the difficulty of observing copper corrosion.
According to some embodiments, the width W of the non-transparent region 110a of the mask layer 1102May be between 130 μm and 600 μm, or between 200 μm and 500 μm, for example 300 μm, or 400 μm. Furthermore, the transparent region 110a of the mask layer 110 has a width W3Width W3And may be greater than 500 μm.
It should be understood that the embodiment in the drawings is exemplified by the photosensitive resin composition 108 using a negative photoresist, but according to other embodiments, the photosensitive resin composition 108 using a positive photoresist can be used, so that the positions of the transparent region 110a and the non-transparent region 110b of the mask layer 110 are opposite to those in the drawings, i.e., the transparent region 110a can be disposed above the gap GP, and the width W of the transparent region 110a3Width W greater than gap GP1。
Referring to fig. 1E, the mask layer 110 may be removed and a developing process may be performed. In detail, according to some embodiments, after exposure using the mask layer 110, an unexposed portion may be removed by a developing process to obtain the patterned photosensitive resin composition 108. As shown in fig. 1D and 1E, light (indicated by arrows in the drawings) can penetrate the transparent region 110a of the mask layer 110 but cannot penetrate the opaque region 110b, the portion 108X of the photosensitive resin composition 108 corresponding to the opaque region 110b is removed in the subsequent developing process, and the portion 108' of the photosensitive resin composition 108 corresponding to the transparent region 110a is not removed in the subsequent developing process.
According to some embodiments, a light source such as a mercury lamp, a light emitting diode, a metal halogen lamp, a halogen lamp, or the like may be used in the exposure step, and light having a wavelength ranging from 250 nm to 450 nm may be used. According to some embodiments, a mask alignment exposure machine, stepper, etc. may be used to uniformly irradiate parallel light across the exposure surface and/or to precisely align the mask and substrate.
In the developing step, a developer such as an organic solvent or an aqueous solution of an alkali compound is used to dissolve a predetermined portion (e.g., an unexposed portion) and remove the dissolved portion, thereby obtaining a pattern.
It is noteworthy that, according to some embodiments, the use of an aqueous solution of a basic compound as a developer is particularly helpful for obtaining well-shaped patterns. According to some embodiments, the concentration of the developer may range, for example, between 0.001 to 0.100 mass%, for example, between 0.040 to 0.050 mass%. According to some embodiments, the developer used in the developing process may comprise an aqueous solution of potassium hydroxide (KOH).
According to some embodiments, the developer may be provided on the multi-layered 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 multi-layer substrate 100 after the development process.
In addition, according to some embodiments, a post-baking process may be performed on the multi-layer substrate 100 after the developing process. According to some embodiments, the drying process may comprise heat drying. According to some embodiments, the temperature range of heating may be between 150 ℃ and 300 ℃, or between 200 ℃ and 250 ℃, for example, 210 ℃, 220 ℃, 230 ℃, or 240 ℃. According to some embodiments, the time of heating 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 noted that the post-bake process will cause the copper layer 104 and the passivation layer 106 adjacent to the gap GP to swell and protrude, which is more beneficial for subsequent observation of the copper corrosion level of the gap GP.
Next, after the post-bake process, the copper corrosion degree of the gap GP was observed. Referring to fig. 2A and 2B, fig. 2A is a schematic cross-sectional view of a multi-layer substrate 100 (and a portion 108' of a photosensitive resin composition 108 formed thereon) after performing the method for detecting copper corrosion according to some embodiments of the present disclosure, and fig. 2B is a schematic top view of the multi-layer substrate 100 shown in fig. 2A. It should be understood that the protection layer 106 on the color non-uniform region 104r of the copper layer 104 is not shown in fig. 2B for clarity of illustration.
As shown in fig. 2A and 2B, according to some embodiments, after the foregoing steps (shown in fig. 1A to 1E) of the method for detecting copper corrosion are performed, a color irregularity region 104r is generated around the gap GP in the multi-layer substrate 100. According to some embodiments, the color irregularity region 104r is substantially in a light red, light orange, light yellow, and white gradation halo, and is respectively light red, light orange, light yellow, and white from the gap GP to the outside (for example, refer to fig. 4, which shows an actual image obtained by an optical microscope). According to some embodiments, the degree of copper corrosion of the breach GP can be observed using an optical microscope.
According to some embodiments, determining the level of copper corrosion includes measuring the width W of the color mura 104r around the gap GP4If the width W of the color uneven area 104r is small4Width W of deducting gap GP1Greater than or equal to 30 μm (W)4-W1Not less than 30 μm), the standard is judged not to be met, namely, the copper corrosion degree is serious; width W of color uneven area 104r4Width W of deducting gap GP1Less than 30 μm (W)4-W1<30 μm), it is judged to be satisfactory, i.e., there is no copper corrosion or the copper corrosion is relatively slight.
It should be noted that the width W of the color unevenness region 104r4Of fingersIs the maximum width of the color irregularity region 104r in the direction perpendicular to the extending direction of the gap GP, and this value may be an average value obtained after three measurements (different positions). Furthermore, it should be understood that, according to various embodiments, the determination of whether the copper corrosion level meets the specified threshold may be adjusted according to the product requirements.
Referring to fig. 3A and 3B, fig. 3A is a schematic cross-sectional view of a multi-layer substrate 100 (and a portion 108' of a photosensitive resin composition 108 formed thereon) after performing the method for detecting copper corrosion according to other embodiments of the present disclosure, and fig. 3B is a schematic top view of the multi-layer substrate 100 shown in fig. 3A.
As shown in fig. 3A and 3B, according to some embodiments, after the steps of the method for detecting copper corrosion (as shown in fig. 1A to 1E), the color irregularity region 104r is not generated around the gap GP in the multi-layer substrate 100, i.e., in this embodiment, the copper corrosion does not occur (for example, see fig. 5, which shows an actual image obtained by an optical microscope).
In view of the foregoing, according to some embodiments of the present disclosure, a method for detecting copper corrosion is provided, which includes evaluating a degree of corrosion of a photosensitive resin composition on a copper wire by using a patterned multi-layer substrate, and performing a photolithography process using a specific multi-layer substrate structure in combination with a photosensitive resin composition, so as to effectively and easily determine whether the copper wire is corroded, and the 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 is provided with low reactivity with the copper wire, so that the risk of corrosion or wire breakage of the copper wire can be effectively reduced.
In order to make the aforementioned and other objects, features, and advantages of the present disclosure more comprehensible, several embodiments, comparative examples and test examples are described in detail below, but the present disclosure is not limited thereto.
Examples 1 to 9/comparative examples 1 to 6
Firstly, preparing a patterned multilayer substrate, and the steps are as follows: plating metal copper with the thickness of 500 nm-1000 nm on the surface of the mother glass, then plating a silicon nitride layer with the thickness of 100 nm-150 nm on the metal copper plating layer, and then using a blade to scratch the silicon nitride layer and the metal copper layer together to form a linear crack, wherein the width of the crack is between 20 mu m and 50 mu m.
Then, the photosensitive resin compositions of examples 1 to 9 and comparative examples 1 to 6 were prepared as shown in the following tables 1 and 2. Specifically, the photosensitive resin compositions having different material ratios shown in tables 1 and 2 were uniformly mixed, and then the photosensitive resin compositions were applied to the patterned multilayer substrate of 5cm by using a spin coating method, thereby completing a wet film test piece.
And then, putting the wet film test piece into a vacuum drier, covering a sealing cover, vacuumizing, setting the air exhaust bottom pressure to be 66pa, maintaining for 20 seconds, breaking vacuum to recover the atmospheric pressure after the air exhaust bottom pressure is finished, taking the wet film test piece out of the vacuum drier, placing the wet film test piece on a heating plate with the temperature of 90 ℃ for heating for 38 seconds, and then cooling at room temperature to finish the step of pre-drying.
Exposing the wet film test piece in an exposure machine with a light volume of 40mJ/cm2And the distance between the mask and the wet film test piece is set to 265 μm, and exposure is performed after the setting is completed. The widths of the transparent region and the non-transparent region of the selected mask are 1000 μm and 1000 μm, respectively, and the non-transparent region covers the gap.
And (3) putting the exposed wet film test piece into a developing machine, using a KOH aqueous solution with the concentration of 0.044% as a developer, setting the developing time to be 60 seconds, setting the developing pressure to be 0.06MPa, and setting the height of a developer nozzle to be 17 cm away from the wet film test piece. After the development was completed, a rinsing step was performed using deionized water, with a rinsing time and pressure set to 40 seconds and 0.1Mpa, respectively, and a height of a rinsing nozzle from the wet film test piece was set to 17 cm. The temperature of the developer and the deionized water for cleaning are maintained in a temperature range of 23 +/-1 ℃ by using a heating and cooling device.
And (3) putting the wet film test piece into an oven with the temperature of 230 ℃ for post-baking, taking out the wet film test piece after baking for 20 minutes, and cooling to finish the manufacture of the test piece (the multilayer substrate with the photosensitive resin composition thereon).
Next, an optical microscope (manufacturer, model:. OLYMPUS DSX 500. ANG.) was used to observe whether or not copper corrosion occurred at the crack, and the specific procedure for determining the degree of copper corrosion was as described above, and the results are shown in tables 1 and 2.
TABLE 1
TABLE 2
The percentages of the components in tables 1 and 2 are expressed in terms of solid contents (%), wherein pigment R254 is pigment (A-1) of the colorant (A), SH5052A is the resin (B), DPHA is the photopolymerizable monomer (C), I-819, PBG-345, PBG-365, PBG-380, and PBG-327 are the photoinitiator (D), and DAA, PGME, and PGMEA are the solvent (E).
As is clear from the results shown in tables 1 and 2, when the photoinitiator contained in the photosensitive resin composition was a non-oxime photoinitiator and the solid content of the photoinitiator was not more than 8 wt% (examples 1 to 3), the degree of copper corrosion of the crack GP was observed to be 0 μm, which satisfied the standard. When the photosensitive resin composition contains a photoinitiator which is an oxime-based photoinitiator and does not contain a nitro group (-NO)2) Or a sulfur (-S) structure, and when the solid content of the photoinitiator is not more than 5 wt% (examples 4 to 7), the observed degree of copper corrosion of the crack GP is between 12.6 μm and 25.5 μm, which is in accordance withAnd (4) standard. Further, when the photosensitive resin composition contains a photoinitiator which is an oxime-based photoinitiator and contains a nitro group (-NO)2) Or a sulfur (-S) structure, and the solid content of the photoinitiator is not more than 2.5 wt% (examples 8 to 9), the copper corrosion degree of the crack GP is observed to be between 17.8 μm and 27.2 μm, which meets the standard.
Although embodiments of the present disclosure and their advantages have been described above, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the disclosure by those skilled in the art. Features of the disclosed embodiments can be combined in any suitable manner without departing from the spirit or ambit of the invention. Moreover, the scope of the present disclosure is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. Accordingly, the scope of the present disclosure includes the processes, machines, manufacture, compositions of matter, means, methods, and steps described above. The scope of the present disclosure is to be determined by the claims appended hereto.
Claims (15)
1. A multilayer substrate for copper corrosion detection, comprising:
a base layer;
a copper layer disposed on the substrate layer; and
a protective layer disposed on the copper layer.
2. The multilayer substrate for copper corrosion detection according to claim 1, 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, a transparent conductive oxide, or a combination of the foregoing.
3. The multilayer substrate for copper corrosion detection according to claim 1, wherein the copper layer has a thickness of 500nm to 1000 nm; and/or the thickness of the protective layer is between 100nm and 200 nm.
4. A method for detecting copper corrosion, comprising:
providing a multi-layer substrate, wherein the multi-layer substrate comprises a copper layer;
forming a gap in the multi-layer 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 multi-layer substrate, and performing an exposure process;
removing the mask layer and performing a developing process;
performing a post-baking process on the multi-layer substrate; and
the breach was observed for copper corrosion.
5. The method of claim 4, wherein the mask layer comprises a transparent region and a non-transparent region, the non-transparent region is disposed above the opening, and the width of the non-transparent region is greater than the width of the opening.
6. The method as claimed in claim 5, wherein the width of the gap is between 30 μm and 100 μm.
7. The method as claimed in claim 5, wherein a distance between an edge of the slit and an edge of the opaque region is between 100 μm and 500 μm.
8. The method of claim 4, wherein the mask layer comprises a transparent region and a non-transparent region, the transparent region is disposed above the opening, and the width of the transparent region is greater than the width of the opening.
9. The method of claim 4, wherein the step of observing the copper corrosion level of the breach comprises:
measuring the width of a color uneven area around the gap, if the width of the color uneven area minus the width of the gap is greater than or equal to 30 μm, determining that the color uneven area does not meet the standard, and if the width of the color uneven area minus the width of the gap is less than 30 μm, determining that the color uneven area meets the standard.
10. The method as claimed in claim 4, wherein the multi-layer substrate further comprises a passivation layer disposed on the copper layer, wherein the slit penetrates the passivation layer.
11. The method of claim 4, wherein the multi-layer substrate further comprises a base layer, wherein the slit exposes a top surface of the base layer.
12. The method of claim 4, wherein the photosensitive resin composition comprises at least one photoinitiator, the at least one photoinitiator is not an oxime (oxime) photoinitiator, and the photoinitiator has a solid content of not more than 8 wt%, wherein the copper corrosion level of the crack is determined to meet the standard.
13. The method of claim 4, wherein the photosensitive resin composition comprises at least one photoinitiator, the at least one photoinitiator being an oxime photoinitiator and not comprising a nitro group (-NO)2) Or a sulfur (-S) based structure, and the at least one photoinitiator has a solid content of not more than 5 wt%, wherein the degree of copper corrosion observed in the breach is judged to be satisfactory.
14. The method of claim 4, wherein the photosensitive resin composition comprises at least one photoinitiator, the at least one photoinitiator is an oxime photoinitiator and comprises a nitro or thio structure, and the solid content of the at least one photoinitiator is not greater than 2.5 wt%, wherein the copper corrosion level of the crack is determined to meet the standard.
15. The method for detecting copper corrosion according to claim 4, wherein the multilayer substrate is selected from the multilayer substrates for copper corrosion detection according to any one of claims 1 to 3.
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| CN102134055A (en) * | 2011-02-12 | 2011-07-27 | 中国科学院光电技术研究所 | Method for forming metal nano structure by utilizing crevice corrosion |
| CN102628788A (en) * | 2011-06-09 | 2012-08-08 | 京东方科技集团股份有限公司 | Detection structure of barrier property of corrosion barrier layer and detection method |
| CN103373820A (en) * | 2012-04-11 | 2013-10-30 | 钜永真空科技股份有限公司 | Colored glass and its manufacturing process |
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| JP7008732B2 (en) * | 2018-01-29 | 2022-01-25 | 富士フイルム株式会社 | Photosensitive resin composition, resin, cured film, laminate, method for manufacturing cured film, semiconductor device |
| JP7023379B2 (en) * | 2018-09-27 | 2022-02-21 | 富士フイルム株式会社 | Resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device |
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| CN102134055A (en) * | 2011-02-12 | 2011-07-27 | 中国科学院光电技术研究所 | Method for forming metal nano structure by utilizing crevice corrosion |
| CN102628788A (en) * | 2011-06-09 | 2012-08-08 | 京东方科技集团股份有限公司 | Detection structure of barrier property of corrosion barrier layer and detection method |
| CN103373820A (en) * | 2012-04-11 | 2013-10-30 | 钜永真空科技股份有限公司 | Colored glass and its manufacturing process |
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