CN112881270B - Copper corrosion detection method - Google Patents
Copper corrosion detection method Download PDFInfo
- Publication number
- CN112881270B CN112881270B CN202110034401.9A CN202110034401A CN112881270B CN 112881270 B CN112881270 B CN 112881270B CN 202110034401 A CN202110034401 A CN 202110034401A CN 112881270 B CN112881270 B CN 112881270B
- Authority
- CN
- China
- Prior art keywords
- layer
- copper
- width
- substrate
- photosensitive resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Environmental Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Ecology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The present disclosure provides a method for detecting copper corrosion. The method for detecting copper corrosion comprises the following steps: providing a multilayer substrate, wherein the multilayer substrate comprises a copper layer; forming a breach in the multi-layer substrate, wherein the depth of the breach reaches the copper layer; forming a photosensitive resin composition on the multilayer substrate, the photosensitive resin composition covering the slit and contacting the copper layer; providing a photomask 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-layered substrate; and observing the copper corrosion level of the crack.
Description
Technical Field
The present disclosure relates to a multilayer 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 by a photosensitive resin composition.
Background
In recent years, array (array) wiring in panel manufacturing processes gradually uses copper wire manufacturing processes to replace traditional aluminum wire manufacturing processes, and because copper metal has good conductivity, the wiring line width can be reduced, so that more complex and higher resolution panel wiring design can be satisfied, and the light transmittance of the panel can be improved.
In view of the foregoing, it is still one of the problems of the current research in the industry to develop a method for effectively detecting corrosion of copper wires and improving the reliability of the detection method in response to the requirement of using copper wires in the panel process. In addition, development of a formulation of a photosensitive resin composition which is less likely to cause disconnection or corrosion defects of copper wiring is one of the subjects of intensive studies in the industry.
Disclosure of Invention
Because copper and aluminum are substantially different, process compatibility is a problem, for example, when materials originally used in aluminum wire manufacturing process are applied to copper wire manufacturing process, unexpected chemical reaction may occur, which may further cause corrosion or breakage of copper wires on the array substrate, and extend reliability problem of subsequent products. The foregoing problems often occur with panel products designed with color filters (color filter on array, COA) on an array.
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, 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, comprising: providing a multilayer substrate, wherein the multilayer substrate comprises a copper layer; forming a breach in the multi-layer substrate, wherein the depth of the breach reaches the copper layer; forming a photosensitive resin composition on the multilayer substrate, the photosensitive resin composition covering the slit and contacting the copper layer; providing a photomask 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-layered substrate; and observing the copper corrosion level of the crack.
In order to make the features and advantages of the present disclosure more comprehensible, several embodiments accompanied with figures are described in detail below.
Drawings
FIGS. 1A-1E are 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 etching test 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 etching test method according to some embodiments of the present disclosure;
FIG. 3B is a schematic top view of a multi-layered substrate during a copper corrosion detection method according to some embodiments of the present disclosure;
FIG. 4 is a schematic view of an image of a multi-layered substrate obtained by an optical microscope during a copper corrosion detection method according to some embodiments of the present disclosure;
fig. 5 shows an image of a multi-layer substrate taken with an optical microscope during the performance of a method for detecting copper corrosion according to some embodiments of the present disclosure.
[ symbolic description ]
100 multilayer substrate
102 substrate layer
102t top surface
104 copper layer
104r color non-uniformity region
106 protective layer
108 photosensitive resin composition
108': part
108X part of
110 mask layer
110a light transmitting region
110b non-light-transmitting region
D 1 Distance to
GP breach
T 1 Thickness of (A)
T 2 Thickness of (A)
W 1 Width of
W 2 Width of
W 3 Width of
W 4 Width of
Detailed Description
The following describes the method for detecting copper corrosion in the embodiments of the present disclosure in detail. 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 details set forth below are merely to provide a thorough description of certain embodiments of the present disclosure. These are, of course, merely examples and are not intended to be limiting of the present disclosure. Moreover, similar and/or corresponding reference numerals may be used in different embodiments to identify similar and/or corresponding elements in order 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 is not intended to represent any relevance between the various embodiments and/or structures discussed.
The embodiments of the present disclosure may be understood in conjunction with the accompanying drawings, which are also considered a part of the disclosure. It should be understood that the drawings of the present disclosure are not drawn to scale, and that virtually any enlargement or reduction of the size of the elements is possible in order to clearly demonstrate 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 appreciated that if the device of the drawings is turned upside down, elements described as being on the "lower" side would then be elements on the "upper" side. Furthermore, when a first material layer is described as being on or over a second material layer, this includes situations where the first material layer is in direct contact with the second material layer. Alternatively, one or more other material layers may be spaced apart, in which case there may not be direct contact between the first material layer and the second material layer.
As used herein, the term "about," "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 about amounts, i.e., without specifying "about", "substantially" what is meant by "about". Furthermore, the term "range between 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 appreciated 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 includes a method for evaluating the corrosion degree of a photosensitive resin composition on a copper wire by using a patterned multilayer substrate. In detail, the method includes performing a photolithography process with a specific multi-layered substrate structure in combination with a photosensitive resin composition, thereby efficiently and simply determining whether corrosion of copper wires occurs, and providing a method for detecting copper corrosion with good reliability. According to some embodiments of the present disclosure, the provided photosensitive resin composition with a specific composition has low reactivity with copper wires, so that the risk of corrosion or wire breakage of the copper wires can be effectively reduced.
Referring to fig. 1A to 1E, fig. 1A to 1E are schematic cross-sectional views of a multi-layer substrate 100 during a copper corrosion detection method according to some embodiments of the disclosure. It should be appreciated that according to some embodiments, additional operational steps may be provided before, during, and/or after the detection of copper corrosion. According to some embodiments, some of the operational steps described 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 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 substrate layer 102 may comprise 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 a material including silicon (Si), silicon carbide (SiC), gallium nitride (GaN), silicon dioxide (SiO) 2 ) Other suitable materials, or a combination of the foregoing, but are not limited thereto.
According to some embodiments, the copper layer 104 has a thickness T 1 Thickness T 1 May range between 500nm and 1000nm, or between 600nm and 900nm, for example 700nm, or 800nm.
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, and the like.
Furthermore, according to some embodiments, the protective layer 106 has a thickness T 2 Thickness T 2 Can range from 100nm to 200nm, or betweenBetween 100nm and 150nm, for example 110nm, 120nm, 130nm, or 140nm.
According to some embodiments, the material of the protective layer 106 may comprise silicon nitride (SiN), transparent conductive oxide (transparent conductive oxide, TCO), or a combination of the foregoing. For example, the transparent conductive oxide may include Indium Tin Oxide (ITO), antimony zinc oxide (antimony zinc oxide, AZO), tin oxide (tin oxide, snO), zinc oxide (zinc oxide, znO), indium zinc oxide (indium zinc oxide, IZO), indium gallium zinc oxide (indium gallium zinc oxide, IGZO), indium tin zinc oxide (indium tin zinc oxide, ITZO), antimony tin oxide (antimony tin oxide, ATO), other suitable transparent conductive materials, or combinations of the foregoing.
Notably, according to some embodiments, the protective layer 106 is substantially transparent or light permeable, and thus, the extent of corrosion of the underlying copper layer 104 may 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 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), an atomic layer deposition process (ALD), or the like.
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 breach GP may completely penetrate the protective layer 106 and the copper layer 104, and expose the top surface 102t of the base layer 102. According to other embodiments, the breach GP may extend completely through the protective layer 106 but be only partially formed in the copper layer 104, i.e., the breach GP does not expose the top surface 102t of the substrate layer 102.
According to some embodiments, the breach GP has a width W 1 Width W 1 May range between 30 μm and 100 μm, or between 40 μm and 90 μm, for example, 50 μm, 60 μm, 70 μm, or 80 μm. Notably, ifWidth W of breach GP 1 Too small (e.g., less than 30 μm), the difficulty in observing the copper corrosion phenomenon may be increased.
According to some embodiments, the slits GP may be formed in the multi-layered substrate 100 through a dicing process. For example, the dicing process may include a knife dicing process, a laser dicing process, other suitable dicing 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, colorant (A) may comprise pigment (A-1) and dye (A-2). In this context, the terms "colorant (A), pigment (A-1), dye (A-2), resin (B), photo-polymerizable monomer (C), photo-initiator (D), solvent (E) and the like" may independently include a single or a plurality of components such as colorant (A), pigment (A-1), dye (A-2), resin (B), photo-polymerizable monomer (C), photo-initiator (D), solvent (E) and the like.
According to some embodiments, 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.; yellow pigments of 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, etc.; c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. blue pigments of 60, 80, etc.; violet pigments of c.i. pigment violet 1, 19, 23, 29, 32, 36, 38, etc.; green pigments such as c.i. pigment green 7, 36, 58; brown pigments such as c.i. pigment brown 23, 25, etc.; black pigments such as c.i. pigment black 1 and 7. 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 may be mixed and used.
In accordance with some embodiments, the dye (a-2) of colorant (a) may comprise a dye that is 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, azo dyes, anthocyanin dyes (cyanine dyes), triphenylmethane dyes (triphenylmethane dye), oxazene dyes (xanthone dyes), phthalocyanine dyes (phthalocyanine dye), naphthoquinone dyes (naphthoquinone dye), quinone imine dyes (quinone imine dyes), methine dyes (methine dyes), azomethine dyes (azomethine dyes), squaraine dyes (squaraine dyes), acridine dyes (acridine dyes), styrene dyes (styryl dyes), coumarin dyes (coumarin dyes), quinoline dyes (quinone dyes), nitrone dyes (nitrone dyes), and the like can be exemplified. 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 oxazin dye (xanthone dye) as well as an azo dye (azo dye). Furthermore, the foregoing dyes may be used alone, or may be used in a mixture of 2 or more.
According to some embodiments, the resin (B) may be an alkali soluble resin. For example, the alkali-soluble resin may comprise an unsaturated monomer containing a carboxylic acid group, a copolymer of an unsaturated monomer containing a carboxylic acid group and an unsaturated monomer containing a vinyl group, or a combination of the foregoing. For example, according to some embodiments, the aforementioned carboxylic acid-based unsaturated monomer may be selected from Acrylic Acid (AA) -based compounds, methacrylic compounds, or combinations of the foregoing. According to some embodiments, the foregoing ethylenically unsaturated monomer may be selected from methyl acrylate (methyl acrylate), methyl methacrylate (methyl methacrylate), phenyl acrylate (benzoyl 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 (hydroxylpropyl acrylate), hydroxypropyl methacrylate (hydroxylpropyl methacrylate), isobutyl acrylate (isobutyl methacrylate), isobutyl methacrylate (isobutyl methacrylate), ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), 1, 4-butanediol diacrylate (1,4butanediol diacrylate), diethylene glycol diacrylate (diethylene glycol diacrylate), pentaerythritol triacrylate (pentaerythritol triacrylate), ethoxylated pentaerythritol tetraacrylate (ethoxylated pentaerythritol tetraacrylate), ethoxylated trimethylpropane triacrylate (ethoxylated trimethylpropane triacrylate), dipentaerythritol pentaacrylate (dipentaerythritol pentaacrylate), pentaerythritol tetraacrylate (pentaerythritol tetraacrylate), dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate), dicyclopentene methacrylate (dihydrodicyclopentadienyl acrylate, DCPA), epoxydicyclopentene methacrylate (epoxy dicyclopentenyl acrylate), EDA, maleic anhydride (CPacrylic acid), and maleimide (CPacrylic acid), methyl tricyclodecyl acrylate (tricyclodecyl methacrylate), vinyl toluene (vinyl toside), N-ethylmaleimide (N-cyclohexlylmenimide), 2-ethylhexyl acrylate (2-ethylhexyl acrylate), glycidyl methacrylate (glycidyl methacrylate), cyclohexyl methacrylate (cyclohexyl methacrylate), t-butyl methacrylate (tert-butyl methacrylate), or a combination of the foregoing. According to some embodiments, resin (B) may be a resin in combination with monomer AA in monomer EDCPA. According to some embodiments, resin (B) may be SH5052A.
Furthermore, 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, ethylenically unsaturated bonds having polymerizability, such as (meth) acrylate compounds. The compounds described using brackets herein are meant to include the presence and absence of the words in brackets, such as the aforementioned (meth) acrylate compounds, including acrylate compounds, and 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-vinylpyrrolidone; polymerizable compounds having two ethylenically unsaturated bonds, such as 1, 6-hexane diol 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-methylpentane diol di (meth) acrylate; and polymerizable compounds 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, hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tri (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, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. According to some embodiments, the photopolymerizable monomer (C) may be dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate, DPHA).
The photoinitiator (D) may be a compound capable of generating active radicals, acids, etc. by the action of light or heat, and thus initiating polymerization. For example, according to some embodiments, the photoinitiator (D) may comprise an O-acyl oxime (O-acyloxime) compound, an alkylphenyl ketone compound, a bisimidazole compound, a triazine compound, an acylphosphine oxide (acyl phosphine oxide), a benzoin compound, a diphenyl ketone compound, a quinone-based compound, 10-butyl-2-chloroacridone, benzyl, methyl benzoyl formate, a titanium cyclopentadienyl compound, or a combination of the foregoing. According to some embodiments, the photoinitiator (D) may be 2,4, 6-trimethylbenzoyl diphenyl phosphine 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 method for detecting copper corrosion, it is further found that the photosensitive resin composition 108 having a specific photoinitiator composition has low reactivity with copper wires, and thus the risk of copper wire corrosion or wire breakage can be effectively reduced.
Specifically, according to some embodiments, the photo-initiator included in the photosensitive resin composition 108 is not an oxime-based photo-initiator (i.e., does not contain an oxime structure), and the solid content of the photo-initiator is not more than 8wt% (+.ltoreq.8 wt%) and the observed copper corrosion level of the split GP is judged to be standard, i.e., no copper corrosion phenomenon or a relatively slight copper corrosion level. According to other embodiments, the photo-initiator included in the photosensitive resin composition 108 is an oxime-based photo-initiator (i.e., contains an oxime structure) and does not include a nitro group (-NO) 2 ) Or a thio (-S) structure, and the solid content of the photoinitiator is not more than 5 wt.% (.ltoreq.5 wt.%) and the observed copper corrosion level of the breach GP is judged to be standard, i.e. no copper corrosion phenomenon or a relatively slight copper corrosion level. According to other embodiments, the photo-initiator included in the photosensitive resin composition 108 is an oxime-based photo-initiator and includes a nitro group (-NO) 2 ) Or a thio (-S) structure, and the solid content of the photoinitiator is not more than 2.5 wt.% (. Ltoreq.2.5 wt.%) and the observed copper corrosion level of the breach GP is judged to be standard, i.e. no copper corrosion phenomenon or a relatively slight copper corrosion level. Detailed implementations of embodiments of the present disclosure are described 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 dispersing agent, a binder, or other additives, such as a leveling agent, a polymerization initiator, 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 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 applied by a spin coater, a slot coater (also known as die coater), a curtain coater (curtain flow coater), or a non-spin coater (spin coater), or an inkjet coater.
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, through-air drying, reduced pressure drying, heat drying (also known as pre-baking), or a combination of the foregoing. According to some embodiments, vacuum drying may be followed by heat drying. According to some embodiments, the vacuum drying pressure may range between 40pa and 90pa, or between 50pa and 80 pa. According to some embodiments, the temperature range of the heat drying may be between 30 ℃ and 120 ℃, or between 40 ℃ and 100 ℃, and the time of the heating may be between 10 seconds and 60 minutes, or between 30 seconds and 30 minutes.
Thereafter, as shown in fig. 1D, a mask layer 110 is provided on the multi-layer substrate 100 to perform an exposure process. 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 breach GP, and the width W of the non-transparent region 110b 2 Width W greater than breach GP 1 That is, the opaque region 110 may completely cover the breach GP. According to some embodiments, in the normal direction of the substrate layer 102, the opaque region 110b overlaps the breach GP and overlaps the copper layer 104 and the protective layer 106 adjacent to a portion of the breach GP.
According to some embodiments, there is a distance D between the edge of the breach GP and the edge of the non-transparent area 110b 1 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 distance D 1 Refers to the minimum distance between the edge of the breach GP and the edge of the non-transparent region 110b in a direction parallel to the top surface of the substrate layer 102.
It is noted that one of the reasons for the corrosion of the copper layer 104 may be the reaction of the solvent used in the exposure of the photosensitive resin composition 108 with copper, and thus, if the distance D 1 Too small or too large (e.g., less than 100 μm or greater than 500 μm) may increase the difficulty in observing copper corrosion.
According to some embodiments, the width W of the opaque region 110a of the mask layer 110 2 May be between 130 μm and 600 μm, or between 200 μm and 500 μm, for example 300 μm, or 400 μm. Furthermore, the mask layer 11The light-transmitting region 110a of 0 has a width W 3 Width W 3 May be greater than 500 μm.
It should be understood that the embodiments in the drawings take the photosensitive resin composition 108 using a negative photoresist as an example, but according to other embodiments, the photosensitive resin composition 108 using a positive photoresist may 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 may be disposed above the slit GP, and the width W of the transparent region 110a 3 Width W greater than breach GP 1 。
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, the unexposed portions may be removed by a development process to obtain the patterned photosensitive resin composition 108. As shown in fig. 1D and 1E, light (indicated by arrows in the drawings) can pass through the transparent region 110a of the mask layer 110 but cannot pass through the non-transparent region 110b, and the portion 108X of the photosensitive resin composition 108 corresponding to the non-transparent region 110b is removed in the subsequent development process, while the portion 108' of the photosensitive resin composition 108 corresponding to the transparent region 110a is not removed in the subsequent development process.
According to some embodiments, in the exposing step, a mercury lamp, a light emitting diode, a metal halogen lamp, a halogen lamp, etc. light source may be used, 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 the entire exposure surface with parallel light rays and/or to precisely align the mask and the substrate.
Further, in the developing step, a developer such as an organic solvent or an aqueous solution of an alkaline compound may be used to dissolve predetermined portions (e.g., unexposed portions) 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 patterns. According to some embodiments, the concentration of the developer may range, for example, from 0.001 mass% to 0.100 mass%, for example, from 0.040 mass% to 0.050 mass%. According to some embodiments, the developer used in the development process may comprise an aqueous potassium hydroxide (KOH) solution.
According to some embodiments, the developer may be provided on the multi-layered substrate 100 by a paddle 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 developing process.
Furthermore, according to some embodiments, after the developing process, a post bake process may be performed on the multi-layered substrate 100. According to some embodiments, the drying process may comprise heat drying. According to some embodiments, the temperature of the heating may range between 150 ℃ and 300 ℃, or between 200 ℃ and 250 ℃, e.g., 210 ℃, 220 ℃, 230 ℃, or 240 ℃. 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 should be noted that the post bake process will expand and protrude the copper layer 104 and the passivation layer 106 adjacent to the breach GP, which is more beneficial for subsequent observation of the copper corrosion level of the breach GP.
Then, after the post bake process, the copper corrosion level of the crack GP is observed. Referring to fig. 2A and 2B, fig. 2A is a schematic cross-sectional structure of the multi-layer substrate 100 (and the portion 108' of the 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 corresponding to fig. 2A. It should be appreciated that for clarity of illustration, the passivation layer 106 is not shown on the color non-uniformity region 104r of the copper layer 104 in FIG. 2B.
As shown in fig. 2A and 2B, according to some embodiments, after the foregoing steps of the method for detecting copper corrosion (as shown in fig. 1A to 1E) are performed, a color non-uniformity region 104r is generated around the breach GP in the multi-layer substrate 100. According to some embodiments, the color non-uniform region 104r is substantially in the form of a light red, light orange, light yellow, white vignetting, and is light red, light orange, light yellow, white, respectively, from the slit GP outwards (see fig. 4, which shows an actual image obtained by an optical microscope, for example). According to some embodiments, the copper corrosion level of the breach GP may be observed using an optical microscope.
According to some embodiments, determining the copper corrosion level includes measuring the width W of the color non-uniformity region 104r around the gap GP 4 If the width W of the color unevenness region 104r 4 Width W of deducted breach GP 1 Greater than or equal to 30 μm (W) 4 -W 1 Not less than 30 μm), it is judged that the standard is not met, that is, the copper corrosion degree is serious; if the width W of the color unevenness region 104r 4 Width W of deducted breach GP 1 Less than 30 μm (W) 4 -W 1 <30 μm), it is determined that the standard is met, i.e., no copper corrosion phenomenon or a relatively slight degree of copper corrosion.
It should be noted that the width W of the color unevenness region 104r 4 The maximum width of the color unevenness region 104r in the direction perpendicular to the extending direction of the slit GP is defined, and the value may be the average value obtained after three measurements (different positions). In addition, it should be understood that, according to different embodiments, the determination of whether the copper corrosion level meets the specified threshold value may be adjusted according to the requirements of the product.
Further, referring to fig. 3A and 3B, fig. 3A is a schematic cross-sectional structure of the multi-layer substrate 100 (and the portion 108' of the photosensitive resin composition 108 formed thereon) after performing the method for detecting copper corrosion according to another embodiment of the disclosure, and fig. 3B is a schematic top view of the multi-layer substrate 100 corresponding to fig. 3A.
As shown in fig. 3A and 3B, after the foregoing steps of the method for detecting copper corrosion (as shown in fig. 1A to 1E) are performed, the color non-uniformity region 104r is not generated around the breach GP in the multi-layer substrate 100, i.e., in this embodiment, no copper corrosion occurs (for example, please refer to 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 a method for evaluating a corrosion degree of a photosensitive resin composition on a copper wire by using a patterned multi-layer substrate, and includes performing a photolithography process with the 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. In addition, according to some embodiments of the present disclosure, the provided 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.
In order to make the above and other objects, features and advantages of the present disclosure more comprehensible, several embodiments accompanied with figures, comparative examples and test examples are described in detail below, which should not be construed as limiting the present disclosure.
Examples 1 to 9/comparative examples 1 to 6
Firstly, preparing a patterned multilayer substrate, which comprises the following steps: plating metal copper with the thickness of 500-1000 nm on the surface of plain glass, plating a silicon nitride layer with the thickness of 100-150 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 split, wherein the width of the split is 20-50 mu m.
Thereafter, photosensitive resin compositions of examples 1 to 9 and comparative examples 1 to 6 were prepared in accordance with the contents shown in the following tables 1 and 2. Specifically, the photosensitive resin compositions of different material ratios shown in table 1 and table 2 were uniformly mixed, and then the photosensitive resin composition was coated on the patterned multilayer substrate of 5cm×5cm by spin coating, thereby completing the wet film test piece.
Then, the wet film test piece was put into a vacuum dryer, vacuum was applied after the sealing cover was covered, the suction bottom pressure was set to 66pa and maintained for 20 seconds, after the completion, the vacuum was broken to restore the atmospheric pressure, the wet film test piece was taken out of the vacuum dryer and placed on a heating plate at 90 ℃ for heating for 38 seconds, and then cooled in room temperature, thereby completing the pre-drying step.
Placing the wet film test pieceExposing in an exposure machine, and setting the light accumulation amount to 40mJ/cm 2 And the distance between the mask and the wet film test piece was set to 265 μm, and exposure was performed after the completion of the setting. The width of the transparent region and the non-transparent region of the selected photomask is 1000 μm and 1000 μm respectively, and the non-transparent region covers the split.
The wet film test piece after the exposure was put into a developing machine, a KOH aqueous solution having a concentration of 0.044% was used as a developer, the development time was set to 60 seconds, the development pressure was set to 0.06MPa, and the height of the developer nozzle was 17 cm from the wet film test piece. After the development was completed, a cleaning step was performed using deionized water, and the cleaning time and pressure were set to 40 seconds and 0.1Mpa, respectively, with the cleaning nozzle height being 17 cm from the wet film test piece. The developer and the deionized water for cleaning are maintained at a temperature range of 23+ -1deg.C by using a heating and cooling device.
The wet film test piece was put into an oven at 230℃for a post-baking step, baked for 20 minutes, and then taken out for cooling, thereby completing the production of a test piece (a multilayer substrate having a photosensitive resin composition thereon).
Next, the presence or absence of copper corrosion at the crack was observed by an optical microscope (manufacturer, model: _ OLYMPUSDSX 500_), and the results are shown in Table 1 and Table 2.
TABLE 1
/>
TABLE 2
The percentages of the components in Table 1 and Table 2 are expressed in terms of solid (%), 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, PBG-327 is the photoinitiator (D), and DAA, PGME, PGMEA is the solvent (E).
From the results shown in tables 1 and 2, it is found that when the photoinitiator contained in the photosensitive resin composition is a non-oxime photoinitiator and the solid content of the photoinitiator is not more than 8wt% (examples 1 to 3), the copper corrosion level of the crack GP observed is 0 μm, and meets the standard. When the photo-initiator contained in the photosensitive resin composition is an oxime-based photo-initiator and contains NO nitro group (-NO) 2 ) Or a thio (-S) structure, and the solid content of the photoinitiator is not more than 5% by weight (examples 4 to 7), the observed copper corrosion level of the split GP is between 12.6 μm and 25.5 μm, conforming to the standard. Furthermore, when the photo-initiator contained in the photosensitive resin composition is an oxime-based photo-initiator and contains a nitro group (-NO) 2 ) Or a thio (-S) structure, and the solid content of the photoinitiator is not more than 2.5wt% (examples 8 to 9), the observed copper corrosion level of the split GP is between 17.8 μm and 27.2 μm, conforming to the standard.
Although embodiments and advantages of the present disclosure have been disclosed, it should be understood that various changes, substitutions and alterations can be made herein by those of ordinary skill in the art without departing from the spirit and scope of the disclosure. Features of the embodiments of the present disclosure may be mixed and matched at will without departing from the spirit or conflict of the present disclosure. Furthermore, the scope of the present application 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, which will be readily apparent to those of ordinary skill in the art from the present disclosure, unless otherwise indicated herein, such that the process, machine, manufacture, composition of matter, means, methods and steps described in the specification are performed with substantially the same function or result in substantially the same way as the embodiments described herein. Accordingly, the scope of the present application includes manufacture, machine, manufacture, composition of matter, means, methods and steps described in the specification. The scope of the present disclosure is defined by the appended claims.
Claims (9)
1. A method for detecting copper corrosion, comprising:
providing a multilayer substrate, wherein the multilayer substrate comprises a basal layer, a copper layer and a protective layer, the copper layer is arranged on the basal layer, and the protective layer is arranged on the copper layer;
forming a slit in the multi-layer substrate, wherein the slit penetrates through the protection layer and reaches the copper layer;
forming a photosensitive resin composition on the multilayer substrate, wherein the photosensitive resin composition covers the split and contacts the copper layer;
providing a photomask 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-layered substrate; and
observing the copper corrosion degree of the split, including measuring the width of a color uneven area around the split, if the width of the color uneven area minus the width of the split is greater than or equal to 30 μm, determining that the standard is not met, and if the width of the color uneven area minus the width of the split is less than 30 μm, determining that the standard is met.
2. The method of claim 1, 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.
3. The method of claim 2, wherein the slit has a width of between 30 μm and 100 μm.
4. The method of claim 2, wherein a distance between an edge of the slit and an edge of the opaque region is between 100 μm and 500 μm.
5. The method of claim 1, 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.
6. The method of claim 1, wherein the breach exposes a top surface of the substrate layer.
7. The method of claim 1, wherein the photosensitive resin composition comprises at least one photo-initiator, the at least one photo-initiator is not an oxime (oxime) based photo-initiator, and the solid content of the photo-initiator is not more than 8wt%, wherein the copper corrosion level of the crack observed is determined to be in accordance with a standard.
8. The method of claim 1, wherein the photosensitive resin composition comprises at least one photoinitiator, the at least one photoinitiator being an oxime-based photoinitiator and not comprising a nitro group (-NO) 2 ) Or a thio (-S) structure, and the solid content of the at least one photoinitiator is not greater than 5wt%, wherein the copper corrosion level at which the breach is observed is judged to be in compliance with a standard.
9. The method of claim 1, wherein the photosensitive resin composition comprises at least one photoinitiator, the at least one photoinitiator is an oxime-based photoinitiator and comprises a nitro or thio structure, and the solid content of the at least one photoinitiator is not more than 2.5wt%, wherein the copper corrosion level observed for the crack is determined to be in compliance with a standard.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW109122487 | 2020-07-03 | ||
| TW109122487A TWI765291B (en) | 2020-07-03 | 2020-07-03 | Method for detecting copper corrosion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112881270A CN112881270A (en) | 2021-06-01 |
| CN112881270B true CN112881270B (en) | 2023-09-22 |
Family
ID=76045085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110034401.9A Active CN112881270B (en) | 2020-07-03 | 2021-01-12 | Copper corrosion detection method |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112881270B (en) |
| TW (1) | TWI765291B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019146611A1 (en) * | 2018-01-29 | 2019-08-01 | 富士フイルム株式会社 | Photosensitive resin composition, resin, cured film, laminated body, method for manufacturing cured film, and semiconductor device |
| CN112805317B (en) * | 2018-09-27 | 2023-02-28 | 富士胶片株式会社 | Resin composition, cured film, laminate, method for producing cured film, and semiconductor device |
-
2020
- 2020-07-03 TW TW109122487A patent/TWI765291B/en active
-
2021
- 2021-01-12 CN CN202110034401.9A patent/CN112881270B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202202336A (en) | 2022-01-16 |
| TWI765291B (en) | 2022-05-21 |
| CN112881270A (en) | 2021-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI391783B (en) | Photosensitive resin composition, thin film panel made with photosensitive resin composition, and method for manufacturing thin film panel | |
| JP5481844B2 (en) | Colored photosensitive resin composition | |
| KR101596383B1 (en) | Colored photosensitive resin composition | |
| KR102054030B1 (en) | Resin composition and display apparatus comprising black bank formed by using the same | |
| KR100332326B1 (en) | Radiation-sensitive composition | |
| JPH09145915A (en) | Radiation sensitive composition for color filter | |
| TWI781917B (en) | Resin film, method for producing resin film, optical filter, laminate, solid-state imaging element, image display device, and infrared sensor | |
| KR101974965B1 (en) | Colored photosensitive resin composition | |
| JP2010054561A (en) | Photosensitive composition for protective film and color filter using the same | |
| TW202136438A (en) | Colored curable composition | |
| JP2016166951A (en) | Photosensitive composition | |
| JP2008058551A (en) | Radiation-sensitive composition for colored layer formation and color filter | |
| CN112881270B (en) | Copper corrosion detection method | |
| TWI414539B (en) | Photosensitive resin composition and light blocking layer using the same | |
| TW200540465A (en) | Color filter | |
| US20120270142A1 (en) | Photosensitive composition and method of manufacturing a substrate for a display device using the same | |
| CN106896642B (en) | Photosensitive resin composition, and color photoresist structure and display using the same | |
| JP2021152145A (en) | Colored curable resin composition | |
| TWI790257B (en) | Method for manufacturing pattern, laminate and method for manufacturing touch panel | |
| TWI245164B (en) | Photocurable composition, color filter, and crystal display device | |
| JP7039229B2 (en) | A method for manufacturing a transfer film, a method for forming a resist pattern, and a method for manufacturing a conductive wiring pattern. | |
| JP2019124929A (en) | Negative photosensitive resin composition, and photospacer and image display device including the same | |
| TW201931009A (en) | Photosensitive resin composition, and color resistor structure and display using the same | |
| TWI770994B (en) | Coloring resin composition, method of manufacturing the same, and method of manufacturing photoresist structure | |
| TW202225202A (en) | Coloring resin composition, and photoresist structure, color filter and display device using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |