Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device

Abstract

To provide a photosensitive resin composition that allows marking by a green laser marker, having superior insulation reliability and excellent stability during storage.SOLUTION: The photosensitive resin composition comprises (A) a polyimide precursor represented by the following general formula (A1), (B) a dye, (C) a photosensitizer, and (D) free chlorine, covalently bonded chlorine, Fe element, Ca element, and / or Na element, with the total amount of (D) being from 0.05 to 1000 ppm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a method for producing a cured relief pattern, and a semiconductor device. [Background technology]

[0002] Semiconductor devices (hereinafter sometimes referred to simply as "elements" in this specification) are mounted on printed circuit boards using various methods depending on the purpose. Conventional elements have generally been fabricated using wire bonding, in which thin wires connect the external terminals (pads) of the element to the lead frame. However, as elements have become faster and their operating frequencies have reached GHz, differences in the wiring length of each terminal during mounting have come to affect the operation of the element. Therefore, when mounting elements for high-end applications, it has become necessary to accurately control the length of the mounting wiring. However, it has been difficult to meet this requirement using wire bonding.

[0003] To address this issue, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on top of the rewiring layer, and then the chip is flipped over and mounted directly on a printed circuit board. This flip-chip mounting method allows for precise control of the wiring distance. For this reason, flip-chip mounting is being adopted for high-end devices that handle high-speed signals, and for mobile phones and other devices due to its small mounting size, and demand for this method is rapidly expanding.

[0004] Polyimides, which have excellent heat resistance and electrical properties, have traditionally been used as insulating materials for electronic components, as well as for passivation films, surface protection films, and interlayer insulating films for semiconductor devices. Laser markers equipped with a 532 nm green laser are commonly used to form relief patterns on the surfaces of resins constituting passivation films, surface protection films, and interlayer insulating films, as well as to inscribe characters and marks, such as product specifications, lot numbers, and manufacturing dates, of semiconductor devices onto the surfaces. To form and inscribe desired relief patterns during laser processing, the passivation films, surface protection films, and interlayer insulating films must absorb the laser wavelength.

[0005] Here, a method for coloring a polyimide film to impart appropriate light absorption to the polyimide film is known. For example, Patent Document 1 discloses that a polyimide film is colored by incorporating dyes such as CI Solvent Blue 63, CI Solvent Red 18, and CI Disperse Yellow 201. Furthermore, Patent Document 2 discloses that by incorporating dyes such as OIL GREEN 502 and OIL BLACK BS, it becomes possible to engrave marks using a green laser. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6891880 [Patent Document 2] Patent No. 5501938 Summary of the Invention [Problem to be solved by the invention]

[0007] However, compositions containing the above dyes may have reduced insulation reliability due to metal impurities contained in the dyes, and the dyes may precipitate when such compositions are stored for a long period of time.

[0008] The present invention has been devised in view of the above circumstances. Specifically, an object of the present invention is to provide a photosensitive resin composition that can be marked with a green laser marker, has good insulation reliability, and also has good storage stability. Another object of the present invention is to provide a method for producing a cured relief pattern using such a photosensitive resin composition, and a semiconductor device. [Means for solving the problem]

[0009] One aspect of the present invention is as follows. [1] (A) the following general formula (A1): [ka] (In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are hydrogen atoms, polymerizable groups, or saturated aliphatic groups having 1 to 4 carbon atoms, provided that R1 and R2 are not both hydrogen atoms.) A polyimide precursor represented by the formula: (B) dye; (C) a photosensitizer, and (D) Free chlorine, covalently bound chlorine, Fe element, Ca element, and / or Na element Including, A photosensitive resin composition, wherein the total amount of (D) is 0.05 to 1000 ppm. [2] The photosensitive resin composition according to [1], wherein the total amount of (D) in the composition is 0.05 to 500 ppm. [3] In the general formula (A1), R1 and R2 are each represented by the following general formula (R h ): [ka] (In the formula, R3, R4, and R5 are hydrogen atoms or organic groups having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10.) The photosensitive resin composition according to [1] or [2], which contains a structure represented by the following formula: [4] In the general formula (A1), the X is represented by the following formula (2): [ka] The photosensitive resin composition according to any one of [1] to [3], which contains a structure represented by the following formula: [5] In the general formula (A1), the Y is represented by the following formula (8): [ka] and / or the following formula (9): [ka] The photosensitive resin composition according to any one of [1] to [4], which contains a structure represented by the following formula: [6] The photosensitive resin composition according to any one of [1] to [5], wherein the dye (B) is an anthracene derivative. [7] The photosensitive resin composition according to any one of [1] to [6], further comprising (E) at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), 3-methoxy-N,N-dimethylpropanamide, and ethyl lactate. [8] (1) A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of [1] to [7] onto the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) forming a hardened relief pattern by heat treating the relief pattern; 1. A method for producing a cured relief pattern, comprising: [9] The method for producing a cured relief pattern according to [8], wherein the substrate is formed from copper or a copper alloy.

[10] A semiconductor device having, as an insulating layer, a cured relief pattern obtained from the photosensitive resin composition according to any one of [1] to [7]. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a photosensitive resin composition that can be used to imprint a mark using a green laser marker, that has good insulation reliability due to the presence of a specific amount of free chlorine or a specific metal ion in the composition, and that also has good storage stability, as well as a method for producing a cured relief pattern and a semiconductor device using the same. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described. The present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0012] [Photosensitive resin composition] The photosensitive resin composition of the present embodiment comprises: (A) a polyimide precursor represented by the following general formula (A1): [ka] (In the formula, X is a tetravalent organic group, Y is a divalent organic group, and R1 and R2 are hydrogen atoms, polymerizable groups, or saturated aliphatic groups having 1 to 4 carbon atoms, provided that R1 and R2 are not both hydrogen atoms.) The composition is characterized by comprising (B) a dye, (C) a photosensitizer, and (D) free chlorine, covalently bonded chlorine, Fe element, Ca element, and / or Na element, and the total amount of (D) in the composition is 0.05 to 1000 ppm. According to such a photosensitive resin composition, a mark can be engraved using a green laser marker. In particular, the presence of a specific amount of free chlorine or a specific metal ion in the composition makes it possible to provide a photosensitive resin composition that has good insulation reliability and also good storage stability.

[0013] <Component (A): Polyimide Precursor> The component (A) of this embodiment is a polyimide precursor represented by the above general formula (A1). At least one of R1 and R2 is preferably a polymerizable group. This allows the photosensitizer (C) to act effectively during exposure, and as a result, makes it easier to obtain a cured relief pattern that is excellent in various properties.

[0014] In the general formula (A1), R1 and R2 are each a group represented by the following general formula (R h ): [ka] It is preferable that the compound contains a structure represented by the following formula: {wherein R3, R4, and R5 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p represents an integer of 2 to 10.} This makes it easier to achieve the effects of the present invention.

[0015] <X in the above general formula (A1)> In the general formula (A1), the tetravalent organic group represented by X is, for example, an organic group derived from tetracarboxylic dianhydride, which is a raw material for component (A). Such an organic group is preferably an organic group having 6 to 40 carbon atoms, and more preferably (1) The -COOR1 and -CONH- groups are attached to the same ring; (2) the -COOR1 and -CONH- groups are in the ortho position to each other; In the above (1), the aromatic ring to which the -COOR1 group is bonded and the aromatic ring to which the -COOR2 group is bonded may be the same or different. In this context, the "ring" is preferably a benzene ring. In addition, R1 in the -COOR1 group in this context is preferably a benzene ring. h ) is preferably a monovalent organic group represented by the formula:

[0016] The tetravalent organic group represented by X is particularly preferably a group represented by the following formula: [ka] Examples of the structure include the following: X may be one type or a combination of two or more types.

[0017] In this embodiment, from the viewpoint of exhibiting good film properties, the X is represented by the following formulas (1) to (3): [ka] [ka] [ka] It is preferable that the compound contains at least one structure selected from the group represented by:

[0018] In this embodiment, from the viewpoint of exhibiting good film properties (for example, film elongation), in the component (A), the X is represented by the following formula (2): [ka] It is preferable that the component (A) contains a structure represented by the following formula: In other words, the component (A) preferably contains a structure derived from ODPA (4,4'-oxydiphthalic anhydride).

[0019] At least one of R1 and R2X in the general formula (A1) is h When the monovalent organic group is represented by the general formula (Rh In the formula (I), R3 is preferably a hydrogen atom or a methyl group, and R4 and R5 are each preferably a hydrogen atom from the viewpoint of photosensitivity. Also, from the viewpoint of photosensitivity, p is preferably an integer of 2 or more and 10 or less, more preferably an integer of 2 or more and 4 or less.

[0020] <Y in the above general formula (A1)> In the general formula (A1), the divalent organic group represented by Y is, for example, an organic group derived from the diamine that is the raw material for the component (A). Such an organic group is preferably an aromatic group having 6 to 40 carbon atoms, and is, for example, a group represented by the following formula: [ka] {In the above formula, each A is independently a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), a butyl group (-C4H9), or a trifluoromethyl group (-CF3).} Y may be one type or a combination of two or more types.

[0021] In this embodiment, from the viewpoint of exhibiting good film properties, the above Y is represented by the following general formulas (4) to (7): [ka] [ka] [ka] [ka] It is preferable that the compound contains at least one structure selected from the group represented by the following formula: {In the above formula, each A is independently a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), a butyl group (-C4H9), or a trifluoromethyl group (-CF3).}

[0022] In particular, in this embodiment, from the viewpoint of exhibiting good film properties (for example, film elongation), in the component (A), the above Y is preferably represented by the following formula (8): [ka] and / or the following formula (9): [ka] In other words, the component (A) preferably contains a structure derived from DADPE (4,4'-diaminodiphenyl ether) and / or a structure derived from m-TB (2,2'-dimethyl-4,4'-diaminobiphenyl).

[0023] <Examples of combinations of X and Y in the above general formula (A1)> In this embodiment, in general formula (A1), X is represented by the following formula (2): [ka] and wherein Y is a group represented by the following formula (8): [ka] It is preferable that the copolymer contains a structure represented by the following formula (I): from the viewpoint of further enhancing adhesiveness and exhibiting good film properties.

[0024] In this embodiment, in general formula (A1), X is represented by the following formula (2): [ka] and wherein Y is a group represented by the following formula (9): [ka] And the following formula (10): [ka] It is preferable from the viewpoint of exhibiting good film properties that the polymer contains at least one structure selected from the group represented by the following formula:

[0025] Including the above, examples of combinations of X and Y in this embodiment are as follows. These combinations make it easy to improve various properties of the photosensitive resin composition and / or the cured relief pattern obtained therefrom. The combination of X and Y at a given number and the combination of X and Y at another number may be used in combination. [Table 1-1] [Table 1-2]

[0026] <Physical properties of component (A)> The weight-average molecular weight of component (A) is preferably 1,000 or more, more preferably 5,000 or more, and preferably 100,000 or less, from the viewpoint of the heat resistance and mechanical properties of the polyimide film obtained after heating (curing). From the viewpoint of solubility in organic solvents, the weight-average molecular weight of component (A) is more preferably 50,000 or less. The photosensitive resin composition of this embodiment has photosensitivity. From the viewpoint of achieving both exposure sensitivity, resolution of the pattern obtained after exposure and development, and film properties after heating (curing) of such pattern, the weight-average molecular weight of component (A) is preferably 6,000 or more, 7,000 or more, or 8,000 or more, and preferably 40,000 or less, 30,000 or less, or 22,000 or less. The "weight-average molecular weight" is calculated as a polystyrene-equivalent value by gel permeation chromatography.

[0027] ≪(B) component; dye≫ The photosensitive resin composition of this embodiment contains the above-mentioned component (B). The dye as component (B) is different from a "pigment," which is defined as not interacting with and not soluble in a solvent, in that it dissolves in a solvent (mainly water). Preferred examples of component (B) include organic dyes having a maximum absorption wavelength in the range of 450 to 800 nm.

[0028] Specific examples of component (B) include at least one derivative selected from the group consisting of azines, azomethines, anthracenes, quinacridones, dioxazines, diketopyrrolopyrroles, anthrapyridones, isoindolinones, indanthrones, perinones, perylenes, indigo compounds, thioindigo compounds, quinophthalones, quinolines, and triphenylmethanes. Preferred examples of component (B) include at least one of azine derivatives and anthracene derivatives. These component (B) exhibit high compatibility with component (A), making them preferred for use in terms of storage stability.

[0029] Component (B) is preferably a combination of multiple dyes that satisfy at least one of the following: favorable absorption of wavelengths in the visible range, favorable compatibility with polymers such as component (A), and low scattering properties for laser light. Furthermore, component (B) preferably contains an organic dye that is resistant to fading when exposed to high temperatures during the heating (curing) process of component (A) or the high temperatures experienced during melting due to laser light irradiation, has excellent heat resistance, and favorable absorption of laser light wavelengths. The "laser light" referred to here may be, for example, laser light from a green laser with a wavelength of 532 nm.

[0030] Examples of azine derivatives include black azine condensation mixtures such as those listed in the Color Index as CI Solvent Black 5, CI Solvent Black 7, and CI Acid Black 2. Such azine dye derivatives can be obtained, for example, by oxidizing and dehydrating condensation of aniline, aniline hydrochloride, and nitrobenzene in the presence of iron chloride at a reaction temperature of 160 to 180°C.

[0031] As the anthracene derivative, the anthracene derivatives shown below are particularly preferred because they exhibit good heat resistance and high absorbance at 532 nm: That is, as the anthracene derivative, anthracene oil-soluble dyes are preferred, specifically, CISolvent Blue 11, 12, 13, 14, 26, 35, 36, 44, 45, 48, 49, 58, 59, 63, 68, 69, 70, 78, 79, 83, 87, 90, 94, 97, 98, 101, 102, 104, 105, 122, 129, and 132; CI Disperse Blue 14, 35, 102, and 197; CISolvent Violet 13, 14, 15, 26, 30, 31, 33, 34, 36, 37, 38, 40, 41, 42, 45, 47, 48, 51, 59, and 60; Preferred examples include dyes commercially available under the color indexes CI Disperse Violet 1, 4, 26, and 31.

[0032] As other dyes, the following red dyes are preferred because they have high absorbance at 532 nm. Specifically, preferred examples include commercially available dyes with color indexes of CI Solvent Red 1, 3, 8, 18, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, and 122.

[0033] To easily achieve the effects of the present invention, the content of component (B) is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of component (A). When the content of component (B) is at least the above-mentioned lower limit, marking with a green laser marker is facilitated. When the content of component (B) is at most the above-mentioned upper limit, the physical properties of the resulting polyimide film are likely to be good. The component (B) may be used alone or in combination of two or more types.

[0034] Dyes may be synthesized using coupling reactions with halogen-containing metal catalysts, and may contain large amounts of metals and chlorine. The inventors have found that when the dye contains a large amount of chlorine or metal impurities, the polymer interacts with the chlorine or metal impurities, becoming insoluble and reducing insulation reliability. This is thought to be because the chlorine contained in the resin corrodes metals or makes it easier for current to flow through the metals contained in the resin. Therefore, the dye may need to be purified as needed, but as will be described later, it is not desirable to completely remove chlorine and metal impurities.

[0035] If the dye needs to be purified, it can be purified, for example, by the following method. Specifically, a solution of 3 g of dye in 297 g of γ-butyrolactone (GBL) is washed with ion-exchanged water, and then 200 g of a cation exchange resin (DuPont AMBERLITE HPR1024 H) substituted with GBL and 200 g of anion exchange resin (DuPont AMBERLITE HPR4010 Cl) are added to a flask and treated in a batchwise manner. The batch treatment time can be adjusted depending on the target metal and chlorine content. The purified dye solution is then added dropwise to 5 L of ion-exchanged water, and the precipitated dye is separated, washed, and then vacuum-dried at 50°C for 48 hours to obtain a dye with reduced chlorine and metal elements.

[0036] <Component (C): Photosensitizer> The photosensitizer (C) used in the present invention will now be described. The component (C) is, for example, a photopolymerization initiator for UV curing, and is preferably a photoradical polymerization initiator. The amount of component (C) in the photosensitive resin composition is preferably 1 to 50 parts by mass per 100 parts by mass of component (A). The amount is 1 part by mass or more from the viewpoint of photosensitivity or patterning ability, and 50 parts by mass or less from the viewpoint of curability of the photosensitive resin composition or the physical properties of the cured photosensitive resin layer.

[0037] (Polymerization initiator and photoacid generator) First, the case where the photosensitive resin composition is a negative type will be described. In this case, a photopolymerization initiator and / or a photoacid generator is used as component (C). As the photopolymerization initiator, a photoradical polymerization initiator is preferred, and examples thereof include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal;

[0038] Benzoin, benzoin derivatives such as benzoin methyl ether, oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide are preferred. However, the photopolymerization initiator is not limited to these. Among the above photopolymerization initiators, oximes are more preferred, particularly from the viewpoint of photosensitivity.

[0039] When a photoacid generator is used as component (C), it exhibits acidity upon exposure to actinic rays such as ultraviolet light, and its action crosslinks the crosslinking agent (described below) with the resin (component (A)) or polymerizes crosslinking agents themselves. Examples of photoacid generators include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonates, nitrobenzyl esters, oximesulfonates, aromatic N-oxyimidosulfonates, aromatic sulfamides, haloalkyl-containing hydrocarbon compounds, haloalkyl-containing heterocyclic compounds, and naphthoquinone diazide-4-sulfonates. Two or more of these compounds can be used in combination, or in combination with other sensitizers, as needed. Among the photoacid generators listed above, aromatic oximesulfonates and aromatic N-oxyimidosulfonates are more preferred, particularly in terms of photosensitivity.

[0040] When the photosensitive resin composition is a negative type, the amount of these photosensitizers to be added is 1 to 50 parts by mass per 100 parts by mass of component (A), and from the viewpoint of photosensitivity, it is preferably 2 to 15 parts by mass. By adding 1 part by mass or more of component (C) per 100 parts by mass of component (A), excellent photosensitivity is achieved, and by adding 50 parts by mass or less, excellent thick-film curing properties are achieved.

[0041] The onium salts include iodonium salts, sulfonium salts, phosphinium salts, phosphonium salts, ammonium salts, and diazonium salts, and are preferably onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts.

[0042] Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferred.

[0043] ≪(D) ​​Component≫ The photosensitive resin composition of this embodiment contains, as component (D), free chlorine, covalently bonded chlorine, Fe, Ca, and / or Na, with the total amount being 0.05 to 1000 ppm. While the reasons why the above-described configuration provides excellent storage stability and insulation reliability of the photosensitive resin composition are unclear, the present inventors believe the following: Specifically, when the free chlorine, covalently bonded chlorine, or specific metal element is present in a specific amount or more, the dye can form a stable ion pair or complex in an organic solvent, improving solubility in the organic solvent and resulting in excellent storage stability. Furthermore, when the free chlorine, covalently bonded chlorine, or specific metal element is present in a specific amount or less, aggregates formed by the polymer's interaction with metal impurities or chlorine are prevented from forming, improving solubility in the solvent and resulting in excellent storage stability. Furthermore, for the aforementioned reasons, it is believed that the insulation reliability is also improved. The lower limit of the total amount is preferably 0.10 ppm or more from the viewpoint of ease of ion pair or complex formation. The upper limit of the total amount is preferably 500 ppm or less, more preferably 100 ppm or less, and even more preferably 10 ppm or less from the viewpoint of insulation reliability.

[0044] The photosensitive resin composition of the present embodiment may contain a solvent (E) to dissolve these resins.

[0045] Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, and γ-butyronitrile. Lactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, and the like can be used.

[0046] Among the solvents, those that completely dissolve the resulting polymer and dye are preferred, and examples thereof include N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), 3-methoxy-N,N-dimethylpropanamide, and ethyl lactate.

[0047] The amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of the component (A).

[0048] [Method for producing cured relief pattern] The method for producing a cured relief pattern of this embodiment includes the steps of: (1) forming a resin layer on a substrate by applying the photosensitive resin composition of the present invention onto the substrate; (2) exposing the resin layer to light; (3) developing the exposed resin layer to form a relief pattern; (4) forming a hardened relief pattern by heat treating the relief pattern. A typical embodiment of each step will be described below.

[0049] [(1) Process] In this step, the photosensitive resin composition is applied to a substrate, and then dried as necessary to form a resin layer. The substrate may be made of, for example, copper or a copper alloy. The application method may be a method conventionally used for applying photosensitive resin compositions, such as application using a spin coater, bar coater, blade coater, curtain coater, or screen printer, or spray application using a spray coater.

[0050] As a method for forming a relief pattern using a photosensitive resin composition, not only can the photosensitive resin composition be applied to a substrate to form a resin layer on the substrate, but also the photosensitive resin composition can be formed into a film and the layer of the photosensitive resin composition can be laminated on a substrate to form a resin layer. Alternatively, a film of the photosensitive resin composition according to the present invention can be formed on a supporting substrate, and the supporting substrate can be removed after lamination when using the film, or before lamination.

[0051] If necessary, the coating film made of the photosensitive resin composition can be dried. Drying methods include air drying, heat drying using an oven or a hot plate, vacuum drying, etc. Specifically, when air drying or heat drying is performed, drying can be carried out under conditions of 20°C to 140°C for 1 minute to 1 hour. As described above, a resin layer can be formed on a substrate.

[0052] [(2) Process] In this step, the resin layer formed above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern.

[0053] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as necessary for the purpose of improving photosensitivity, etc. The baking conditions preferably range from 40 to 120°C for a temperature of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition of the present invention.

[0054] In this step, the exposed or unexposed portion of the photosensitive resin layer after exposure is developed and removed. When a negative photosensitive resin composition is used, the unexposed portion is developed and removed. As the development method, any method can be selected from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. Furthermore, after development, post-development baking may be performed at any combination of temperature and time, as necessary, for the purpose of adjusting the shape of the relief pattern, etc.

[0055] The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that is insoluble in an alkaline aqueous solution, good solvents such as N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, GBL, and α-acetyl-γ-butyrolactone are preferred, while poor solvents such as toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, and propylene glycol methyl ether acetate are preferred. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Furthermore, two or more types of each solvent, for example, several types, can be used in combination.

[0056] [(4) Process] In this step, the relief pattern obtained by the development is heated to convert it into a hardened relief pattern. Various methods can be selected for heat curing, such as using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 180°C to 400°C for 30 minutes to 5 hours. The atmospheric gas used for heat curing may be air, or an inert gas such as nitrogen or argon.

[0057] [Semiconductor Devices] The semiconductor device of this embodiment includes a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention.

[0058] One aspect of this embodiment is a semiconductor device including a substrate that is a semiconductor element, and a cured relief pattern of resin formed on the substrate by the above-described method for producing a cured relief pattern.

[0059] This embodiment can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern as part of its steps. In this embodiment, the cured relief pattern formed by the above-described method for manufacturing a cured relief pattern is formed as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and can be manufactured by combining this with a known method for manufacturing a semiconductor device.

[0060] In addition to application to the semiconductor devices described above, the photosensitive resin composition is also useful for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. [Example]

[0061] The present embodiment will be described in detail below with reference to examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the polymer or negative-type photosensitive resin composition were measured and evaluated according to the following methods.

[0062] [Weight average molecular weight] The weight-average molecular weight (Mw) of each resin was measured by GPC (standard polystyrene equivalent). The column used was a "Shodex 805M / 806M series" column manufactured by Showa Denko K.K. The standard monodisperse polystyrene was "Shodex STANDARD SM-105" manufactured by Showa Denko K.K. The developing solvent was NMP, and the detector was "Shodex RI-930" manufactured by Showa Denko K.K.

[0063] [Measurement of free chlorine content of resin composition] After preparing the photosensitive resin composition, it was left to stand at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%) for 3 days, and then the amount of free chlorine in the resin composition was measured. The ion concentration was measured at 23.0°C using a ThermoFicher ICS-3000. Based on the measurement results, the content of chlorine ions in the resin composition was calculated under the following measurement conditions. 2 g of the photosensitive resin composition was weighed out and added to 4 mL of NMP, which was stirred for 10 minutes on a shaker to dissolve. 30 mL of ion-exchanged water was then added, and the mixture was stirred for 10 minutes on a shaker. The insoluble matter was removed using a centrifuge (CF15RN, manufactured by Himac), and the resulting mixture was filtered through a disc filter (JP050AN, manufactured by DISMIC) before use. 1 mL of the treated sample solution was automatically inserted into the column using an autosampler. Guard column for anion analysis: IonPac AS4A-SC (4mm x 250mm) Guard column pump flow rate: 0.500 mL / min Separation column for anion analysis: IonPac AS4A-SZ (4mm x 50mm) Sample introduction line pump flow rate: 0.500 mL / min Anion Chemical Suppressor: ACRS-500 (for 4mm)

[0064] [Measurement of total chlorine content in resin composition] After preparing the photosensitive resin composition, it was left to stand at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%) for three days, after which the total chlorine content (the sum of free chlorine and covalently bound chlorine) of the resin composition was measured. The photosensitive resin composition was combusted and decomposed at 800°C, and the decomposition gas was absorbed in ultrapure water. The total chlorine content in the resin composition was determined by ion chromatography. The ion chromatography consisted of a Dionex IC-1000 and an IonPac AS12A (4 mm) column. The eluent was a 0.3 mM NaHCO3 / 2.7 mM Na2CO3 aqueous solution, and measurements were performed at a flow rate of 1.5 mL / min.

[0065] [Measurement of Metal Element Amount in Resin Composition] After preparing the photosensitive resin composition, it was left to stand at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%) for 3 days, and then the amount of metal elements in the resin composition was measured. The measurement was carried out at 23.0°C using an iCAP6500 or iCAP7400 manufactured by ThermoFicher Scientific Inc. Based on the measurement results, the amount of metal elements in the resin composition was determined under the following measurement conditions. 4 g of the photosensitive resin composition was weighed into a crucible and heated stepwise (up to 300°C) on a hot plate to remove the solvent (carbonization). It was then placed in a muffle furnace and heat-treated (up to 500°C) to incinerate it. 1 mL of high-purity hydrochloric acid (500 gr TAMAPURU-AA-100, 30% concentration) was added, and the mixture was heated on a hot plate at 80°C for 15 minutes. Then, 4 mL of high-purity nitric acid (500 gr TAMAPURU-AA-100, 68% concentration) was added. The liquid in the crucible was transferred to a syringe and passed through a disc filter (DISMIC JP050AN) to prepare a weighed sample. The treated sample solution was automatically inserted into a column using an autosampler.

[0066] [Stability test] The photosensitive resin compositions prepared above were stored in a freezer at -10°C for two months, and those in which the varnish had solidified were classified as "D," those in which the varnish had gelled but not solidified were classified as "C," those in which the varnish had become cloudy but neither solidified nor gelled were classified as "B," and those in which neither solidified, gelled, nor became cloudy were classified as "A." In stability test results, a rank of C or higher is considered to be good for practical use.

[0067] [Insulation reliability test] The sample preparation method and evaluation method for the insulation reliability test will be explained. <Sample preparation method> The photosensitive resin laminate with a 25 μm-thick photosensitive resin layer prepared above was laminated onto the conductor of a flexible copper-clad laminate (ESPANEX: MC12-25-00HRM, product name of Nippon Steel Chemical & Materials) on which a comb-shaped wiring for ion migration evaluation had been patterned with a length / space of 50 μm / 50 μm. While peeling off the protective film, the laminate was laminated using a roll-type thermal vacuum laminator (MCK Corporation, MVR-250) to obtain a three-layer laminate consisting of, from top to bottom, temporary support film / photosensitive resin layer / flexible copper-clad laminate (lamination conditions were a roll temperature of 80°C, an air pressure of 0.4 MPa, a degree of vacuum of 100 Pa, and a speed of 2.0 m / min).

[0068] After leaving it to stand for 15 minutes, a PET mask and a Stoufer 21-step step tablet (the first step is optical density 0.00, and each step increases the optical density by 0.15) were placed side by side on the support film, and the optimal exposure amount (defined as in 2. Developability Evaluation) for each composition was determined from the PET mask and step tablet side, and the film was exposed using a parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.). The PET mask used had a pattern in which the unexposed areas were circular holes.

[0069] After leaving the sample to stand for 15 minutes or more, the temporary support was peeled off, and the sample was developed using a Fuji Kiko Co., Ltd. developing device. A 1% by mass Na2CO3 aqueous solution at 30°C was sprayed at a developer spray pressure of 0.12 MPa using a full-cone nozzle for a development time twice the time required for the photosensitive resin film layer to completely dissolve (the breakpoint), dissolving and removing the unexposed portions of the photosensitive resin layer. A water washing step was then performed using a flat nozzle at a water washing spray pressure of 0.06 MPa for the same time as the development step, and the washed sample was dried by air blowing. Then, a scattered light exposure machine was used to spray 3000 mJ / cm2 from the photosensitive layer side. 2 After exposure, the film was heated in a hot air circulating oven at 150° C. for 60 minutes to be cured, thereby obtaining a laminate for a flexible printed wiring board.

[0070] Subsequently, an electromagnetic wave shielding film (SF-PC5600-C, manufactured by Tatsuta Electric Wire Co., Ltd.) was positioned so that it would be partially connected to the cathode side electrode of the photosensitive resin layer of the flexible printed wiring board, and laminated using a vacuum press (manufactured by Kitagawa Seiki) under conditions of 170°C, 3 MPa, and 5 minutes. After that, it was heated in a hot air circulating oven under conditions of 150°C and 60 minutes to be cured.

[0071] <Evaluation method> The insulation resistance of the printed wiring board with the electromagnetic field shielding film produced by the above method was measured using the following equipment and conditions, and the insulation reliability was evaluated by checking the time until the insulation resistance value decreased. A voltage of 50 VDC was applied to the printed wiring board continuously for 1000 hours under the conditions described below using the following equipment. Ion migration device: AMI-050-U-5 (manufactured by Espec Corporation) Constant temperature and humidity oven: PR-2KT (manufactured by Espec Corporation) Temperature and humidity conditions: 85°C / 85%RH Voltage: 50VDC

[0072] The results of the insulation reliability test were judged as follows. A: The time until the insulation resistance value changes is 500 hours or more. B: The time until the insulation resistance value changes is 250 hours or more but less than 500 hours C: The time until the insulation resistance value changes is 100 hours or more but less than 250 hours D: The time until the insulation resistance value changes is less than 100 hours In the insulation reliability test, a result of C rank or higher is considered to be good for practical use.

[0073] [(A) component; Production examples 1 to 4] <Production Example 1> (Polyimide precursor (Polymer A-1)) 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of GBL were added, and the mixture was stirred at room temperature. 79.1 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had subsided, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0074] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of GBL was added to the reaction mixture over 40 minutes with stirring, followed by the addition of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 mL of GBL over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 400 mL of GBL. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0075] The resulting reaction solution was added to 3 L of ethyl alcohol, producing a precipitate consisting of a crude polymer. The resulting crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the resulting precipitate was filtered off and vacuum dried to obtain a powdered polymer (Polymer A-1). The weight-average molecular weight (Mw) of Polymer A-1 was 20,000.

[0076] <Production Example 2> (Polyimide precursor (Polymer A-2)) Polymer A-2 was obtained by carrying out a reaction in the same manner as in Production Example 1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The weight average molecular weight (Mw) of Polymer A-2 was 22,000.

[0077] <Production Example 3> (Polyimide precursor (Polymer A-3)) Polymer A-3 was obtained in the same manner as in Production Example 1, except that 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (190.7 g) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example 1. The weight average molecular weight (Mw) of Polymer A-3 was 21,000.

[0078] <Production Example 4> (Polyimide precursor (Polymer A-4)) Polymer A-4 was obtained in the same manner as in Production Example 1, except that 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) (98.6 g) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example 1. The weight average molecular weight (Mw) of Polymer A-4 was 21,000.

[0079] [Examples 1 to 13 and Comparative Examples 1 to 4] Example 1 Negative-tone photosensitive resin compositions were prepared using polymers A-1 and A-2 by the following method, and the photosensitive resin compositions were evaluated. 60 g of polymer A-1, 40 g of polymer A-2, 4 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 2), 8 g of tetraethylene glycol dimethacrylate, 3 g of Solvent Black 7 (component B), 1.5 g of N-[3-(triethoxysilyl)propyl]phthalamic acid (component C), and 0.1 g of iron oxide (component D) were added and dissolved in a mixed solvent consisting of NMP (80 g) and ethyl lactate (20 g) (E). The viscosity of the resulting solution was adjusted to approximately 35 poise by further adding a small amount of the mixed solvent, yielding a negative-tone photosensitive resin composition. The amount of free chlorine and the amount of covalently bonded chlorine in the photosensitive resin composition, the amount of free chlorine, the amount of metal elements, the storage stability, and the insulating property were evaluated according to the methods described above. The results are shown in Table 3.

[0080] <Examples 2 to 13 and Comparative Examples 1 to 4> Photosensitive resin compositions were prepared by dissolving in a solvent and adjusting the viscosity in the same manner as in Example 1, except that the compounding ratios shown in Table 2 were used according to the method described above. The amounts of free chlorine, covalently bonded chlorine, and free chlorine, as well as the amounts of metal elements, in the photosensitive resin compositions were then evaluated according to the methods described above, and stability evaluations and insulation reliability tests were conducted. The results are shown in Table 3.

[0081] Each number in the table below represents the following compound.

[0082] (B) Component; Dye In purifying the dye, 200 g of a cation exchange resin (AMBERLITE HPR1024 H manufactured by DuPont) and 200 g of an anion exchange resin (AMBERLITE HPR4010 Cl manufactured by DuPont) were used, and the purification time indicates the processing time in a batch system.

[0083] B-1: Solvent Black 7 [ka] The purification process is classified as follows: B-1-1: Solvent Black 7 purified with cation and anion exchange resin for 5 hours B-1-2: Solvent Black 7 purified with cation and anion exchange resin for 2 hours B-1-3: Solvent Black 7 purified with anion exchange resin for 1 hour B-1-4: Solvent Black 7 purified with anion exchange resin for 30 minutes B-1-5: Solvent Black 7 purified with anion exchange resin for 2 days B-1-6: Solvent Black 7 not purified with cation and anion exchange resins

[0084] B-2: Disperse Violet 26 [ka] The purification process is classified as follows: B-2-1: Disperse Violet 26 purified with cation-anion exchange resin for 5 hours B-2-2: Disperse Violet 26 purified with cation-anion exchange resin for 1 hour B-2-3: Disperse Violet 26 purified with cation and anion exchange resin for 2 days B-2-4: Disperse Violet 26 not purified with cation-anion exchange resin

[0085] B-3: Solvent Red 24 purified with cation-anion exchange resin for 5 hours [ka]

[0086] B-4: Solvent Black 3 purified with cation and anion exchange resin for 5 hours [ka]

[0087] B-5: Solvent Green 3 purified with cation-anion exchange resin for 5 hours [ka]

[0088] (C) Component: Photosensitizer C-1: Photopolymerization initiator represented by the following formula [ka]

[0089] (D) Component: Solvent D-1: N-methyl-2-pyrrolidone (NMP) D-2: Ethyl lactate D-3: γ-butyrolactone (GBL) D-4: Dimethyl sulfoxide (DMSO)

[0090] [Table 2]

[0091] [Table 3]

[0092] As is clear from Tables 2 and 3, in Examples 1 to 13 in which the total amount of free chlorine, covalent chlorine, Fe element, Ca element, and / or Na element as component (D) was 0.05 to 1000 ppm, higher storage stability and insulating reliability were obtained compared to Comparative Examples 1 to 4 in which the total amount of component (D) was less than 0.05 or more than 1000 ppm. [Industrial Applicability]

[0093] The photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials that are useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) The following general formula (A1): 【Chemical 1】 (wherein X is a tetravalent organic group, Y is a divalent organic group, and R １ and R ２ is a hydrogen atom, a polymerizable group, or a saturated aliphatic group having 1 to 4 carbon atoms. １ and R ２ is not a hydrogen atom at the same time.) A polyimide precursor represented by the formula: (B) dye; (C) a photosensitizer, and (D) Free chlorine, covalently bonded chlorine, Fe element, Ca element, and / or Na element Including, A photosensitive resin composition, characterized in that the total amount of (D) is 0.05 to 1000 ppm.

2. 2. The photosensitive resin composition according to claim 1, wherein the total amount of (D) in the composition is 0.05 to 500 ppm.

3. In the general formula (A1), the R １ and R ２ is represented by the following general formula (R ｈ ): 【Chemistry 2】 (In the formula, R ３ , R ４ and R ５ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10. The photosensitive resin composition according to claim 1, comprising a structure represented by the following formula:

4. In the general formula (A1), the X is represented by the following formula (2): 【Chemistry 3】 The photosensitive resin composition according to claim 1, comprising a structure represented by the following formula:

5. In the general formula (A1), the Y is represented by the following formula (8): 【Chemistry 4】 and / or the following formula (9): 【Chemistry 5】 The photosensitive resin composition according to claim 1, comprising a structure represented by the following formula:

6. 2. The photosensitive resin composition according to claim 1, wherein the dye (B) is an anthracene derivative.

7. 2. The photosensitive resin composition according to claim 1, further comprising (E) at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), 3-methoxy-N,N-dimethylpropanamide, and ethyl lactate.

8. (1) forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of claims 1 to 7 onto the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) forming a hardened relief pattern by heat-treating the relief pattern; 1. A method for producing a cured relief pattern, comprising:

9. The method for producing a cured relief pattern according to claim 8 , wherein the substrate is formed from copper or a copper alloy.

10. A semiconductor device having, as an insulating layer, a cured relief pattern obtained from the photosensitive resin composition according to any one of claims 1 to 7.

Images