JP6212861B2 - Manufacturing method of semiconductor device - Google Patents

Description

  The present invention relates to a method for manufacturing a semiconductor device.

  Conventionally, a polyimide resin film, a polybenzoxazole resin film, and the like having both excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for a surface protective film and an interlayer insulating film of a semiconductor device (for example, Patent Document 1). These polyimide resin films and polybenzoxazole resin films can be formed of a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor.

  In recent years, electronic devices such as digital cameras and mobile phones have been rapidly reduced in size, thickness, and weight. Along with this, semiconductor devices have also been reduced in size and density. A packaging method called CSP (chip size package) has been widely used as a semiconductor device corresponding to such downsizing and high density. In general, a CSP has a wiring pattern as a rewiring, an interlayer insulating layer, a conductive ball for external connection, etc. on a silicon wafer.

International Publication No. 2009/022732 Pamphlet

  However, if the main component of rewiring is copper, a patterned resin film obtained by applying, exposing, and developing a photosensitive resin composition on the rewiring, or a cured pattern film obtained by curing the resin film is formed. In this case, there is a problem that a residue is generated in the pattern opening. Further, there is a problem that the residue generated in the pattern opening on the rewiring cannot be easily removed by an etching agent or plasma treatment.

  Further, the conventional rewiring has a problem that peeling occurs between the insulating layer and the rewiring, and the adhesiveness is insufficient.

  An object of the present invention is to provide a semiconductor device that reduces residue generated in a pattern opening of a pattern resin film (insulating film) and has excellent adhesion between a rewiring and an insulating layer. Another object of the present invention is to provide a method of manufacturing a semiconductor device that can reduce the occurrence of residue in the pattern opening of the pattern resin film and can sufficiently secure the adhesion between the rewiring and the insulating layer. It is to be.

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す。）
５．前記絶縁層が、下記式（２）で表されるポリベンゾオキサゾール前駆体を含む樹脂組成物を加熱硬化して得られたものである１〜４のいずれかに記載の半導体装置。

（式中、Ｕは４価の有機基を示し、Ｒ^１及びＲ^２は各々独立に１価の有機基を示す。ｎは６〜２０の整数を示す。）
６．再配線を有する基板を１４０〜１６０℃で加熱して前記再配線上に酸化銅層を形成する工程と、前記酸化銅層の上に、ポリベンゾオキサゾールを含む絶縁層を形成する工程とを含む半導体装置の製造方法。
７．前記酸化銅層を形成する工程の前に、前記再配線を酸により洗浄して酸化皮膜を除去する工程を含む６に記載の半導体装置の製造方法。
８．前記酸化銅を形成する工程における加熱時間が１〜５分である６又は７に記載の半導体装置の製造方法。 The present inventors have studied in detail to reduce the generation of residues and improve the adhesiveness.
First, a technique for forming a copper oxide layer on the rewiring was studied by making use of the knowledge disclosed in Japanese Patent Laid-Open No. 5-198562. However, even when a copper oxide layer is formed on the rewiring, there is room for improvement in terms of sufficiently reducing the occurrence of residue in the pattern opening while improving the adhesion between the rewiring and the insulating layer. There was found.
As a result of various investigations on the state of the formation process of the copper oxide layer in order to investigate the cause of the above phenomenon, the present inventors have found that the thickness of the formed copper oxide layer affects the adhesion and the generation of residues. I found out. Therefore, it was inferred from the knowledge so far that if the thickness of the copper oxide layer is 35 nm or less, the generation of residues can be sufficiently reduced and the adhesiveness can be improved.
However, as a result of investigation, it has been found that even if the thickness of the formed copper oxide layer is 35 nm or less, the above problem may not be solved if the thickness is too thin.
Thus, as a result of re-examination, it was found that by forming copper oxide having a specific thickness on the rewiring, the adhesion between the rewiring and the insulating layer can be improved, and the residue of the pattern opening can be reduced. Was completed.
According to the present invention, the following semiconductor devices and the like are provided.
1. A semiconductor device including a substrate having rewiring and an insulating layer containing polybenzoxazole on the rewiring, wherein the copper oxide layer is obtained by Auger spectroscopy, including a copper oxide layer on a surface of the rewiring A semiconductor device having an average thickness of 3 to 35 nm.
2. 2. The semiconductor device according to 1, wherein the copper oxide layer has an average thickness of 3 to 20 nm.
3. 3. The semiconductor device according to 1 or 2, wherein a main component of the rewiring is copper.
4). The semiconductor device according to any one of 1 to 3, wherein the insulating layer is obtained by heat curing a resin composition containing a polybenzoxazole precursor represented by the following formula (1).

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)
5. The semiconductor device according to any one of 1 to 4, wherein the insulating layer is obtained by heat curing a resin composition containing a polybenzoxazole precursor represented by the following formula (2).

(In the formula, U represents a tetravalent organic group, R ¹ and R ² each independently represent a monovalent organic group, and n represents an integer of 6 to 20.)
6). Heating a substrate having rewiring at 140 to 160 ° C. to form a copper oxide layer on the rewiring, and forming an insulating layer containing polybenzoxazole on the copper oxide layer. A method for manufacturing a semiconductor device.
7). 7. The method of manufacturing a semiconductor device according to 6, further comprising a step of removing the oxide film by washing the rewiring with an acid before the step of forming the copper oxide layer.
8). The manufacturing method of the semiconductor device of 6 or 7 whose heating time in the process of forming the said copper oxide is 1 to 5 minutes.

  ADVANTAGE OF THE INVENTION According to this invention, the residue which generate | occur | produces in the pattern opening part of a pattern resin film (insulating film) can be reduced, and the semiconductor device excellent in the adhesiveness of rewiring and an insulating layer can be provided. In addition, according to the present invention, there is provided a method for manufacturing a semiconductor device that can reduce the generation of residues in the pattern opening of the pattern resin film and can sufficiently secure the adhesiveness between the rewiring and the insulating layer. it can.

It is a figure which shows the relationship between oxygen concentration and copper oxide layer average thickness used in Auger electron spectroscopy measurement. It is sectional drawing which shows the outline | summary of the semiconductor device which is one Embodiment of this invention. It is sectional drawing which shows the outline | summary of the semiconductor device of the multilayer wiring structure which is one Embodiment of this invention.

  Hereinafter, an embodiment of a semiconductor device and a manufacturing method thereof according to the present invention will be described in detail. The present invention is not limited to the following embodiments.

[Semiconductor device]
The semiconductor device of the present invention includes a substrate having rewiring and an insulating layer containing polybenzoxazole on (above) the rewiring. Further, a copper oxide layer is formed on the surface of the rewiring, and the average thickness of the copper oxide layer is 3 to 35 nm.

By combining a copper oxide layer having an average thickness of 3 to 35 nm and an insulating layer containing polybenzoxazole, generation of residues in the pattern opening of the patterned resin film or the cured pattern film (insulating film) is reduced. In addition, sufficient adhesion between the rewiring and the insulating layer can be ensured. It is considered that the generation of residues can be reduced by suppressing the reaction between the structure of the photosensitizer and the rewiring (for example, carboxyl group and copper in the photosensitizer structure) by the copper oxide layer having an appropriate thickness. Moreover, it is thought that the adhesiveness of rewiring and an insulating layer can fully be ensured because a copper oxide layer reacts with another component (for example, adhesion aid).
In addition, if it is copper oxide of said thickness, the electrical continuity at the time of the connection with the exterior will not be prevented.

  Although there is no particular limitation on the rewiring used in the present invention, in general, the rewiring is one of the semiconductor package types, in the wafer level chip size package (wafer level CSP) technology, on the wafer level CSP chip. It is formed from the electrodes to solder bumps (conductive balls) arranged on the package surface. By rewiring, a small semiconductor package close to the size of the chip can be obtained without being limited by the arrangement of the element electrodes arranged at a narrow pitch on the semiconductor chip.

The rewiring is preferably based on copper. “Containing copper as a main component” means that the content of copper in the rewiring is 80% or more, preferably 90% or more as an element, or 100% which may contain inevitable impurities. The rewiring mainly composed of copper can be formed on the substrate on which the device is formed by a known method such as electrolytic plating, electroless plating, sputtering, or vacuum deposition. The rewiring may be formed in a pattern on the substrate, or may be formed on the entire surface of the substrate.
The thickness of the rewiring is not particularly limited, but is preferably 15 μm or less, more preferably 10 μm or less, and further preferably 6 μm or less. The lower limit of the rewiring thickness is not particularly limited, but is preferably 0.01 μm or more.

The copper oxide layer is formed on the surface of the rewiring and has an average thickness of 3 to 35 nm. Generation | occurrence | production of a residue can be reduced as average thickness is 3 nm or more, and adhesiveness can be made favorable as it is 35 nm or less.
The average thickness of the copper oxide layer is more preferably 3 to 30 nm, further preferably 3 to 20 nm, particularly preferably 3 to 15 nm, and most preferably 5 to 15 nm.

The average thickness of the copper oxide layer is determined by Auger electron spectroscopy (AES). Specifically, a substrate having a rewiring formed with copper oxide is introduced into an AES analyzer (for example, SAM-670 (PHI, FE type)). The measurement is performed under the following conditions.
Electron beam: 5 kV, 10 nA Beam size = 0.05 μm
Ion beam: Ar, 3 kV, sputtering rate = 4.6 nm / min (in the case of SiO ₂ )
Measurement location: A range of 150 μm × 150 μm is analyzed on the surface.

Specifically, the measurement location is analyzed in the depth direction while ion sputtering is performed, and the components Cu, O, and C are analyzed, and converted from the concentration [atomic%], the sputter depth [nm], and the sputtering rate to oxidize. Obtain the average copper thickness.
In the copper oxide layer, the oxygen concentration usually decreases gradually from the surface toward the inside in the thickness direction. In the present invention, the thickness from the surface when the oxygen concentration is 10% is defined as the average thickness of the copper oxide layer.
An example of a schematic diagram of a plot obtained by AES measurement is shown in FIG. In this case, since the thickness (Sputter Depth) when the oxygen concentration is 10% is 3.3 nm, the average thickness of the copper oxide layer is 3.3 nm.

The insulating layer preferably contains a polybenzoxazole and is formed by heat curing a photosensitive resin composition containing a polybenzoxazole precursor described later.
Although there is no restriction | limiting in particular in the thickness of an insulating layer, It is preferable that it is 1-15 micrometers from a viewpoint of applicability | painting, It is more preferable that it is 2-10 micrometers, It is further more preferable that it is 3-7 micrometers.

  Next, an example of the semiconductor device of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following description.

FIG. 2 shows a cross-sectional structure of an example of the semiconductor device of the present invention.
An integrated circuit (not shown) is provided on the silicon substrate 10, and connection pads 11 made of an aluminum-based metal are formed so as to be connected to the integrated circuit. An insulating layer 20 and a surface protective film layer 30 are provided thereon, and a rewiring 40 is formed on the exposed pad 11 portion.

  A copper oxide layer 41 is formed on the surface of the rewiring 40, and an insulating layer 50 is formed thereon. A connection pad and a barrier metal are formed in an opening provided in the insulating layer 50, and a solder ball (conductive ball) 60 is provided.

  FIG. 3 shows a cross-sectional structure of another example of the semiconductor device of the present invention. This semiconductor device has a multilayer wiring structure. An Al wiring layer 102 is formed on the interlayer insulating layer 101, an insulating layer 103 (for example, a P-SiN layer) is further formed thereon, and a surface protective film layer 104 of the element is further formed. A rewiring 106 is formed from the pad portion 105 of the Al wiring layer 102. On the surface of the rewiring 106, a copper oxide layer 106a is formed. The copper oxide layer 106a extends to the upper part of the core 108 which is a connection portion with the conductive ball 107 formed of solder, gold or the like as an external connection terminal. Further, an insulating layer 109 is formed on the surface protective film layer 104.

  The rewiring 106 is connected to the conductive ball 107 through the barrier metal 110, and a collar 111 is provided to hold the conductive ball 107. An underfill 112 is provided in order to relieve stress when the package having such a structure is mounted.

  The semiconductor device of the present invention shown in FIGS. 2 and 3 is not particularly limited except that it has a rewiring, a copper oxide layer, and an insulating layer, and can have various structures.

  The insulating layer used in the present invention is preferably formed by heat curing a photosensitive resin composition containing a polybenzoxazole precursor. By forming in this way, it is excellent in heat resistance, mechanical properties, and electrical properties.

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す。）
式（１）におけるヒドロキシ基を含有するアミドユニットは、硬化時の脱水閉環により、最終的には耐熱性、機械特性、電気特性に優れるオキサゾール体に変換される。 [Photosensitive resin composition]
Hereinafter, each component of the photosensitive resin composition which can be used for this invention is demonstrated.
(1) Polybenzoxazole precursor The polybenzoxazole precursor (polyhydroxyamide) is preferably represented by the following formula (1).

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)
The amide unit containing a hydroxy group in formula (1) is finally converted into an oxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration and ring closure during curing.

（式中、Ｕは４価の有機基を示し、Ｖ及びＷは各々独立に２価の有機基を示す。ｊ及びｋは各々独立にモル分率を示す。ｊとｋの和は１００モル％であり、ｊは６０〜１００モル％、ｋは４０〜０モル％である。） The polybenzoxazole precursor only needs to have the structural unit represented by the above formula (1), but may contain other structural units. Examples of such a polybenzoxazole precursor include a polybenzoxazole precursor having a structural unit represented by the following formula (4).

(In the formula, U represents a tetravalent organic group, V and W each independently represent a divalent organic group. J and k each independently represents a mole fraction. The sum of j and k is 100 mol.) %, J is 60 to 100 mol%, and k is 40 to 0 mol%.)

  Since the solubility of the polyhydroxyamide in the aqueous alkali solution is derived from the phenolic hydroxyl group, it is preferable that the hydroxy group-containing amide unit in the above formula (4) contains a certain amount or more. That is, the molar fraction of j and k in formula (4) is preferably j = 80 to 100 mol% and k = 20 to 0 mol%.

The polybenzoxazole precursors described above, that is, polyhydroxyamides having one type of structural unit or two or more types of structural units are generally dicarboxylic acid derivatives, hydroxy group-containing diamines, and other than these as required. It can be synthesized from diamines.
Specifically, it can be synthesized by reacting with a diamine after converting a dicarboxylic acid derivative into a dihalide derivative. As the dihalide derivative, a dichloride derivative is preferable.

  The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorideation reaction of carboxylic acid can be used.

As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, or reacting in an excess halogenating agent and then distilling off the excess.
As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

The amount of these halogenating agents used is preferably 1.5 to 3.0 mol and more preferably 1.7 to 2.5 mol with respect to 1 mol of the dicarboxylic acid derivative when reacted in a solvent. When making it react in a halogenating agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable.
The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

The reaction between the dichloride derivative and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent.
As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used.
As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used.
The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

In the formulas (1) and (4), the tetravalent organic group represented by U is preferably a tetravalent aromatic group (a group containing an aromatic ring), preferably having 6 to 40 carbon atoms, A tetravalent aromatic group having 6 to 40 carbon atoms is more preferable. As the tetravalent aromatic group, those in which all four bonding sites are present on the aromatic ring are preferable.
In addition, since the tetravalent organic group represented by U is a polybenzoxazole precursor, in general, each of two hydroxy groups and two amino groups that react with a dicarboxylic acid to form a polyamide structure. It is a residue of a diamine that has two sets of structures having an hydroxy group and an amino group located in the ortho position on an aromatic ring.

  Such diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane. Bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-) 4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3- Although hexafluoropropane etc. are mentioned, it is not limited to these. These compounds can be used alone or in combination of two or more.

As described above, the polybenzoxazole precursor used in the present invention may have a structural unit other than the structural unit represented by the formula (1) (for example, the formula (4)).
In this case, the following diamines can be used. For example, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) And aromatic diamine compounds such as 1,4-bis (4-aminophenoxy) benzene.
In addition to these, diamines containing silicone groups include LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, and X-22-161E ( Any of these include, but are not limited to, Shin-Etsu Chemical Co., Ltd., trade name).
These compounds can be used alone or in combination of two or more.

In the formulas (1) and (4), the divalent organic group represented by V is a residue of dicarboxylic acid that reacts with diamine to form a polyamide structure, and the heat resistance and mechanical properties of the cured film. In view of the above, a divalent aromatic group having 6 to 40 carbon atoms, a divalent organic group having an aliphatic straight chain structure having 6 to 30 carbon atoms, or a divalent organic containing an aromatic group and an aliphatic group It is preferably a group.
As the divalent aromatic group, those in which two bonding sites are both present on the aromatic ring are preferred.
In addition, from the viewpoint of further suppressing the residue of the pattern opening, V is a bivalent aromatic group having 6 to 40 carbon atoms or an aliphatic straight chain structure having 6 to 30 carbon atoms including two or more aromatic rings. It is preferable that it is a divalent organic group. Furthermore, even if the temperature at the time of thermosetting is lowered to 280 ° C. or lower, V has an aliphatic linear structure having 6 to 30 carbon atoms from the viewpoint of sufficiently obtaining heat resistance and mechanical properties of the cured film. A valent organic group is preferred.

（式中、Ｚは各々独立に炭素数１〜６の炭化水素基であり、ｎは１〜６の整数である。） Examples of such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid Aromatic dicarboxylic acids such as 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, And dicarboxylic acids having an alicyclic structure such as 1,3-cyclopentanedicarboxylic acid, As those having an aliphatic straight chain structure, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2- Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimerin Acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid Acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid And dicarboxylic acid represented by the following formula (5). However, it is not limited to these. These compounds can be used alone or in combination of two or more.

(In the formula, each Z is independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6)

（式中、Ｕは４価の有機基を示し、Ｒ^１及びＲ^２は各々独立に１価の有機基を示す。ｎは６〜２０の整数を示す。）
Ｒ^１、Ｒ^２の有機基としては、水素、炭素数１〜６の脂肪族基（例えば、メチル基、エチル基、プロピル基、ブチル基等）等が挙げられる。Ｒ^１及びＲ^２が水素であることが好ましい。 Further, the polybenzoxazole precursor used in the present invention is preferably represented by the following formula from the viewpoint of further suppressing the residue of the pattern opening, and from the viewpoint of improving the heat resistance and mechanical properties of the formed insulating film. It is represented by (2).

(In the formula, U represents a tetravalent organic group, R ¹ and R ² each independently represent a monovalent organic group, and n represents an integer of 6 to 20.)
Examples of the organic group for R ¹ and R ² include hydrogen and an aliphatic group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and the like). R ¹ and R ² are preferably hydrogen.

  The molecular weight of the polybenzoxazole precursor used in the present invention is preferably 3,000 to 200,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight. The molecular weight is determined by gel permeation chromatography and converted from a standard polystyrene calibration curve.

(2) Compound that generates acid upon irradiation with light The photosensitive resin composition described above may contain a compound that generates acid upon irradiation with light (hereinafter also referred to as a photoacid generator). Good. The photoacid generator has a function of increasing the solubility of the light irradiation part in an alkaline aqueous solution.
Examples of the photoacid generator include diazonaphthoquinone, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. Among them, diazonaphthoquinone is preferable because it has high sensitivity.

Diazonaphthoquinone can be obtained, for example, by subjecting o-quinonediazide sulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent.
Examples of o-quinonediazidosulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride, and the like. Can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro- 1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1- ] Indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) hexafluo Propane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like can be used.

  The o-quinonediazide sulfonyl chloride, the hydroxy compound and / or the amino compound are preferably blended so that the total of the hydroxy group and the amino group is 0.5 to 1 equivalent with respect to 1 mol of the o-quinonediazide sulfonyl chloride. A preferred ratio of the dehydrochlorinating agent and o-quinonediazidesulfonyl chloride is 0.95 / 1 to 1 / 0.95 (equivalent ratio). A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As the reaction solvent, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  The blending amount of the photoacid generator is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the polybenzoxazole precursor component in order to improve the sensitivity and resolution during exposure. It is more preferable to set it as 01-20 weight part, and it is further more preferable to set it as 0.5-20 weight part.

（式中、Ｘは水素原子、単結合又は１〜４価の有機基であり、Ｘ’はＨ、ＯＨ、ＯＲ、ＣＯＯＨ又はＣＯＯＲであり（Ｒは炭素数１〜２０の一価の有機基である）、Ｘ''は熱によりポリベンゾオキサゾール前駆体と架橋し得るか又は架橋剤同士で重合し得る基であり、Ｒ^２１は１価の有機基であり、ｎは１〜４の整数であり、ｇは１〜４の整数であり、ｈは０〜４の整数である。） (3) Compound capable of crosslinking or polymerizing with polybenzoxazole precursor by heat The photosensitive resin composition described above contains a compound capable of crosslinking or polymerizing with a polybenzoxazole precursor by heat (hereinafter also referred to as a crosslinking agent). You may do it.
The cross-linking agent preferably has a substituent that efficiently cross-links with the polybenzoxazole precursor. The temperature at which the crosslinking agent can be crosslinked is preferably 150 ° C. or higher so that crosslinking does not proceed in the coating, drying, exposure, and development steps of the photosensitive resin composition. The cross-linking agent cross-links with the end group of the polybenzoxazole precursor, and may be a compound that polymerizes between molecules together with this. Among them, those listed in the following formula (3) are more preferable even when cured at a low temperature of 220 ° C. or lower, with a small drop in film properties and excellent film properties.

(In the formula, X is a hydrogen atom, a single bond, or a monovalent to tetravalent organic group, and X ′ is H, OH, OR, COOH, or COOR (R is a monovalent organic group having 1 to 20 carbon atoms). X ″ is a group that can be crosslinked with a polybenzoxazole precursor by heat or polymerized with a crosslinking agent, R ²¹ is a monovalent organic group, and n is an integer of 1 to 4. And g is an integer of 1 to 4, and h is an integer of 0 to 4.)

（式中、Ｘ’は、各々独立に、アルキレン基（例えば、炭素数１〜１０のもの）、アルキリデン基（例えば、炭素数２〜１０のもの）、それらの水素原子の一部又は全部をハロゲン原子で置換した基、スルホン基、カルボニル基、エ−テル結合、チオエ−テル結合、アミド結合等から選択されるものであり、Ｒ^３４は、水素原子、ヒドロキシ基、アルキル基又はハロアルキル基であり、複数存在する場合は互いに同一でも異なっていてもよく、ｘは１〜１０の整数である。） In the formula (3), examples of the organic group represented by X include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group and propylene group, alkylidene groups having 2 to 10 carbon atoms such as ethylidene group, and phenylene. An arylene group having 6 to 30 carbon atoms such as a group, a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom, a sulfone group, a carbonyl group, an ether bond, a thioether Examples include a tellurium bond and an amide bond. Moreover, the divalent organic group shown by following formula (15) is mentioned as a preferable thing.

(In the formula, each X ′ independently represents an alkylene group (for example, one having 1 to 10 carbon atoms), an alkylidene group (for example, one having 2 to 10 carbon atoms), or a part or all of these hydrogen atoms. R ³⁴ is selected from a group substituted with a halogen atom, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, etc., and R ³⁴ is a hydrogen atom, a hydroxy group, an alkyl group or a haloalkyl group. And when there are a plurality, they may be the same or different from each other, and x is an integer of 1 to 10.)

Specifically, as the monovalent organic group of R ²¹ in the above formula (3), carbonization such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, amyl group, etc. Although a hydrogen group is mentioned, it is not limited to these.

（式中、Ｒ''は水素原子又は一価の有機基、Ｐは炭素数１〜２０の一価の有機基である。この一価の有機基は、窒素原子や不飽和結合を有していてもよい。） As the cross-linking agent, X ″ is a group represented by —CH ₂ OR ²⁶ (R ²⁶ is a hydrogen atom or a monovalent organic group) or a group which is converted into an isocyanate by heat. It is preferable because it is excellent. The group that is converted to isocyanate by heat is not particularly limited as long as it is converted to isocyanate by heat, and examples thereof include those having a structure as shown in the following formula (16).

(Wherein R ″ is a hydrogen atom or a monovalent organic group, and P is a monovalent organic group having 1 to 20 carbon atoms. This monovalent organic group has a nitrogen atom or an unsaturated bond. May be.)

（式中、２つのＹは各々独立に水素原子、炭素数１〜１０のアルキル基又はその一部に酸素原子もしくはフッ素原子を含む基であり、Ｒ^２３〜Ｒ^２６は、各々独立に水素原子又は一価の有機基であり、ｏ及びｐは、各々独立に１〜３の整数であり、ｇ及びｈは、各々独立に０〜４の整数である。）

（式中、複数のＲ^２７は、各々独立に水素原子又は一価の有機基であり、複数のＲ^２８は、各々独立に水素原子又は一価の有機基であり、互いが結合することで置換基を有してもよい環構造となっていてもよい。） Furthermore, the compounds listed in the following formula (4) are excellent in photosensitivity, and the compounds listed in the following formula (5) are excellent in the solvent resistance and flux resistance of the cured film when cured at a low temperature of 220 ° C. or lower. It is mentioned as a particularly preferable agent.

(In the formula, two Y are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group containing an oxygen atom or a fluorine atom in a part thereof, and R ^{23 to} R ²⁶ are each independently a hydrogen atom. Or a monovalent organic group, o and p are each independently an integer of 1 to 3, and g and h are each independently an integer of 0 to 4.)

(Wherein a plurality of R ²⁷ are each independently a hydrogen atom or a monovalent organic group, and a plurality of R ²⁸ are each independently a hydrogen atom or a monovalent organic group, and are bonded to each other) (It may be a ring structure which may have a substituent.)

In formula (4), specifically, those containing an oxygen atom as Y include an alkyloxy group, and those containing a fluorine atom include a perfluoroalkyl group. Specific examples of the monovalent organic group represented by R ^{23 to} R ²⁶ include hydrocarbons such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and an amyl group. Examples include, but are not limited to, groups.

  Moreover, as a compound represented by Formula (5), the compound represented by following formula (17) is mentioned as a preferable thing.

（式中、Ｚは、炭素数１〜１０のアルキル基を表し、複数のＲ^３５は、各々独立に炭素数１〜２０（好ましくは１〜１０）のアルキル基を表す。）

(In formula, Z represents a C1-C10 alkyl group, and several R ^<35 > represents a C1-C20 (preferably 1-10) alkyl group each independently.)

  The content of the crosslinking agent is preferably 5 parts by weight or more based on 100 parts by weight of the polybenzoxazole precursor from the viewpoints of sensitivity during photosensitivity, resolution, chemical resistance of the cured film, and flux resistance. It is more preferable to use parts by weight or more. Further, from the viewpoint of balance with the photosensitive properties, the content of the crosslinking agent is more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the polybenzoxazole precursor.

(4) Solvent The above-mentioned photosensitive resin composition usually contains a solvent, and each of the above components is dissolved or dispersed. The solvent is not particularly limited, and γ-butyrolactone (BLO), propylene glycol monomethyl ether acetate (PGMEA), N-methylpyrrolidone (NMP), toluene, xylene, tetrahydrofuran, alcohol and the like can be used. Although the usage-amount of the said solvent is not restrict | limited in particular, Preferably it uses so that solid content (components other than a solvent) may be 5 to 50 weight%.

[Method for Manufacturing Semiconductor Device]
The method for manufacturing a semiconductor device of the present invention includes a step of heating a substrate having a rewiring at 140 to 160 ° C. to form a copper oxide layer on the rewiring, and an insulation containing polybenzoxazole on the copper oxide layer. Forming a layer.

Hereinafter, a method for manufacturing a semiconductor device of the present invention will be described with reference to the drawings.
A cross-sectional view of a semiconductor device according to an embodiment of the present invention is shown in FIG.
A connection pad 11 made of an aluminum-based metal is formed on a silicon substrate 10 provided with an integrated circuit (not shown) so as to be connected to the integrated circuit. An insulating layer 20 is formed thereon, and the pad 11 portion is opened. Next, the surface protective film layer 30 is applied, and the pad 11 portion is exposed by an exposure and development process. Next, the rewiring 40 is formed by sputtering or plating.
Since an oxide film is usually formed on the surface of the rewiring 40, preferably, before forming the copper oxide layer 41, the rewiring is washed with an acid to remove the oxide film.

Usually, an oxide film is formed on the surface of the rewiring composed mainly of copper by oxygen in the air, but the thickness is as thick as 40 nm or more, or the thickness is not uniform. Therefore, if the insulating layer is formed on the rewiring as it is, the adhesiveness between the insulating layer and the rewiring becomes insufficient.
Therefore, it is preferable to remove the oxide film on the surface of the rewiring 40 once and then form the copper oxide layer 41 having an appropriate thickness, that is, use the copper oxide layer 41 while controlling the thickness.

  Removal of the oxide film formed on the surface of the rewiring 40 is efficiently performed by cleaning the surface of the rewiring with an appropriate concentration of an organic acid such as acetic acid or citric acid or an inorganic acid such as hydrochloric acid or sulfuric acid. be able to.

The copper oxide layer 41 is preferably formed to an appropriate thickness by removing the oxide film as described above and then performing a treatment for 0.5 to 10 minutes in a hot plate or oven heated to 130 to 170 ° C. be able to.
The heating temperature is preferably 140 to 160 ° C., and the heating time is preferably 1 to 5 minutes.

  Thereafter, the insulating layer 50 is formed on the rewiring 40 (copper oxide layer 41) by the application, exposure, and development processes using the above resin composition. Next, an opening is provided in the insulating layer 50, a connection pad and a barrier metal are formed in the opening, and a solder ball (conductive ball) 60 is formed.

  Examples of the method for applying the resin composition to the rewiring 40 (copper oxide layer 41) include spin coating and slit coating. Moreover, after application | coating of a resin composition, you may dry from a viewpoint of operativity.

The exposure of the resin film is performed using a stepper, an aligner, or the like on the resin film formed by applying the resin composition. The exposed resin film is developed with an alkaline developer such as a 2.38% TMAH aqueous solution to obtain a patterned resin film (pattern resin film).
A pattern cured film can be formed by heat-curing the pattern resin film. Heat curing is preferably performed at 160 to 400 ° C., and for example, a quartz tube furnace, a hot plate, a vertical diffusion furnace, an infrared curing furnace, a microwave curing furnace, or the like can be used.

  Examples and Comparative Examples are described below, but the present invention is not limited to the following Examples and Comparative Examples.

[Synthesis of polybenzoxazole precursor]
Synthesis example 1
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g (60 mmol) of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and the flask was cooled to 5 ° C. Thereafter, 23.9 g (120 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid dichloride.

  Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 87.5 g of N-methylpyrrolidone was charged, and 18.30 g (50 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. Dissolved with stirring. Thereafter, 9.48 g (120 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid dichloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes.

  The stirred solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then dried under reduced pressure to obtain carboxyl group-terminated polyhydroxyamide (Polymer I). The polymer I was subjected to GPC measurement under the following measurement conditions, and the weight average molecular weight was determined from the obtained measurement value in terms of GPC standard polystyrene. The weight average molecular weight obtained was 17,600, and the degree of dispersion was 1.6.

(Measurement conditions of weight average molecular weight by GPC method)
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
Recorder: C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm
The measurement was performed using a solution of 1 mL of a solvent [THF / DMF = 1/1 (volume ratio)] per 0.5 mg of the polymer.
In Synthesis Examples 2 and 3, the same measurement was performed to determine the weight average molecular weight.

Synthesis example 2
Polyhydroxyamide was synthesized in the same manner as in Synthesis Example 1 except that dodecanedioic acid was used instead of diphenyl ether dicarboxylic acid (Polymer II). The weight average molecular weight calculated | required by standard polystyrene conversion of the polymer II was 27,200, and dispersion degree was 1.9.

Synthesis example 3
Polyhydroxyamide was synthesized in the same manner as in Synthesis Example 1 except that 1,2-phenylenediacetic acid was used in place of diphenyl ether dicarboxylic acid (Polymer III). The weight average molecular weight calculated | required by standard polystyrene conversion of the polymer III was 21,400, and dispersion degree was 2.2.

Synthesis example 4
[Preparation of photosensitive resin composition]
For use in Examples 1 to 8 and Comparative Examples 1 to 4 to be described later, the polymers I to III prepared in Synthesis Examples 1 to 3, a compound that generates an acid upon irradiation with light (photoacid generator), and heat A solvent in which a compound (crosslinking agent) capable of crosslinking or polymerizing with a polybenzoxazole precursor is mixed in the blending amount (parts by weight) shown in Table 1 and γ-butyrolactone / propylene glycol monomethyl ether acetate in a weight ratio of 9: 1. To prepare a photosensitive resin composition.
In Table 1, in each column of components other than the polybenzoxazole precursor, each numerical value indicates an addition amount (part by weight) relative to 100 parts by weight of the polybenzoxazole precursor unless otherwise specified. The amount of the solvent used is 200 parts by weight with respect to 100 parts by weight of the polybenzoxazole precursor.

In addition, the following B1 was used as a photoacid generator, and the following C1 was used as a crosslinking agent.

Example 1
A 1.5 μm copper layer was formed on a silicon wafer (thickness: 625 μm) by sputtering, and then a desired wiring pattern (patterned rewiring) was obtained by photoetching. Next, the silicon wafer on which this wiring pattern was formed was washed for 2 minutes using a copper oxide remover (manufactured by World Metal: Z-200), rinsed with pure water, and then heated to 140 ° C. Then, a heat treatment was performed for 3 minutes to form a copper oxide film on the copper wiring pattern. The thickness of the copper oxide film was measured by Auger spectroscopy (AES) under the conditions described later.

Next, a photosensitive resin composition having the composition shown in Table 1 is spin-coated on the surface of the silicon wafer on which the wiring pattern created under the above conditions is formed, and heated at 120 ° C. for 3 minutes. A coating film having a dry film thickness of 7 to 12 μm was formed. The obtained coating film was exposed by irradiating the wafer with a predetermined pattern at 300 mJ / cm ² through an interference filter using an ultrahigh pressure mercury lamp as a light source. Development was performed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) until the exposed silicon wafer was exposed, followed by rinsing with water to obtain a patterned resin film. At this time, no post-development residue was formed in the through-hole portion.

  Next, the silicon wafer on which the pattern resin film was formed was heat-treated at 320 ° C. for 1 hour to obtain a silicon wafer with a patterned cured film.

The measurement conditions for the average thickness of the copper oxide layer are as follows.
AES equipment: SAM-670 (PHI, FE type)
Electron beam: 5 kV, 10 nA Beam size = 0.05 μm
Ion beam: Ar, 3 kV, sputtering rate = 4.6 nm / min (in the case of SiO ₂ )
Measurement location: A range of 150 μm × 150 μm was analyzed.
Analysis was performed in the depth direction while ion-sputtering the measurement location, and the components Cu, O, and C were analyzed, and calculated from the concentration [atomic%], the sputter depth [nm], and the sputter speed.

The following evaluation was performed about the obtained silicon wafer with a pattern cured film. The results are shown in Table 1.
(Adhesive evaluation)
Using the obtained silicon wafer with a cured pattern film, the adhesion of the cured pattern film to the wiring pattern was evaluated. Adhesion was evaluated using a stud pull tester. The cured film was placed in a pressure cooker and treated for 500 hours under conditions of 121 ° C., 2 atm, 100% HR (PCT treatment). The adhesive strength before and after the PCT treatment was evaluated using a stud pull tester (ROMULUS, manufactured by Quad Group Inc.).

  Specifically, an aluminum pin with an epoxy resin is placed on a cured film on a wafer with a patterned cured film treated for 500 hours under the above PCT conditions (121 ° C./100 RH% / 2 atm), and 150 ° C. in an oven. / 1 hour was applied to adhere the stud pin with the epoxy resin to the cured film. The pin was pulled using the stud pull tester, and the peeled state when peeled off was visually observed.

In the stud pull test, any sample other than Comparative Example 2 showed a sufficient adhesive strength of 600 to 800 kg / cm ² , but a difference was observed in the peeling mode (form). The peeling mode is one of the important indicators for estimating the adhesive strength.

  The evaluation criteria for the peeling mode were as follows. When five or more of the same substrates are prepared and evaluated, if 3 or more are peeled off at the interface between the wiring pattern and the cured film, it indicates that the adhesive force between the wiring pattern and the cured film is not sufficient, and therefore, C is set. When it peeled off, it was set to B, and when the space | interval between a cured film and an epoxy adhesive layer fractured | ruptured, since sufficient adhesive strength with a silicon substrate was hold | maintained, it evaluated as A.

Example 2
A patterned cured film was prepared and evaluated in the same manner as in Example 1 except that the hot plate temperature after washing the copper oxide remover was 150 ° C. The results are shown in Table 1.
When the pattern resin film was produced, no residue was confirmed in the through hole portion.

Example 3
A patterned cured film was prepared and evaluated in the same manner as in Example 1 except that the hot plate temperature after washing the copper oxide remover was set to 160 ° C. The results are shown in Table 1.
When the pattern resin film was produced, no residue was confirmed in the through hole portion.

Example 4
A patterned cured film was prepared and evaluated in the same manner as in Example 1 except that the hot plate temperature after washing the copper oxide remover was 150 ° C. and the heat treatment time was 2 minutes. The results are shown in Table 1.
When the pattern resin film was produced, no residue was confirmed in the through hole portion.

Example 5
A patterned cured film was prepared and evaluated in the same manner as in Example 1 except that the hot plate temperature after washing the copper oxide remover was 150 ° C. and the heat treatment time was 3 minutes 30 seconds. The results are shown in Table 1.
When the pattern resin film was produced, no residue was confirmed in the through hole portion.

Example 6
A patterned cured film was prepared and evaluated in the same manner as in Example 1 except that the hot plate temperature after washing the copper oxide remover was 150 ° C. and the heat treatment time was 4 minutes. The results are shown in Table 1.
When the pattern resin film was produced, no residue was confirmed in the through hole portion.

Example 7
A cured pattern film was prepared in the same manner as in Example 1 except that the polymer II was used as the polybenzoxazole precursor, the hot plate temperature after washing the copper oxide remover was 150 ° C., and the heat treatment time was 3 minutes. And evaluated. The results are shown in Table 1.
When the pattern resin film was produced, no residue was confirmed in the through hole portion.

Example 8
A cured pattern film was prepared in the same manner as in Example 1 except that the polymer III was used as the polybenzoxazole precursor, the hot plate temperature after washing the copper oxide remover was 150 ° C., and the heat treatment time was 3 minutes. And evaluated. The results are shown in Table 1.
When the pattern resin film was produced, it was confirmed that a small amount of residue was present in the through hole portion.

Comparative Example 1
A patterned cured film was prepared and evaluated in the same manner as in Example 1 except that the hot plate temperature after washing the copper oxide remover was 120 ° C. The results are shown in Table 1.
When the pattern resin film was produced, a residue was confirmed in the through hole portion.

Comparative Example 2
A pattern cured film was prepared and evaluated in the same manner as in Example 1 except that the hot plate temperature after washing the copper oxide remover was 180 ° C. The results are shown in Table 1.

Comparative Example 3
A patterned cured film was prepared and evaluated in the same manner as in Example 1 except that heating was not performed after washing the copper oxide remover. The results are shown in Table 1.

  In each of Examples 1 to 8, in which the copper oxide film thickness is 3 to 35 nm and the insulating layer is formed using the polybenzoxazole precursor, the residue of the pattern opening can be sufficiently reduced. Adhesion was good.

  The semiconductor device of the present invention can be used for various electronic devices.

DESCRIPTION OF SYMBOLS 10 Board | substrate 101 Interlayer insulating layer 102 Al wiring layer 20,103 Insulating layer 30,104 Surface protection film layer 11,105 Wiring layer pad part 40,106 Rewiring 41,106a Copper oxide layer 60,107 Conductive ball 108 Core 50, 109 Insulating layer 110 Barrier metal 111 Color 112 Underfill

Claims (8)

A semiconductor device including a substrate having rewiring and an insulating layer containing polybenzoxazole on the rewiring, wherein the copper oxide layer is obtained by Auger spectroscopy, including a copper oxide layer on a surface of the rewiring Is an average thickness of 3 to 35 nm,
A semiconductor device wherein the insulating layer is obtained by heat curing a resin composition containing a polybenzoxazole precursor represented by the following formula (1).

(In the formula, U represents a tetravalent organic group, and V represents a divalent aromatic group having 6 to 40 carbon atoms or an aliphatic straight chain structure having 6 to 30 carbon atoms including two or more aromatic rings. It represents a divalent organic group possessed .)   The semiconductor device according to claim 1, wherein the copper oxide layer has an average thickness of 3 to 20 nm.   The semiconductor device according to claim 1, wherein a main component of the rewiring is copper. The semiconductor device according to any one of claims 1 to 3 , wherein V is a C6-C40 divalent aromatic group containing two or more aromatic rings. The insulating layer, the semiconductor device according to any one of claims 1 to 3 was obtained by heating and curing the resin composition comprising a polybenzoxazole precursor represented by the following formula (2).

(In the formula, U represents a tetravalent organic group, R ¹ and R ² each independently represent a monovalent organic group, and n represents an integer of 6 to 20.) Heating a substrate having rewiring at 140 to 160 ° C. to form a copper oxide layer on the rewiring, and forming an insulating layer containing polybenzoxazole on the copper oxide layer. the method of manufacturing a semiconductor device for obtaining a semiconductor device according to any one of claims 1-5. The method of manufacturing a semiconductor device according to claim 6 , further comprising a step of removing the oxide film by washing the rewiring with an acid before the step of forming the copper oxide layer. The method of manufacturing a semiconductor device according to claim 6 or 7 the heating time is 1 to 5 minutes in the step of forming the copper oxide.

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