JP2012078542A - Positive photosensitive resin composition, cured film, protective film, insulating film. semiconductor device and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which has high sensitivity and has high resolution, and has a high cyclization rate even when the resin composition is cured at a low temperature, and to provide a semiconductor device and a display device.SOLUTION: The positive photosensitive resin composition contains (A) an alkali-soluble resin, (B) a photosensitive agent and (C) a nitrogen-containing compound represented by the general formula (1). The cured film is formed of a cured material of the positive photosensitive resin composition. The semiconductor device and the display device have the cured film.

Description

  The present invention relates to a positive photosensitive resin composition, a cured film, a protective film, an insulating film, a semiconductor device, and a display device.

Conventionally, polybenzoxazole resins, polyimide resins, and the like that are excellent in heat resistance and have excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protection films and interlayer insulating films of semiconductor elements. On the other hand, in order to simplify the process, a positive photosensitive resin composition in which a polyazoxazole resin, a polyimide resin, or the like is combined with a diazoquinone compound as a photosensitive agent is also used.
This photosensitive resin composition becomes hardly soluble in an alkaline aqueous solution in an unexposed portion due to the effect of inhibiting the dissolution of a diazoquinone compound in a resin such as polybenzoxazole resin or polyimide resin. On the other hand, in the exposed area, the diazoquinone compound undergoes a chemical change, and the photosensitive resin composition becomes soluble in an alkaline aqueous solution. By utilizing the difference in solubility between the exposed portion and the unexposed portion and dissolving and removing the exposed portion with an alkaline aqueous solution, it becomes possible to create a coating film pattern of only the unexposed portion.

  The polybenzoxazole resin precursor in the positive photosensitive resin composition in which the coating film pattern is formed is finally dehydrated and closed by curing at a high temperature close to 300 ° C., and becomes a polybenzoxazole resin rich in heat resistance. On the other hand, in recent years, due to remarkable miniaturization and high integration of semiconductor elements, the heat resistance of the memory elements has been lower than that of conventional ones. is needed. What is important when curing at a low temperature is the cyclization rate of the resin after curing. When the cyclization rate is low, the water absorption is increased due to the influence of the remaining alkali-soluble groups, so that not only the moisture resistance reliability and chemical resistance are lowered, but also the dielectric constant is increased. In order to improve the cyclization rate, for example, Patent Document 1 discloses a polybenzoxazole resin precursor using bis (aminophenol) containing an ether bond in order to facilitate movement of a molecular chain. There is a problem that it is difficult to form a pattern because the transparency of the resin is very low with respect to ultraviolet rays (i-line) having a wavelength of 365 nm, which is often used as an actinic ray.

Further, when these positive photosensitive resin compositions are actually used, the sensitivity of the photosensitive resin composition is particularly important. If the sensitivity is low, the exposure time becomes long and the throughput (processing speed per unit time) decreases. Therefore, in order to improve the sensitivity of the photosensitive resin composition, for example, the phenolic hydroxyl group in the polybenzoxazole precursor resin is protected with an appropriate organic group, and the intramolecular hydrogen bond is suppressed so that it is highly transparent to i-line. However, in order to protect the phenolic hydroxyl group which is an alkali-soluble group, it cannot be sufficiently dissolved in an alkaline aqueous solution, resulting in low sensitivity, as well as the carbonyl carbon of the amide group and the phenolic hydroxyl group. It becomes difficult to close the ring when the distance between them is increased.
Thus, it is a positive photosensitive resin composition using a polybenzoxazole resin precursor, which is highly sensitive and has high cyclization rate even when cured at low temperature, both workability and reliability Recently, development of a positive photosensitive resin composition satisfying these characteristics has been strongly desired. That is, in the conventional positive photosensitive resin composition, it has been difficult to achieve both high sensitivity and a high cyclization rate when cured at a low temperature by using a polybenzoxazole resin precursor.

Japanese Patent No. 3078175

  The present invention provides a positive photosensitive resin composition, a semiconductor device, and a display device that have high sensitivity and high resolution, and also have a high cyclization rate even when cured at low temperatures.

（Ｒは有機基を表す。Ａは電子吸引性基を表す。）
［２］ 前記アルカリ可溶性樹脂（Ａ）が、一般式（２）で示される繰り返し単位を有するポリアミド系樹脂である、前記［１］項に記載のポジ型感光性樹脂組成物。

（式中、Ｘ、Ｙは有機基である。Ｒ_１は水酸基、−Ｏ−Ｒ_３、アルキル基、アシルオキシ基、シクロアルキル基であり、同一でも異なっても良い。Ｒ_２は水酸基、カルボキシル基、−Ｏ−Ｒ_３、−ＣＯＯ−Ｒ_３のいずれかであり、同一でも異なっても良い。ｍは０〜８の整数、ｎは０〜８の整数である。Ｒ_３は炭素数１〜１５の有機基である。ここで、Ｒ_１が複数ある場合は、それぞれ異なっていても同じでもよい。Ｒ_１として水酸基がない場合は、Ｒ_２は少なくとも１つはカルボキシル基でなければならない。また、Ｒ_２としてカルボキシル基がない場合、Ｒ_１は少なくとも１つは水酸基でなければならない。）
［３］ 前記一般式（２）で示される繰り返し単位を有するポリアミド系樹脂のＸが、下記式（３）からなる群より選択される１種以上を含む、前記［２］項に記載のポジ型感光性樹脂組成物。

（ここで＊はＮＨ基に結合することを示す。式（３）中のＤは、−ＣＨ_２−、−ＣＨ（Ｃ
Ｈ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合でありである。Ｒ_４は、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。ｓ＝０〜３の整数である。）
［４］ 前記一般式（２）で示される繰り返し単位を有するポリアミド系樹脂のＹが、下記式（４）からなる群より選択される１種以上を含む、前記［２］または［３］項に記載のポジ型感光性樹脂組成物。

（ここで＊はＣ＝Ｏ基に結合することを示す。式（４）中のＥは−ＳＯ_２−、−ＣＯ−、−Ｏ−、である。Ｒ_５ は、アルキル基、アルキルエステル基、アルキルエーテル基、ベ
ンジルエーテル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｔ＝０〜４の整数である。）
［５］ 前記一般式（１）で示される含窒素化合物（Ｃ）のＡが、スルホニル基である前記［１］ないし［４］項のいずれか１項に記載のポジ型感光性組成物。
［６］ 前記一般式（１）で示される含窒素化合物（Ｃ）のＡが、カルボニル基である前記［１］ないし［４］項のいずれか１項に記載のポジ型感光性組成物。
［７］ 前記アルカリ可溶性樹脂（Ａ）１００重量部に対して、一般式（１）で示される含窒素化合物（Ｃ）を１〜３０重量部含むものである、前記［１］ないし［６］項のいずれか１項に記載のポジ型感光性樹脂組成物。
［８］ 前記感光剤（Ｂ）が、感光性ジアゾキノン化合物である、前記［１］ないし［７］項のいずれか１項に記載のポジ型感光性樹脂組成物。
［９］ 前記［１］ないし［８］項のいずれか１項に記載のポジ型感光性樹脂組成物の硬化物で構成されている硬化膜。
［１０］ 前記［９］項に記載の硬化膜で構成されている保護膜。
［１１］ 前記［９］項に記載の硬化膜で構成されている絶縁膜。
［１２］ 前記［９］項に記載の硬化膜を有している半導体装置。
［１３］ 前記［９］項に記載の硬化膜を有している表示体装置。 Such an object is achieved by the present inventions [1] to [13] below.
[1] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and a nitrogen-containing compound (C) represented by the general formula (1).

(R represents an organic group. A represents an electron-withdrawing group.)
[2] The positive photosensitive resin composition according to the above [1], wherein the alkali-soluble resin (A) is a polyamide-based resin having a repeating unit represented by the general formula (2).

(In the formula, X and Y are organic groups. R ₁ is a hydroxyl group, —O—R ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₂ is a hydroxyl group or a carboxyl group. , —O—R ₃ , —COO—R ₃ , which may be the same or different, m is an integer of 0 to 8, n is an integer of 0 to 8. R ₃ is an integer of 1 to Here, when there are a plurality of R _{1 s} , they may be different or the same, and when R ₁ has no hydroxyl group, at least one R ₂ must be a carboxyl group. In addition, when R ₂ has no carboxyl group, at least one R ₁ must be a hydroxyl group.
[3] The positive electrode according to [2], wherein X of the polyamide-based resin having a repeating unit represented by the general formula (2) includes one or more selected from the group consisting of the following formula (3). Type photosensitive resin composition.

(Here, * indicates bonding to an NH group. D in the formula (3) represents —CH ₂ —, —CH (C
H ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond. is there. R ₄ is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. s = 0 is an integer of 0 to 3. )
[4] The item [2] or [3], wherein Y of the polyamide-based resin having the repeating unit represented by the general formula (2) includes one or more selected from the group consisting of the following formula (4). The positive photosensitive resin composition described in 1.

(Here, * indicates bonding to a C═O group. E in the formula (4) is —SO ₂ —, —CO—, —O—, and R ₅ represents an alkyl group or an alkyl ester group.) And represents one selected from an alkyl ether group, a benzyl ether group, and a halogen atom, which may be the same or different, each of which is an integer of t = 0 to 4.)
[5] The positive photosensitive composition according to any one of [1] to [4], wherein A of the nitrogen-containing compound (C) represented by the general formula (1) is a sulfonyl group.
[6] The positive photosensitive composition according to any one of [1] to [4], wherein A of the nitrogen-containing compound (C) represented by the general formula (1) is a carbonyl group.
[7] In the above [1] to [6], the amount of the nitrogen-containing compound (C) represented by the general formula (1) is 1 to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). The positive photosensitive resin composition according to any one of the above.
[8] The positive photosensitive resin composition according to any one of [1] to [7], wherein the photosensitive agent (B) is a photosensitive diazoquinone compound.
[9] A cured film composed of a cured product of the positive photosensitive resin composition according to any one of [1] to [8].
[10] A protective film composed of the cured film according to the item [9].
[11] An insulating film composed of the cured film according to the item [9].
[12] A semiconductor device having the cured film according to the item [9].
[13] A display device having the cured film according to the item [9].

  The positive-type photosensitive resin composition of the present invention has high sensitivity and high resolution with the characteristics that there is little film loss, the pattern shape does not collapse, and there is no remaining (scum) of the photosensitive resin composition in the exposed area. It has an excellent feature. Furthermore, it also has an excellent feature that it has a high cyclization rate even when cured at a low temperature.

The present invention is a positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and a nitrogen-containing compound (C) represented by the general formula (1). is there. By using the positive photosensitive resin composition having such a configuration, there are excellent effects such as sensitivity, resolution, and a high cyclization rate even in cyclization at low temperatures.
Hereinafter, the present invention will be described in detail.

The alkali-soluble resin (A) according to the present invention is not particularly limited, and examples thereof include acrylic resins such as cresol type novolac resin, hydroxystyrene resin, methacrylic acid resin, and methacrylic ester resin, hydroxyl group, and carboxyl. Examples thereof include cyclic olefin resins containing a group and polyamide resins. Among these, polyamide resins are preferred from the viewpoint of excellent heat resistance and good mechanical properties. Specifically, they have at least one of a polybenzoxazole structure and a polyimide structure, and have hydroxyl groups or carboxyl groups in the main chain or side chain. , A resin having an ether group or an ester group, a resin having a polybenzoxazole resin precursor structure, a resin having a polyimide resin precursor structure, a resin having a polyamic acid ester structure, and the like. As such a polyamide-type resin, the polyamide-type resin shown by the said General formula (2) can be mentioned, for example.

In a polyamide resin represented by the general formula (2), _-O-R 3 as a substituent of the _-O-R 3, Y as a substituent of X, _{-COO-R 3} represents a hydroxyl group, a carboxyl group For the purpose of adjusting the solubility in an aqueous alkali solution, it is a group protected by R ₃ which is an organic group having 1 to 15 carbon atoms, and a hydroxyl group or a carboxyl group may be protected if necessary. Examples of R ₃ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.
The polyamide resin having the repeating unit represented by the general formula (2) is, for example, a compound selected from diamine containing X or bis (aminophenol), 2,4-diaminophenol, and tetracarboxylic acid containing Y. It is obtained by reacting a compound selected from dianhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative and the like. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

  Examples of X in the general formula (2) include aromatic compounds such as benzene ring and naphthalene ring, heterocyclic compounds such as bisphenols, pyrroles, and furans, and siloxane compounds. What is shown by following formula (5) can be mentioned preferably. These may be used alone or in combination of two or more.

（ここで、＊はＮＨ基に結合することを示す。式中Ｂは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合である。Ｒ_６はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、Ｒ_７はアルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。u＝０〜４の整数であ
る。）

（ここで＊はＮＨ基に結合することを示す。Ｒ_８〜Ｒ_１１は有機基である。）
上記一般式（２）で示すように、ＸにはＲ_１が０〜８個結合される（式（５）において、Ｒ_１は省略）。

(Here, * indicates bonding to an NH group. In the formula, B represents —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ₆ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom. R ₇ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different, and is an integer of u = 0 to 4.)

(Here, * indicates bonding to the NH group. R _{8 to} R ₁₁ are organic groups.)
As shown by the general formula (2), 0 to 8 R ₁ are bonded to X (in the formula (5), R ₁ is omitted).

（式中、＊はＮＨ基に結合することを示す。式（６）中のＤは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合であり、Ｆは、−ＳＯ_２−、−Ｏ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、または単結合である。Ｒ_４は、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。Ｒ_６はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。s＝０〜３、u＝０〜４の整数である。）

（式中、＊はＮＨ基に結合することを示す。） Preferred examples of the formula (5) include those represented by the following formula (6), which are particularly excellent in heat resistance and mechanical properties.

(Wherein * is D in formula (6) denotes a bond to the NH _{group, -CH 2 -., - CH} (CH 3) -, - C (CH 3) 2 -, - O-, _{-S -, - SO 2 -,} - CO -, - NHCO -, - C (CF 3) 2 -, or a single bond, F _{is, -SO 2 -, - O -} , - CH 2 -, - C (CH ₃ ) ₂ — or a single bond R ₄ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, and may be the same or different, and R ₆ is an alkyl group, an alkyl group It represents one selected from an ester group and a halogen atom, and may be the same or different, each being an integer of s = 0 to 3, u = 0 to 4.)

(In the formula, * indicates binding to an NH group.)

  Further, among the formulas (6), those represented by the above formula (3) are particularly preferable. When X of the polyamide-based resin represented by the general formula (2) is the above formula (3), the sensitivity is further improved by the combination with the nitrogen-containing compound (C) represented by the general formula (1).

  Y in the general formula (2) is an organic group, and examples thereof include those similar to X. For example, aromatic compounds such as benzene ring and naphthalene ring, bisphenols, pyrroles, pyridines, furans, etc. The heterocyclic compound, siloxane compound, etc. of these are mentioned, More specifically, what is shown by following formula (7) can be mentioned preferably. These may be used alone or in combination of two or more.

（ここで＊はＣ＝Ｏ基に結合することを示す。式中（７）のＢは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合である。Ｒ_１２はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同一でも異なっても良い。また、Ｒ_１３は水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを示す。
ｒ＝０〜４の整数である。）

(Here, * indicates bonding to a C═O group. In the formula (7), B represents —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—). , —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ₁₂ is selected from an alkyl group, an alkyl ester group, and a halogen atom. R ₁₃ may be the same or different from each other, and R ₁₃ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom.
r is an integer of 0-4. )

（ここで＊はＣ＝Ｏ基に結合することを示す。Ｒ_１４〜Ｒ_１７は有機基である。）

(Here, * indicates bonding to a C═O group. R _{14 to} R ₁₇ are organic groups.)

As shown by the general formula (2), 0 to 8 R ₂ are bonded to Y (in the formula (7), R ₂ is omitted).
As a preferable thing in Formula (7), what is shown by following formula (8) which is excellent in heat resistance and a mechanical characteristic is mentioned.
As for the structure derived from tetracarboxylic dianhydride in the following formula (8), the position where both C═O groups are bonded to the meta position, and both the para positions are listed. A structure including each of the para positions may be used.

（式中、＊はＣ＝Ｏ基に結合することを示す。式（８）中のＥとＧは、−ＳＯ_２−、−ＣＯ−、−Ｏ−、である。Ｒ_５は、アルキル基、アルキルエステル基、アルキルエーテル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。Ｒ_１８は、水素原子または、炭素数１〜１５の有機基から選ばれた１つを示し、一部が置換されていても良い。ｔ＝０〜４の整数である。）

(In the formula, * indicates bonding to a C═O group. E and G in the formula (8) are —SO ₂ —, —CO—, —O—, and R ₅ is an alkyl group. Represents one selected from an alkyl ester group, an alkyl ether group, and a halogen atom, and may be the same or different, and R ₁₈ is selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms. 1 may be partially substituted, and is an integer of t = 0 to 4.)

（式中、＊はＣ＝Ｏ基に結合することを示す。）
さらに、式（８）の中でも、上記式（４）で示されるものが特に好ましい。一般式（２）で示されるポリアミド系樹脂のＹが上記式（４）である場合、一般式（１）で示される含窒素化合物（Ｃ）との組み合わせにより、感度がより優れる。

(In the formula, * indicates binding to a C═O group.)
Further, among the formulas (8), those represented by the above formula (4) are particularly preferable. When Y of the polyamide-based resin represented by the general formula (2) is the above formula (4), the sensitivity is further improved by the combination with the nitrogen-containing compound (C) represented by the general formula (1).

In addition, the polyamide-based resin having the repeating unit represented by the general formula (2) is an aliphatic group having a terminal of the polyamide-based resin as an amino group, the amino group having at least one alkenyl group or alkynyl group, Alternatively, it is preferable to cap the amide using an acid anhydride containing a cyclic compound group. Thereby, preservability can be improved. Examples of such a group derived from an acid anhydride containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include formula (9), formula (
And the group represented by 10). These may be used alone or in combination of two or more.

（上式（９）中のＲ_１９は水素、またはメチル基を表す。）

(R ₁₉ in the above formula (9) represents hydrogen or a methyl group.)

（式（１０）中のＲ_２０は水素、またはメチル基を表す。）

(R ₂₀ in formula (10) represents hydrogen or a methyl group.)

Of these, a group selected by the following formula (11) is particularly preferable. Thereby, especially storability can be improved.

The method is not limited to this method, and the terminal acid contained in the polyamide-based resin is converted into an amide using an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. It can also be capped.

The polyamide-based resin having a repeating unit represented by the general formula (2) may have a nitrogen-containing heterocyclic compound in at least one of the side chain and the other end. Thereby, adhesiveness with a metal wiring (especially copper wiring) etc. can be improved. The reason is that in the case where one end of the polyamide-based resin represented by the above formula (2) is an organic group having an unsaturated group, the resin reacts, so that mechanical properties such as tensile elongation of the cured film are excellent, This is because, when the nitrogen-containing heterocyclic compound is present in at least one of the side chain and the other end, the nitrogen-containing heterocyclic compound reacts with the metal wiring of copper and copper alloy, and thus the adhesion is excellent.
Examples of the nitrogen-containing heterocyclic compound include 1- (5-1H-triazoyl) methylamine, 3- (1H-pyrazoyl) amine, 4- (1H-pyrazoyl) amine, 5- (1H-pyrazoyl) amine, 1 -(3-1H-pyrazolyl) methylamine, 1- (4-1H-pyrazoyl) methylamine, 1- (5-1H-pyrazoyl) methylamine, (1H-tetrazol-5-yl) amine, 1- (1H -Tetrazol-5-yl) methyl-amine, 3- (1H-tetrazol-5-yl) benz-amine and the like. Among these, the compound selected by the formula (12) is preferable. Thereby, especially adhesiveness with the metal wiring of copper and a copper alloy can be improved more.

The photosensitive agent (B) used in the present invention is a compound that generates an acid by light.
Examples of the compound that generates an acid by light include onium salts such as diphenyliodonium salt and triphenylsulfonium salt, 2-nitrobenzyl esters, N-iminosulfonates, arylsulfonate esters, and halogens such as chlorine. Examples include heterocyclic compounds and photosensitive diazoquinone compounds.
Among these compounds, a photosensitive diazoquinone compound is preferred because it has the highest sensitivity and resolution in the wavelength range of actinic radiation mainly used for exposure. Examples of the photosensitive diazoquinone compound include esters of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Specific examples include ester compounds represented by formula (13) to formula (17). These may be used alone or in combination of two or more.

（上記式（１３）中のＲ_２１は、水素、またはメチル基である。）

(R ₂₁ in the above formula (13) is hydrogen or a methyl group.)

（上記式（１５）中のＲ_２２は、水素、またはメチル基である。）

(R ₂₂ in the above formula (15) is hydrogen or a methyl group.)

（上記式（１６）中のＲ_２３は、水素、またはメチル基である。）

(R ₂₃ in the above formula (16) is hydrogen or a methyl group.)

（上記式（１７）中のＲ_２４は、水素、またはメチル基である。）

(R ₂₄ in the above formula (17) is hydrogen or a methyl group.)

In the formulas (13) to (17), Q is selected from a hydrogen atom or any one of the following formulas (18) and (19). Here, at least one of Q of each compound is represented by formula (18) or formula (19).

  The addition amount of the photosensitive agent (B) according to the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). More preferably, it is 10 to 40 parts by weight. When the addition amount is within the above range, the sensitivity is particularly excellent.

In the positive photosensitive resin composition according to the present invention, the nitrogen-containing compound (C) represented by the general formula (1) is used.
Examples of the electron-withdrawing group of the nitrogen-containing compound (C) represented by the general formula (1) include a sulfonyl group, a sulfinyl group, a carbonyl group, a thiocarbonyl group, an imino group, a nitro group, a nitroso group, and a cyano group. It is done. The presence of electron withdrawing groups on both sides of the NH group activates the NH group very strongly. By this action, the acidity of the molecule is increased, and it is considered that the effect of high sensitivity, high resolution, and high cyclization rate when cured at a low temperature is exhibited.
Among electron-withdrawing groups, a sulfonyl group and a carbonyl group are excellent in that they have high sensitivity and high resolution, and have a high cyclization rate even when cured at a low temperature.
When the nitrogen-containing compound (C) represented by the above general formula (1) is used, the dissolution rate of the exposed portion with respect to the developer is increased and the sensitivity is improved and the occurrence of scum is suppressed as compared with the conventional case. Furthermore, a high cyclization rate is obtained even when cured at a low temperature. Examples of the nitrogen-containing compound (C) represented by the general formula (1) of the present invention include compounds represented by the following formulas (20) and (21) when the electron-withdrawing group is a sulfonyl group.

If the electron withdrawing group is a carbonyl compound, a compound represented by the following formula (22) may be mentioned.

Among these, a compound selected from the following formula (23) is particularly preferable. This improves the effect of achieving high cyclization rate when cured at high sensitivity, high resolution, and low temperature.

  The addition amount of the nitrogen-containing compound (C) represented by the general formula (1) according to the present invention is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). More preferably, it is 1-30 weight part. When the addition amount is within the above range, the sensitivity is particularly excellent.

[Other ingredients]
(Adhesion aid)
The photosensitive resin composition of the present invention may contain an adhesion assistant.
The adhesion assistant is a component having a function of improving the bonding strength between the coating film obtained by curing the photosensitive resin composition and the substrate on which the coating film is formed.
Examples of such adhesion assistants include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Methoxysi 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanate Examples include, but are not limited to, propyltriethoxysilane, a silicon compound obtained by reacting an amino group-containing silicon compound with an acid dianhydride or an acid anhydride, and the like.

The silicon compound having an amino group is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyl. Examples include methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane.
The acid dianhydride or acid anhydride is not particularly limited, and examples thereof include maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, and phthalic anhydride. Moreover, in using, it can be used individually or in combination of 2 or more types.

In the present invention, these components are dissolved in a solvent and used in the form of a varnish.
Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropio And the like, and may be used alone or in combination.

  Further, in the photosensitive resin composition of the present invention, additives such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a crosslinking agent, a terminal blocking agent, and a sensitizer are added as necessary. May be.

<Method for forming cured film>
Next, a method for forming a cured film (protective film, insulating film) using the photosensitive resin composition of the present invention will be described.
First, the photosensitive resin composition of the present invention is applied to an appropriate support (substrate), for example, a silicon wafer, a ceramic substrate, an aluminum substrate or the like. When applied on a silicon wafer (semiconductor element), the coating amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is below the lower limit value, it will be difficult to fully function as a protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. Takes a long time to reduce throughput. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like.

Next, after pre-baking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the desired pattern shape (exposure process). As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.
Next, a pattern is obtained by dissolving and removing the irradiated portion with a developer (developing step).
Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, di- Secondary amines such as n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An aqueous solution of an alkali such as a quaternary ammonium salt and an aqueous solution in which an appropriate amount of a water-soluble organic solvent or a surfactant such as alcohols such as methanol or ethanol is added thereto can be suitably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

Next, the relief pattern formed by development is rinsed (cleaned) (cleaning step). Distilled water is used as the rinse liquid.
Next, a heat treatment is performed to cause the benzoxazole precursor structure and the imide precursor structure to undergo a cyclization reaction to form a benzoxazole ring and an imide ring, resulting in a heat resistant final pattern (cured film, protective film, insulating film) Is obtained (heat treatment step).
The heat treatment temperature is preferably 180 ° C to 380 ° C, more preferably 200 ° C to 350 ° C.

The cured film formed using the photosensitive resin composition of the present invention is used not only for semiconductor devices such as semiconductor elements, but also for display devices such as TFT (Thin Film Transistor) type liquid crystal and organic EL (Electro-Luminescence). It is also useful as an interlayer insulation film for multilayer circuits, a cover coat for flexible copper-clad plates, a solder resist film, and a liquid crystal alignment film.
Examples of semiconductor device applications include a passivation film formed by forming a cured film of the above-described positive photosensitive resin composition on a semiconductor element, and a cured film of the above-described photosensitive resin composition formed on the passivation film. A protective film such as a buffer coat film, an insulating film such as an interlayer insulating film formed by forming a cured film of the above-mentioned positive photosensitive resin composition on a circuit formed on a semiconductor element, and an α ray Examples thereof include a blocking film, a planarizing film, a protrusion (resin post), and a partition wall.
Examples of the display device application include a protective film formed by forming a cured film of the photosensitive resin composition of the present invention on a display element, an insulating film or a planarizing film for TFT elements and color filters, MVA ( For example, protrusions for a multi-domain vertical alignment (liquid crystal display) type liquid crystal display device, partition walls for an organic EL element cathode, and the like can be given.

The usage method is based on forming the positive photosensitive resin composition layer patterned on the substrate on which the display element and the color filter are formed according to the semiconductor device application by the above method. High transparency is required for display device applications, particularly for insulating films and flattening films, but a post-exposure step is introduced before the coating film prepared using the photosensitive resin composition of the present invention is cured. Accordingly, a resin layer having excellent transparency can be obtained, which is more preferable in practical use.
The photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device of the present invention have been described above, but the present invention is not limited to these.
For example, the semiconductor device to which the photosensitive resin composition of the present invention is applied is not limited to the one having the above configuration.
The photosensitive resin composition of the present invention can be used not only for forming a protective film or insulating film of a semiconductor element as described above, but also for forming a spacer of a semiconductor element, for example.

Hereinafter, the present invention will be described specifically by way of examples.
<Example 1>
[Synthesis of Alkali-soluble Resin (A-1)]
Dicarboxylic acid obtained by reacting diphenyl ether-4,4′-dicarboxylic acid 232.4 (0.9 mol) with 1-hydroxy-1,2,3-benzotriazole 243.2 (1.8 mol) 443.2 g (0.9 mol) of the derivative (active ester) and 366.3 g (1 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were added to a thermometer, a stirrer, and raw materials. The flask was placed in a four-necked separable flask equipped with a dry nitrogen gas inlet tube, and 3200 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath.
Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 100 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the target formula (A An alkali-soluble resin represented by -1) was obtained.

[Synthesis of photosensitive diazoquinone compound]
A thermometer containing 11.04 g (0.026 mol) of phenol represented by the formula (P-1), 17.20 g (0.064 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 160 g of acetone. The mixture was stirred and dissolved in a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, a mixed solution of 7.08 g (0.07 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 0.96 g (0.016 mol) of acetic acid was added, and the mixture was further reacted for 30 minutes. After filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (900 ml / 9 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and expressed by the formula (B-1). The indicated photosensitizer was obtained.

[Preparation of positive photosensitive resin composition]
100 g of the alkali-soluble resin represented by the formula (A-1) synthesized, 15 g of the photosensitive diazoquinone compound of the formula (B-1), 10 g of the nitrogen-containing compound represented by the following formula (C-1), and 130 g of γ-butyrolactone Then, the solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to obtain a positive photosensitive resin composition. The following evaluation was performed using the obtained positive photosensitive resin composition.

[Sensitivity, Resolution (Photosensitivity)]
The positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then prebaked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 8.0 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern with a width of 0.88 to 50 μm are drawn), an i-line stepper (manufactured by Nikon Corporation, 4425i) ) was used to irradiate while changing the exposure dose in 10 mJ / cm ² increments from 100 mJ / cm ² to 780mJ / cm ^2.
Next, using a 2.38% tetramethylammonium hydroxide aqueous solution, paddle development was performed by adjusting the development time so that the film thickness difference between the pre-baked and the unexposed areas after development was 1 μm. Then, it rinsed with the pure water for 10 seconds. As a result, it was confirmed that a pattern was formed from a portion irradiated with an exposure amount of 320 mJ / cm ² (sensitivity was 320 mJ / cm ² ).
. The resolution at this time was as high as 4 μm.

[Cyclization rate]
The positive photosensitive resin composition was applied onto two silicon wafers using a spin coater and then prebaked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 10 μm. Next, one silicon wafer with a coating film was heated at 320 ° C. for 30 minutes using an oven, and then immersed in a 2% aqueous hydrofluoric acid solution to obtain a film. The film was measured using a Fourier transform infrared spectrophotometer (manufactured by JASCO) was calculated ratio of the peak (A) associated with the wholly aromatic oxazole ring and 1490cm ^-1 of 1050 cm ^-1. At this time, 320 ° C. 30
The cyclization rate when heated in minutes is converted to 100%. Then, after heating at 250 ° C. 30 minutes in an oven, Interested cured film, a Fourier transform infrared spectrophotometer from measurements by (Nippon Bunko) of 1050 cm ^-1 of the oxazole ring and 1490cm ^-1 The peak ratio (B) associated with total aromatics was calculated. The cyclization rate was a value obtained by multiplying (B / A) by 100. The cyclization rate thus determined was 90%.

<Example 2>
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the amount of the nitrogen-containing compound represented by (C-1) in Example 1 was increased to 30 g. And resolution) evaluation and cyclization rate evaluation.
<Example 3>
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the amount of the nitrogen-containing compound represented by (C-1) in Example 1 was reduced to 1 g. And resolution) evaluation and cyclization rate evaluation.
<Example 4>
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the nitrogen-containing compound represented by (C-1) in Example 1 was changed to the following formula (C-2). Characteristic (sensitivity and resolution) evaluation and cyclization rate evaluation were performed.
<Example 5>
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the nitrogen-containing compound represented by (C-1) in Example 1 was changed to the following formula (C-3). Characteristic (sensitivity and resolution) evaluation and cyclization rate evaluation were performed.

<Example 6>
[Synthesis of alkali-soluble resin (A-2)]
It was obtained by reacting terephthalic acid 149.5 (0.9 mol), isophthalic acid 16.6 (0.1 mol) and 1-hydroxy-1,2,3-benzotriazole 270.3 (2 mol). Of dicarboxylic acid derivative (active ester) 360.2 g (0.9 mol) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 366.3 g (1 mol) Into a four-necked separable flask equipped with a raw material inlet and a dry nitrogen gas inlet tube, 3000 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 500 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the formula (A-2 ) Polyamide resin was obtained.

[Preparation of positive photosensitive resin composition]
100 g of the synthesized polyamide resin of the formula (A-2), 15 g of the photosensitive diazoquinone compound of the above formula (B-1), and 10 g of the nitrogen-containing compound represented by the above formula (C-1) were dissolved in 130 g of γ-butyrolactone. Thereafter, the mixture was filtered through a 0.2 μm Teflon (registered trademark) filter to obtain a positive photosensitive resin composition. Evaluation similar to Example 1 was performed using the obtained positive photosensitive resin composition.

<Example 7>
[Synthesis of photosensitive diazoquinone compound]
A thermometer containing 14.4 g (0.025 mol) of phenol represented by the formula (P-2), 22.3 g (0.083 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 160 g of acetone. The mixture was stirred and dissolved in a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C., a mixed solution of 8.4 g (0.083 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting for 3 hours at room temperature, 0.96 g (0.016 mol) of acetic acid was added, and the mixture was further reacted for 30 minutes. After filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (900 ml / 9 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and of formula (B-2) A photosensitizer was obtained. Evaluation similar to Example 1 was performed using the obtained positive photosensitive resin composition.

［ポジ型感光性樹脂組成物の作製］
上記合成した式（Ａ−１）のポリアミド樹脂１００ｇ、上記式（Ｂ−２）の感光性ジアゾキノン化合物１５ｇ、上記式（Ｃ−１）で示される含窒素含有化化合物１０ｇをγ−ブチロラクトン１３０ｇに溶解した後、０．２μｍのテフロン（登録商標）フィルターで濾過しポジ型感光性樹脂組成物を得た。得られたポジ型感光性樹脂組成物を用いて、実施例１と同様の評価を行った。

[Preparation of positive photosensitive resin composition]
100 g of the synthesized polyamide resin of the formula (A-1), 15 g of the photosensitive diazoquinone compound of the formula (B-2), and 10 g of the nitrogen-containing compound represented by the formula (C-1) are converted into 130 g of γ-butyrolactone. After dissolution, the mixture was filtered through a 0.2 μm Teflon (registered trademark) filter to obtain a positive photosensitive resin composition. Evaluation similar to Example 1 was performed using the obtained positive photosensitive resin composition.

[Example 8]
[Fabrication and evaluation of semiconductor devices]
A semiconductor device having bumps was prepared and evaluated using the positive photosensitive resin composition of the present invention.
FIG. 1 shows an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump according to the present invention. As shown in FIG. 1, an input / output Al pad 2 is provided on a silicon substrate 1 having a semiconductor element and wiring provided on the surface, and a passivation film 3 is formed thereon, and the passivation film 3 is formed on the passivation film 3. A via hole was formed. On this, the positive photosensitive composition prepared above is applied and dried to form a positive photosensitive resin (buffer coat film) 4, and a metal (Cr, Ti, etc.) film 5 is connected to the Al pad 2. The metal film 5 was etched around the solder bump 9 to insulate the pads. A barrier metal 8 and a solder bump 9 are formed on the insulated pad to obtain a semiconductor device.
The semiconductor device obtained as described above has a good yield and high reliability.

<Comparative Example 1>
A positive photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the nitrogen-containing compound represented by the formula (C-1) in Example 1 was excluded.

It is sectional drawing of the pad part of the semiconductor device which shows the Example of this invention.

1 Silicon substrate 2 Al pad 3 Passivation film 4 Buffer coat film 5 Metal (Cr, Ti, etc.) film 6 Wiring (Al, Cu, etc.)
7 Insulating film 8 Barrier metal 9 Solder bump

Claims (13)

A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and a nitrogen-containing compound (C) represented by the following general formula (1).

(R represents an organic group. A represents an electron-withdrawing group.) The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) is a polyamide-based resin having a repeating unit represented by the following general formula (2).

(In the formula, X and Y are organic groups. R ₁ is a hydroxyl group, —O—R ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₂ is a hydroxyl group or a carboxyl group. , —O—R ₃ , —COO—R ₃ , which may be the same or different, m is an integer of 0 to 8, n is an integer of 0 to 8. R ₃ is an integer of 1 to Here, when there are a plurality of R _{1 s} , they may be different or the same, and when R ₁ has no hydroxyl group, at least one R ₂ must be a carboxyl group. In addition, when R ₂ has no carboxyl group, at least one R ₁ must be a hydroxyl group. The positive photosensitive resin composition according to claim 2, wherein X of the polyamide-based resin having a repeating unit represented by the general formula (2) includes one or more selected from the group consisting of the following formula (3). object.

(Here, * indicates bonding to an NH group. D in the above formula (3) is —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, — S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, where R ₄ is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group. And may be the same or different, and is an integer of s = 0 to 3.) The positive photosensitive resin according to claim 2 or 3, wherein Y of the polyamide-based resin having a repeating unit represented by the general formula (2) includes one or more selected from the group consisting of the following formula (4). Resin composition.

(Here, * indicates bonding to a C═O group. E in the above formula (4) is —SO ₂ —, —CO—, —O—, and R ₅ represents an alkyl group or an alkyl ester.) Group, alkyl ether group,
It represents one selected from a benzyl ether group and a halogen atom, and each may be the same or different. t is an integer of 0-4. ) The positive photosensitive composition according to any one of claims 1 to 4, wherein A of the nitrogen-containing compound (C) represented by the general formula (1) is a sulfonyl group. The positive photosensitive composition according to any one of claims 1 to 4, wherein A of the nitrogen-containing compound (C) represented by the general formula (1) is a carbonyl group. The nitrogen-containing compound (C) represented by the general formula (1) is included in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). Positive photosensitive resin composition. The positive photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) is a photosensitive diazoquinone compound. The cured film comprised with the hardened | cured material of the positive photosensitive resin composition of any one of Claim 1 thru | or 8. A protective film comprising the cured film according to claim 9. The insulating film comprised with the cured film of Claim 9. A semiconductor device comprising the cured film according to claim 9. The display body apparatus which has the cured film of Claim 9.

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