JP2013142763A - Method for forming coating film of positive type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a coating film of a positive type photosensitive resin composition capable of removing a resin coating film at an end part with a solvent with no resin residues at the end part of a support in an edge cutting step when a coating film of a positive type photosensitive resin composition is formed on a support.SOLUTION: There is provided a method for forming a coating film of a positive type photosensitive resin composition, the method comprising the steps of: applying a positive type photosensitive resin composition on a support and performing an edge cutting with a solvent, wherein in the edge cutting step, at least a first operation for removing the end part of the coating film is performed by supplying a solvent to the end part of the coating film while rotating the support to which the positive type photosensitive resin composition is applied at a circumferential speed of 1.9 m/s or more and 16 m/s or less and a second operation for drying the solvent is performed by rotating the support slower than the circumferential speed in the first operation after the first operation.

Description

  The present invention relates to a method for forming a coating film of a positive photosensitive resin composition.

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protective films and interlayer insulating films of semiconductor elements.
Here, in order to simplify the process when a polybenzoxazole resin or a polyimide resin is used, a positive photosensitive resin composition in which a diazoquinone compound as a photosensitive material is combined with these resins is also used.
In recent years, due to miniaturization of semiconductor elements, multilayer wiring by high integration, transition to chip size package (CSP), wafer level package (WLP), etc., the damage to semiconductor elements has been reduced, so it has excellent low stress properties There is a need for polybenzoxazole resins and polyimide resins. Generally, these positive-type photosensitive resin compositions are spin-coated on a support substrate such as a silicon wafer to form a uniform film, and are subjected to heat treatment, exposure, development, curing, etching, ashing, and other treatments to produce a semiconductor. Manufacture devices.
The positive photosensitive resin is usually used as a varnish-like solution dissolved in a solvent, and is applied while rotating the substrate on a support substrate such as a silicon wafer. At this time, the resin may adhere to the edge of the substrate and contaminate the inside of the coating / developing machine transport system and the exposure machine. Has been done.
However, in the case of polybenzoxazole resin or polyimide resin, the film thickness is so large that the solvent does not completely dissolve in the solvent in the edge cut process and the resin remains at the place to be removed at the end. was there. In recent years, the size of wafers has increased, making it difficult to perform edge cut processing under appropriate conditions.

JP 2003-218097 A

  The present invention has been made in view of the above circumstances, and the object of the present invention is to provide an edge cut step when forming a coating film of a positive photosensitive resin composition on a support at the end of the support. It is an object of the present invention to provide a method for forming a coating film of a positive photosensitive resin composition that can remove a resin coating film at an end with a solvent without a resin residue. Furthermore, it is providing the coating-film formation method which can perform the optimal edge cut process with a 300 mm board | substrate.

Such an object is achieved by the present invention described in [1] to [6].
[1] A coating film forming method for forming a coating film of a positive photosensitive resin composition on a support,
An application step of applying a positive photosensitive resin composition to a support;
It has an edge cut process that performs an edge cut process with a solvent,
In the edge cutting step, at least the support coated with the positive photosensitive resin composition is rotated at a peripheral speed of 1.9 m / s to 16 m / s, and the solvent is supplied to the edge of the coating film. By the first operation to remove the end of the coating film,
A second operation for drying the solvent by rotating the support slower than the first operation after the first operation;
A method for forming a coating film of a positive photosensitive resin composition.
[2] The method for forming a coating film of the positive photosensitive resin composition according to [1], wherein the peripheral speed of the support in the second operation is 0.4 m / s or more and 4.8 m / s or less.
[3] The method for forming a coating film of the positive photosensitive resin composition according to [1] or [2], wherein the treatment time in the second operation is 1 second or more and 3 seconds or less.
[4] The method for forming a coating film of the positive photosensitive resin composition according to any one of [1] to [3], wherein the solvent used in the first operation has a boiling point of 110 ° C. or higher and 220 ° C. or lower. .
[5] The solvent used in the first operation is one or a mixture of two or more selected from propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, and N-methyl-2-pyrrolidone. The method for forming a coating film of the positive photosensitive resin composition according to any one of [1] to [4].
[6] The positive type according to any one of [1] to [5], wherein a 300 mm substrate having a peripheral speed of the support in the first operation of 7.9 m / s to 16 m / s is used. A method for forming a coating film of a photosensitive resin composition.

  In the manufacturing process of semiconductor devices, in the edge cutting process when forming a coating film of a positive photosensitive resin composition on a support substrate such as a silicon wafer, there is no resin residue at the end of the substrate and the resin at the end with a solvent. An object of the present invention is to provide a method for forming a coating film of a positive photosensitive resin composition capable of removing the coating film.

Hereinafter, the coating film forming method for forming a coating film of the positive photosensitive resin composition on the support of the present invention will be described in detail.
The method of forming a coating film of the positive photosensitive resin composition on the support of the present invention includes an application step of applying the positive photosensitive resin composition to the support, and an edge of the support with a solvent by using a solvent. An edge cutting step of performing a cutting treatment, and in the edge cutting step, at least while rotating the support coated with the positive photosensitive resin composition at a peripheral speed of 1.9 m / s to 16 m / s, The solvent is dried by supplying the solvent to the edge of the coating film to remove the edge of the coating film and rotating the support later than the first operation after the first operation. The second operation is performed.

Hereinafter, the method for forming a coating film of the positive photosensitive resin composition on the support of the present invention will be described in detail.
The coating process according to the present invention is a process for preparing a coating film by coating a positive photosensitive resin composition on a support (substrate). Here, the support is, for example, a silicon wafer, a ceramic substrate, an aluminum substrate, or the like. When applied on the semiconductor element, the applied amount is applied so that the final film thickness after curing is 0.1 μm or more and 30 μm or less. The film thickness can be adjusted by changing the peripheral speed during application. By setting the film thickness within the above range, the function as a protective surface film of the semiconductor element can be sufficiently exhibited, a fine processing pattern can be formed, and the processing time can be shortened.
Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like.

In the edge cutting step of performing edge cutting with the solvent according to the present invention, at least rotating the support on which the positive photosensitive resin composition is applied, the solvent is supplied to the edge of the coating film, By performing a first operation for removing the edge and a second operation for drying the solvent by rotating the support slower than the first operation after the first operation, This is a step of performing edge cut processing at the end.
For the purpose of edge cutting, when transporting and adjusting the position of the substrate on which the resin film is formed, the end of the substrate comes into contact with the transport arm / equipment and the resin may come off and cause particles. This is to prevent such a situation. Therefore, in the manufacturing process of a semiconductor device, an edge cutting process is conventionally performed to remove the resin film at the end.
The first operation is an operation of removing the resin film with the solvent at the end of the support, an operation of supplying the solvent to the end after forming the coating film, and rotating the support to remove the resin at the end. is there.
In general, the removal of the resin at the end by the solvent (edge cut process) is a method of removing the resin film by rotating the support and simultaneously supplying the solvent to the end, and the edge by an edge exposure machine. There is a method in which the resin film is dissolved by a development treatment after the exposure. Among them, the method using the edge exposure machine has an additional disadvantage that the processing time per wafer becomes long because the exposure processing is added. Therefore, many methods have been adopted in which a positive photosensitive resin composition is supplied while a support is rotated to form a coating film, and at the same time, a solvent is discharged to perform an edge cut process.
Therefore, in the first operation according to the present invention, the positive photosensitive resin composition is supplied while the support is rotated to form a coating film, and at the same time, a solvent is supplied to the end portion of the resin coating film. Formation and removal of the resin coating on the edge. In the first operation, the solvent supply method is a method in which the solvent is supplied from a discharge nozzle dedicated to the solvent and the solvent is supplied to the end of the support. At this time, it is possible to appropriately select the diameter and angle of the discharge nozzle, the edge cut width, and the like by setting the conditions of the equipment or the coating and developing machine so as to meet the target conditions.

The edge cutting process using a solvent is performed after the coating film of the positive photosensitive resin composition is formed and before the coating film is dried using a hot plate or the like. Since the positive photosensitive resin composition is used as a varnish dissolved with a solvent or the like, a large amount of the solvent remains.
About the removability of the resin film of the edge part by an edge cut process, it is influenced by the film thickness and dry state of the coating film to form, the solubility with respect to resin of the solvent to be used, etc. Moreover, in the removal of the coating film at the end by the solvent, the coating film at the end is removed while rotating the support, but at this time, the resin moves toward the outer periphery of the support by centrifugal force, A phenomenon in which the resin component exudes again from the outermost peripheral portion of the resin film occurs at the end from which the resin is removed.

In the present invention, as a result of intensive studies on the problem that the resin residue at the end portion remains, the peripheral speed of the support in the first operation is set to 1.9 m / s or more and 16 m / s or less. Thus, it was found that there is no resin residue at the end and the resin at the end can be removed. Here, the peripheral speed is the speed at the maximum radius position of the rotating object. When the rotation speed is n and the maximum radius is R, the peripheral speed is 2πnR.
In the first operation, the rotation at a peripheral speed of 1.9 m / s or more is for moving the resin on the coating film by centrifugal force, and the rotation at 16 m / s or less is caused by a centrifugal force that is too high. This is to prevent ooze out in the outer circumferential direction.
Preferably, it is 3 m / s or more and 15.9 m / s or less.
Further, for a 300 mm substrate, the peripheral speed is preferably 7.9 m / s or more and 16 m / s or less.
Here, the 300 mm substrate is, for example, a wafer having a diameter of 12 inches, and may be a 300 mm substrate having a circuit formed on the surface thereof.

The second operation is an operation of drying the solvent while rotating the support after the first operation. The drying operation is performed while rotating the support at a peripheral speed of 0.4 m / s to 4.8 m / s. It is preferable. The second operation is an operation of removing the solvent in the removed portion while rotating the support. When the peripheral speed is 0.4 m / s or more, the solvent removal effect tends to be low and 4.8 m / s. When the rotation is performed as described above, the centrifugal force is too high, so that the resin easily oozes out in the outer peripheral direction.
Preferably, it is 0.6 m / s or more and 4 m / s or less.
By performing the edge cut processing of the coating film of the positive photosensitive resin composition within the range of the peripheral speed, there is no resin residue on the end on the support, and the end resin can be removed with a solvent. .

As the solvent used in the first operation, the positive photosensitive resin composition dissolved after forming the coating film of the positive photosensitive resin composition and adhering to the back surface, side surface, or outer periphery of the support of the apparatus is used as the solvent. What is necessary is just to be dissolved.
As the solvent used in the positive photosensitive resin composition, since there are many solvent systems having a high boiling point, it is preferable that the solvent used for the first operation is relatively excellent in solubility, and the boiling point of the solvent is 110 ° C. or higher and 220 ° C. The following is preferable. When the boiling point is less than 110 ° C., only the solvent is dried, so that only the resin component remains. Conversely, when it exceeds 220 ° C., the solvent itself is not easily dried but remains with the resin film.
Examples of the solvent 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-methoxypro Examples include pionate and butyl acetate.
In the manufacture of semiconductor devices and the like, a substrate of 300 mm is currently widely used, and from the viewpoint of solubility and boiling point, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, N-methyl-2-pyrrolidone, acetic acid One or a mixture of two or more selected from butyl is preferred.

Moreover, the said coating film may be prebaked after the said application | coating process and an edge cut process, a solvent may be volatilized, and a coating film may be dried.
As the prebaking method, a heating device such as a hot plate or an oven is used, and the heating temperature is preferably 60 to 140 ° C, more preferably 100 to 130 ° C. When heating, it is possible to reduce the oxidation of the coating film by flowing an inert gas such as nitrogen in the heating device.

Here, the positive photosensitive resin composition according to the present invention will be described in detail.
In addition, the following is an illustration and the positive photosensitive resin composition which concerns on this invention is not limited to the following.
Examples of the positive photosensitive resin composition according to the present invention include those containing an alkali-soluble resin (A) and a photosensitive diazoquinone compound (B).

Examples of the alkali-soluble resin (A) include novolak resins, resol resins, hydroxystyrene resins, hydroxystyrene resin derivatives, acrylic resins such as methacrylic acid resins and methacrylic ester resins, cyclic olefins containing hydroxyl groups, carboxyl groups, and the like. Resin, polyamide resin and the like.
Of these, novolak resin, resol resin, hydroxystyrene resin, hydroxystyrene resin derivative, and polyamide-based resin are preferred from the viewpoint of excellent heat resistance and good mechanical properties. Specifically, at least polybenzoxazole structure and polyimide structure are preferred. A resin having a hydroxyl group, carboxyl group, ether group or ester group in the main chain or side chain, a resin having a polybenzoxazole precursor structure, a resin having a polyimide precursor structure, or a polyamic acid ester structure Resin etc. are mentioned.
As such a polyamide-type resin, the polyamide-type resin containing the structure shown by following formula (1) can be mentioned, for example. Moreover, it is preferable that the repeating unit of the structure shown by following formula (1) is 2-300.

（式中、Ｘ、Ｙは有機基である。Ｒ１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および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。）

(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, a carboxyl group, _-O-R 3, are either _{-COO-R 3,} good .m and n be the same or different .R ₃ is an integer from 0 to 8 is an organic group having 1 to 15 carbon atoms. here, when R ₁ is more than one if there is no hydroxyl group as a good .R ₁ be the same or different, respectively, R ₂ is at least one must be a carboxyl group. the carboxyl group as R ₂ In the absence of at least one R ₁ must be a hydroxyl group.)

In the polyamide resin containing the structure represented by the general formula (1), _-O-R 3 as a substituent of the _-O-R 3, Y as a substituent of X, _{-COO-R 3} represents a hydroxyl group, For the purpose of adjusting the solubility of the carboxyl group in an alkaline aqueous solution, it is a group protected by R ₃ , which is an organic group having 1 to 15 carbon atoms. If necessary, the hydroxyl group and the carboxyl group may be protected. 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-based resin having the structure represented by the general formula (1) includes, for example, a compound selected from diamine containing X or bis (aminophenol), 2,4-diaminophenol, and dicarboxylic acid or dicarboxylic acid containing Y. It is obtained by reacting with a compound selected from acid dichloride, dicarboxylic acid derivatives and the like.
In the case of a dicarboxylic acid, an active ester 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 (1) include aromatic compounds such as a benzene ring and a naphthalene ring, heterocyclic compounds such as bisphenols, pyrroles, and furans, and siloxane compounds. What is shown by following formula (2) 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Ａは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_３−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_４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。Ｒ_５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＝０〜２の整数である。Ｒ_６〜Ｒ_９は有機基である。）

(Here, * indicates bonding to an NH group. In the formula, A represents —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₃ —, —O—, —S—, — SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ₄ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, R ₅ may be an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, and may be the same or different, and is an integer of r = 0 to 2. R ₆ to R ₉ is an organic group.)

As shown by the general formula (1), 0 to 8 R ₁ are bonded to X (in the formula (1), R ₁ is omitted).

Particularly preferred among the formulas (2) include those represented by the following formula (3), which are particularly excellent in heat resistance and mechanical properties (however, some of them contain R _{1 in the} formula (1)). It is done.

（式中、＊はＮＨ基に結合することを示す。式中Ｄは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合である。Ｒ_１０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_１１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＝１〜３、ｔ＝０〜２の整数である。）

(In the formula, * indicates bonding to an NH group. In the formula, D represents —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, And —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ₁₀ is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, R ₁₁ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and each may be the same or different, and s = 1 to 3, t = 0. (It is an integer of 2.)

  Y in the general formula (1) 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 of these is mentioned, More specifically, what is shown by following formula (4) 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Ａは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_３−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、又は単結合である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、それぞれ同じでも異なっていてもよい。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つを表す。ｕ＝０〜２の整数である。Ｒ_１４〜Ｒ_１７は有機基である。）

(Here, * indicates bonding to a C═O group. In the formula, A represents —CH ₂ —, —C (CH ₃ ) ₃ —, —O—, —S—, —SO ₂ —, —CO). -, - NHCO -, - C (CF 3) 2 -, or a single bond and is _{R 12} is an alkyl group, an alkyl ester group, represents one selected from among a halogen atom, be the same or different R ₁₃ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, u is an integer of 0 to 2, and R _{14 to} R ₁₇ are organic groups.)

As shown by the general formula (1), 0 to 8 R ₂ are bonded to Y (in the formula (4), R ₂ is omitted).

Among these, particularly preferable are those represented by the following four structures (5) having particularly excellent heat resistance and mechanical properties and those represented by the following four structures containing Si among the above formula (3) (however, the formula ( Some of them include R _{2 of} 1)).
Regarding the structure derived from tetracarboxylic dianhydride in the following formula (5), the position where both C═O groups are bonded is the meta position, and both are the para positions. 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。Ｒ_１８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。Ｒ_１９は、水素原子又は炭素数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よい。ｖ＝０〜２の整数である。）

(In the formula, * represents bonding to a C═O group. R ₁₈ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, R ₁₉ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted, and v is an integer of 0 to 2. is there.)

In addition, the polyamide-based resin represented by the general formula (1) is an acid containing a terminal amino group, an aliphatic group having at least one alkenyl group or alkynyl group, or a cyclic compound group. It is preferred to cap as an amide using an anhydride or acid derivative. Thereby, the preservability of positive photosensitive resin composition can be improved.
Examples of the acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group that reacts with the amino group of the polyamide-based resin include maleic anhydride, bicyclo [2.2. 1] Hepta-5-ene-2,3-dicarboxylic anhydride, 4-ethynylphthalic anhydride, 4- (phenylethynyl) phthalic anhydride, and the like. For example, this is Equation (6). An acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group that reacts with an amino group is a carboxylic acid containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. An acid derivative formed by substituting the OH group of a carboxyl group of an acid or a polyvalent carboxylic acid, such as a halide of carboxylic acid, for example, formula (7) is preferred. These may be used alone or in combination of two or more.

  Of these, a group selected from the following formula (8) is particularly preferable. Thereby, preservability can be improved more.

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

  The photosensitive diazoquinone compound (B) used in the present invention is, for example, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Can be mentioned. Specific examples include ester compounds represented by the formulas (9) to (12). These may be used alone or in combination of two or more.

(式中、Ａは有機基、Ｒ_２０〜Ｒ_２３は水素原子、又はアルキル基、Ｒ_２４〜Ｒ_２７は水
素原子、水酸基、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、シクロアルキル基の中から選ばれる１つを表し、それぞれ同じでも異なっていてもよい。ｎ〜ｑは０〜４の整数である。)

(In the formula, A represents an organic group, R _{20 to} R ₂₃ represent a hydrogen atom or an alkyl group, and R _{24 to} R ₂₇ represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, or a cycloalkyl group. And each of them may be the same or different, and n to q are integers of 0 to 4.)

式中Ｑは、水素原子、式（１３）、式（１４）のいずれかから選ばれるものである。ここで各化合物のＱのうち、少なくとも１つは式（１３）、式（１４）である。

In the formula, Q is selected from a hydrogen atom, formula (13), and formula (14). Here, at least one of Q of each compound is represented by formula (13) or formula (14).

  As for the addition amount of the photosensitive diazoquinone compound (B) used for this invention, 1-50 weight part is preferable with respect to 100 weight part of 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.

The positive photosensitive resin composition used in the present invention may contain an additive such as an acrylic, silicone, fluorine or vinyl leveling agent or a silane coupling agent, if necessary.
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and 3-methacryloxy. Propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanate Although propyl triethoxysilane etc. are mentioned, it is not limited to these.

  In the present invention, these components are preferably 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.

Example 1
[Synthesis of Alkali-soluble Resin (A-1)]
393.96 g of dicarboxylic acid derivative (active ester) obtained by reacting 0.8 mol of diphenyl ether-4,4′-dicarboxylic acid with 1.6 mol of 1-hydroxy-1,2,3-benzotriazole (0 0.8 mol) and 366.26 g (1.0 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were added to a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. The flask was placed in a four-necked separable flask, and 3100 g of γ-butyrolactone was added and dissolved. Thereafter, the mixture was reacted at 82 ° C. for 9 hours using an oil bath.
Next, 34.43 g (0.2 mol) of 4-ethynylphthalic anhydride dissolved in 100 g of γ-butyrolactone was added, and the mixture was further stirred for 10 hours to complete the reaction. After the reaction mixture is filtered, the reaction mixture is put into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, dried under vacuum, and the desired alkali-soluble resin. (A-1) was obtained. (Alkali-soluble resin containing the structure of formula (1))

[Preparation of positive photosensitive resin composition]
After 100 g of the synthesized alkali-soluble resin (A-1) and 16 g of the photosensitive diazoquinone compound having the structure of the following formula (B-1) were dissolved in 180 g of γ-butyrolactone,
The mixture was filtered through a 1 μm Teflon (registered trademark) filter to obtain a positive photosensitive resin composition.

[Evaluation of edge cutability of coating film (200 mm silicon wafer evaluation)]
The positive photosensitive resin composition was applied onto a silicon wafer (diameter 200 mm) using a spin coater. The coating condition was that a positive photosensitive resin composition was dropped at a peripheral speed of 1.60 m / s for 6 seconds, then treated at a peripheral speed of 31.90 m / s for 4 seconds, and then at a peripheral speed of 15.95 m / s for 20 seconds. Processing was performed to obtain a uniform film thickness.
Subsequently, as an edge cutting step, propylene glycol monomethyl ether (PGME): propylene glycol monomethyl ether acetate (PGMEA) was mixed at a weight ratio of 7: 3, and edge cutting was performed with a nozzle diameter of 0.3 mm. .
The first operation for removing the edge of the coating film was processed at a peripheral speed of 6.38 m / s for 20 seconds, and the second operation for drying the solvent was performed at a peripheral speed of 3.19 m / s for 1 second.
After stopping the rotation of the wafer, prebaking was performed at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 5.0 μm.
The edge cut property of the coating film was evaluated by the edge cut width and the resin residue at the edge cut portion. The edge cut width was 3.0 mm as measured with a laser microscope. The evaluation of the resin residue at the edge cut portion was based on the following judgment criteria, and the “area” was the area of the resin remaining portion relative to the area of the edge cut portion, and was good with no resin residue on the coating film.
◎: No resin remaining ○: Some resin remaining (Area <10%)
Δ: Residual resin remaining (area <50%)
×: Resin remains on the entire periphery of the wafer

<< Example 2 >>
In Example 1, except that the alkali-soluble resin was changed to a polyamide-imide resin (alkali-soluble resin (A-2)), the coating film formation, edge cut, and edge of the positive photosensitive resin composition were performed in the same manner as in Example 1. The cut property was evaluated. The edge cut width was 3.0 mm, and the resin residue at the edge cut part was good with no resin residue.
[Synthesis of alkali-soluble resin (A-2)]
4,4.9 g (0.16 mol) of 3,3′-diamino-4,4′-dihydroxydiphenylsulfone and 58.6 g (0.16) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane Mol) and 65.0 g of N-methyl-2-pyrrolidone are placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, and 230.5 g of γ-butyrolactone is added. And dissolved. To this mixed solution, 93.1 g (0.30 mol) of 4,4′-oxydiphthalic anhydride was added together with 120 g of γ-butyrolactone, and then stirred at room temperature for 25 minutes. Then, it was made to react by stirring at 130 degreeC for 5 hours using the oil bath. After cooling the temperature of the reaction mixture to 75 ° C., 5.2 g (0.030 mol) of 5-ethynyl-isobenzofuran-1,3-dione was added together with 40 g of γ-butyrolactone and stirred at 80 ° C. for 2 hours. Then, the reaction was terminated, and a polyamideimide resin (alkali-soluble resin (A-2)) was synthesized.

Example 3
In Example 1, except that the alkali-soluble resin was changed to a cresol novolak resin (alkali-soluble resin (A-3)), coating film formation of the positive photosensitive resin composition, edge cutting, and edge as in Example 1 The cut property was evaluated. The edge cut width was 3.0 mm, and the resin residue at the edge cut part was good with no resin residue.
[Synthesis of alkali-soluble resin (A-3)]
A mixture of 399.6 g (3.7 mol) of metacresol, 680.4 g (6.3 mol) of paracresol, 680 g of 35% aqueous solution of formaldehyde (8.0 mol), and 5 g (0.04 mol) of oxalic acid was added to a mixture of 100 After the reaction at 4 ° C. for 4 hours, the water was removed by distillation at normal pressure until the temperature of the reaction mixture reached 120 ° C., and further distilled under reduced pressure of 0.008 MPa until the temperature of the reaction mixture reached 250 ° C. The reaction cresol was removed to obtain a novolak resin (alkali-soluble resin (A-3)) containing 0.3% by weight of free cresol.

Example 4
In Example 1, except that the peripheral speed of the first operation was set to 12.56 m / s, evaluation of coating film formation, edge cut, and edge cut property of the positive photosensitive resin composition was performed in the same manner as in Example 1. went. The evaluation results of the examples are shown in Table 1.
Example 5
In Example 1, except that the peripheral speed of the second operation was set to 1.06 m / s, evaluation of coating film formation, edge cut, and edge cut property of the positive photosensitive resin composition was performed in the same manner as in Example 1. went. The evaluation results of the examples are shown in Table 1.
Example 6
The coating conditions of Example 1 were changed as follows to produce a 10.0 μm coating film.
A positive photosensitive resin composition is dropped at a peripheral speed of 1.60 m / s for 6 seconds, then processed at a peripheral speed of 31.90 m / s for 4 seconds, and then processed at a peripheral speed of 8.51 m / s for 20 seconds. After pre-baking, a coating film having a film thickness of 10.0 μm was obtained. The obtained coating film was evaluated for edge cut and edge cut performance in the same manner as in Example 1. The evaluation results of the examples are shown in Table 1.
Example 7
In Example 1, except that the solvent used for edge cutting was propylene glycol monomethyl ether acetate (PGMEA), coating film formation of the positive photosensitive resin composition, edge cutting treatment, and edge cutting properties were the same as in Example 1. Was evaluated. The evaluation results of the examples are shown in Table 1.

Example 8
In Example 1, except that the solvent used for edge cutting was propylene glycol monomethyl ether (PGME), evaluation of coating film formation, edge cutting, and edge cutting properties of the positive photosensitive resin composition was performed in the same manner as in Example 1. Went. The evaluation results of the examples are shown in Table 1.
Example 9
In Example 1, the solvent used for edge cutting was γ-butyrolactone (GBL),
Except that the processing time of the second operation was set to 2 seconds, evaluation of coating film formation, edge cut, and edge cut property of the positive photosensitive resin composition was performed in the same manner as in Example 1. The evaluation results of the examples are shown in Table 1.
Example 10
In Example 1, the positive photosensitive resin was the same as in Example 1 except that the solvent used for edge cutting was N-methyl-2-pyrrolidone (NMP) and the processing time of the second operation was 3 seconds. The coating film formation, edge cut, and edge cut property of the composition were evaluated. The evaluation results of the examples are shown in Table 2.
Example 11
In Example 1, except that the solvent used for edge cutting was γ-butyrolactone (GBL) / butyl acetate = 7/3 (weight ratio), the coating film of the positive photosensitive resin composition as in Example 1 The formation, edge cut, and edge cut property were evaluated. The evaluation results of the examples are shown in Table 2.
Example 12
In Example 1, except that the treatment was performed for 3 seconds at a peripheral speed of 3.19 m / s in the second operation, coating film formation of the positive photosensitive resin composition, edge cut, and edge cut properties were the same as in Example 1. Was evaluated. The evaluation results of the examples are shown in Table 2.

Example 13
[Evaluation of edge cut property of coated film (300 mm silicon wafer evaluation)]
The positive photosensitive resin composition used in Example 1 was applied on a silicon wafer (diameter 300 mm) using a spin coater. The coating condition was that a positive photosensitive resin composition was dropped at a peripheral speed of 1.60 m / s for 6 seconds, then treated at a peripheral speed of 31.90 m / s for 4 seconds, and then at a peripheral speed of 15.95 m / s for 20 seconds. Processing was performed to obtain a uniform film thickness.
Subsequently, as an edge cutting step, propylene glycol monomethyl ether (PGME): propylene glycol monomethyl ether acetate (PGMEA) was mixed at a weight ratio of 7: 3, and edge cutting was performed with a nozzle diameter of 0.3 mm. .
The first operation for removing the edge of the coating film was processed at a peripheral speed of 9.57 m / s for 20 seconds, and the second operation for drying the solvent was performed at a peripheral speed of 4.79 m / s for 1 second.
After stopping the rotation of the wafer, prebaking was performed at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 5.0 μm.
Evaluation of the edge cut property of the coating film was performed in the same manner as in Example 1. The evaluation results of the examples are shown in Table 2.

<< Example 14 >>
Evaluation similar to Example 13 was performed except that the alkali-soluble resin (A-2) synthesized in Example 2 was used instead of the alkali-soluble resin (A-1) used in Example 13. The evaluation results of the examples are shown in Table 2.
Example 15
Evaluation similar to Example 13 was performed except that the alkali-soluble resin (A-3) synthesized in Example 3 was used instead of the alkali-soluble resin (A-1) used in Example 13. The evaluation results of the examples are shown in Table 2.
<< Example 16 >>
In Example 13, except that the peripheral speed of the first operation was 15.95 m / s, evaluation of coating film formation, edge cut, and edge cut property of the positive photosensitive resin composition was performed in the same manner as in Example 13. went. The evaluation results of the examples are shown in Table 2.
<< Example 17 >>
In Example 13, except that the peripheral speed of the second operation was 1.60 m / s, evaluation of coating film formation, edge cut, and edge cut property of the positive photosensitive resin composition was performed in the same manner as in Example 13. went. The evaluation results of the examples are shown in Table 2.
<< Example 18 >>
In Example 13, except that the solvent used for the edge cut was propylene glycol monomethyl ether acetate (PGMEA), the coating film formation of the positive photosensitive resin composition, the edge cut treatment, and the edge cut property were the same as in Example 13. Was evaluated. The evaluation results of the examples are shown in Table 2.

Example 19
In Example 13, except that the solvent used for the edge cut was propylene glycol monomethyl ether (PGME), the film formation of the positive photosensitive resin composition, the edge cut treatment, and the edge cut property were the same as in Example 13. Evaluation was performed. The evaluation results of the examples are shown in Table 3.
<< Example 20 >>
In Example 13, the solvent used for edge cutting was γ-butyrolactone (GBL),
Except that the processing time of the second operation was set to 2 seconds, evaluation of coating film formation, edge cut, and edge cut property of the positive photosensitive resin composition was performed in the same manner as in Example 1. The evaluation results of the examples are shown in Table 3.
<< Example 21 >>
In Example 13, the positive photosensitive resin was the same as Example 13 except that the solvent used for edge cutting was N-methyl-2-pyrrolidone (NMP) and the processing time for the second operation was 3 seconds. The coating film formation, edge cut, and edge cut property of the composition were evaluated. The evaluation results of the examples are shown in Table 3.
<< Example 22 >>
A coating film of a positive photosensitive resin composition in the same manner as in Example 13 except that the solvent used for edge cutting in Example 13 was γ-butyrolactone (GBL) / butyl acetate = 7/3 (weight ratio). The formation, edge cut, and edge cut property were evaluated. The evaluation results of the examples are shown in Table 3.

≪Comparative example 1≫
In Example 1, except that the peripheral speed of the second operation was set at 6.38 m / s for 1 second, coating film formation, edge cutting, and edge cutting of the positive photosensitive resin composition were performed in the same manner as in Example 1. Sexuality was evaluated. The edge cut width was 2.0 mm, and the evaluation result of the resin residue at the edge cut portion was that there was resin residue on the entire outer periphery of the wafer. (Evaluation result “×”).
«Comparative example 2»
In Example 1, positive type photosensitivity was obtained in the same manner as in Example 1 except that propylene glycol monomethyl ether was used as the solvent for edge cutting and the peripheral speed of the second operation was processed at 6.38 m / s for 1 second. Evaluation of film formation, edge cut, and edge cut property of the resin composition was performed. The edge cut width was 2.0 mm, and the evaluation result of the resin residue at the edge cut portion was that there was resin residue on the entire outer periphery of the wafer. (Evaluation result “×”).

«Comparative Example 3»
In Example 1, except that the peripheral speed of the first operation was 17.01 m / s, coating film formation and edge cutting of the positive photosensitive resin composition were performed in the same manner as in Example 1. The edge cut process could not be performed and processing was impossible, and the evaluation result of the resin residue at the edge cut part was that there was resin residue on the entire outer periphery of the wafer. (Evaluation result “×”).
<< Comparative Example 4 >>
In Example 1, except that the peripheral speed of the second operation was set to 4.25 m / s, evaluation of coating film formation, edge cut, and edge cut property of the positive photosensitive resin composition was performed in the same manner as in Example 1. went. The edge cut width was 3.0 mm, and the evaluation result of the resin residue at the edge cut part was that there was some resin residue (area <50%). (Evaluation result “△”).
<< Comparative Example 5 >>
In Example 1, except that the processing time of the second operation was set to 5 seconds, the coating film formation, edge cut, and edge cut property of the positive photosensitive resin composition were evaluated in the same manner as in Example 1. The edge cut width was 2.0 mm, and the evaluation result of the resin residue at the edge cut part was that there was some resin residue (area <50%). (Evaluation result “△”).

<Boiling point of each solvent>
PGMEA: 120 ° C
PGME: 145 ° C
GBL: 204 ° C
NMP: 202 ° C
Butyl acetate: 126 ° C

Claims (6)

A coating film forming method for forming a coating film of a positive photosensitive resin composition on a support,
An application step of applying a positive photosensitive resin composition to a support;
It has an edge cut process that performs an edge cut process with a solvent,
In the edge cutting step, at least the support coated with the positive photosensitive resin composition is rotated at a peripheral speed of 1.9 m / s to 16 m / s, and the solvent is supplied to the edge of the coating film. By the first operation to remove the end of the coating film,
A second operation for drying the solvent by rotating the support slower than the first operation after the first operation;
A method for forming a coating film of a positive photosensitive resin composition.   The method for forming a coating film of a positive photosensitive resin composition according to claim 1, wherein the peripheral speed of the support in the second operation is 0.4 m / s or more and 4.8 m / s or less.   The method for forming a coating film of a positive photosensitive resin composition according to claim 1 or 2, wherein the treatment time in the second operation is 1 second or more and 3 seconds or less.   The method for forming a coating film of a positive photosensitive resin composition according to any one of claims 1 to 3, wherein the solvent used in the first operation has a boiling point of 110 ° C or higher and 220 ° C or lower.   The solvent used in the first operation is one or a mixture of two or more selected from propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, N-methyl-2-pyrrolidone, and butyl acetate. A method for forming a coating film of the positive photosensitive resin composition according to any one of claims 1 to 4. The positive photosensitive resin composition according to any one of claims 1 to 5, wherein a 300 mm substrate having a peripheral speed of the support in the second operation of 7.9 m / s or more and 16 m / s or less is used. Coating film forming method.