Positive photosensitive resin composition, photosensitive resin film prepared by using the same, and semiconductor device including the photosensitive resin film

Disclosed is a positive photosensitive resin composition that includes (A) an alkali soluble resin prepared by a phosphorous-containing diamine represented by the following Chemical Formula 1, (B) a photosensitive diazoquinone compound, and (C) a solvent. A photosensitive resin film prepared using the same and a semiconductor device including the photosensitive resin film are also disclosed.In Chemical Formula 1, each substituent is the same as defined in the detailed description.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of Korean Patent Application No. 10-2011-0141439 filed in the Korean Intellectual Property Office on Dec. 23, 2011, the entire disclosure of which is incorporated herein by reference.

FIELD

This disclosure relates to a positive photosensitive resin composition, a photosensitive resin film prepared by using the same, and a semiconductor device including the photosensitive resin film.

BACKGROUND

A polyimide resin used as an insulation layer material for a light emitting diode can have excellent heat resistance, stability in a process conducted at a temperature of greater than or equal to about 200° C., and mechanical strength, a low dielectric constant (low-k), and excellent planarization characteristics on a coating surface. Further, a polyimide resin used as an insulation layer material can include a small amount of impurities, which can deteriorate the reliability of a device, and can easily provide a fine pattern. Thus, a polyimide resin as an insulation layer material has drawn lots of attention.

A conventional polyimide resin for forming an insulation layer or a semiconductor protective layer for an organic light emitting diode requires an additional photoresist process and subsequently an etching process using an organic solvent after the patterning. Thus, the manufacturing process can be complex and require additional costs. Further, the device can exhibit resist pattern swelling as well as cause an environmental problem due to the use of an organic solvent.

On the other hand, an organic material remaining in an exposed part may be removed in a dry etching method during formation of a semiconductor circuit protective layer or a pixel crystal layer for an organic light emitting diode

(OLED) display. As used herein, the dry etching selectively removes a residue in an exposed pattern part. Accordingly, there has been research directed to a resin material which is less influenced by the etching in a non-exposed part.

In addition, the resin material needs to include more carbon in order to provide excellent etching resistance. However, there can be a problem because the resin material can be exposed at a high temperature of greater than or equal to about 400° C.

SUMMARY

One embodiment provides a positive photosensitive resin composition that can have improved photosensitivity, a high residue removal rate at exposed parts, and excellent etching resistance and heat resistance.

Another embodiment provides a photosensitive resin film prepared by using the positive photosensitive resin composition.

Yet another embodiment provides a semiconductor device including the photosensitive resin film.

One embodiment provides a positive photosensitive resin composition that includes (A) an alkali soluble resin prepared using a phosphorous-containing diamine represented by the following Chemical Formula 1; (B) a photosensitive diazoquinone compound; and (C) a solvent.

In Chemical Formula 1,

R′ and R″ are the same or different and are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C3 to C20 cycloalkenyl, substituted or unsubstituted C3 to C20 cycloalkynyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkenyl, substituted or unsubstituted C2 to C20 heterocycloalkynyl, or substituted or unsubstituted C6 to C30 aryl,

R is substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C3 to C20 cycloalkenyl, substituted or unsubstituted C3 to C20 cycloalkynyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkenyl, substituted or unsubstituted C2 to C20 heterocycloalkynyl, or substituted or unsubstituted C6 to C30 aryl, and

n′ and n″ are the same or different and are each independently integers ranging from 0 to 3.

The phosphorous-containing diamine may include a compound represented by the following Chemical Formula 2, Chemical Formula 3 or a combination thereof.

The alkali soluble resin may include a polybenzoxazole precursor including a repeating unit represented by the following Chemical Formula 4.

In Chemical Formula 4,

X1is a residual group derived from the phosphorous-containing diamine represented by the above Chemical Formula 1, and

Y1is a substituted or unsubstituted C6 to C30 aromatic organic group, substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group.

The alkali soluble resin may be prepared from the phosphorous-containing diamine and an aromatic diamine. Examples of the aromatic diamine may include without limitation an aromatic diamine represented by the following Chemical Formula 8, Chemical Formula 9 or a combination thereof.

In Chemical Formulae 8 and 9,

A is a single bond, —O—, —CO—, —CR4R5—, —SO2—, or —S—, wherein R4and R5are the same or different and are each independently hydrogen or substituted or unsubstituted C1 to C30 alkyl,

R1to R3are the same or different and are each independently hydrogen, substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxy group, or a thiol group,

n1is an integer ranging from 0 to 2, and

n2and n3are the same or different and are each independently an integer ranging from 0 to 3.

The phosphorous-containing diamine and the aromatic diamine may be mixed at a weight ratio of about 5:95 to about 95:5.

The alkali soluble resin may include a polybenzoxazole precursor including a repeating unit represented by the following Chemical Formula 4 and a repeating unit represented by the following Chemical Formula 10.

In Chemical Formula 4,

X1is a residual group derived from phosphorous-containing diamine represented by the above Chemical Formula 1, and

Y1is a substituted or unsubstituted C6 to C30 aromatic organic group, substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group.

In Chemical Formula 10,

X2is a residual group derived from an aromatic diamine represented by one of the above Chemical Formulae 8 and 9, or a combination thereof, and

Y2is a substituted or unsubstituted C6 to C30 aromatic organic group, substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group.

The positive photosensitive resin composition may further include (A′) an alkali soluble resin prepared from aromatic diamine, wherein the aromatic diamine may include a diamine represented by the above Chemical Formula 8, Chemical Formula 9 or a combination thereof.

The alkali soluble resin prepared from phosphorous-containing diamine (A) and the alkali soluble resin prepared from aromatic diamine (A′) may be mixed at a weight ratio of about 5:95 to about 95:5.

The alkali soluble resin may have a weight average molecular weight (Mw) of about 3,000 to about 300,000 g/mol.

The positive photosensitive resin composition may include about 5 to about 100 parts by weight of the photosensitive diazoquinone compound (B) and about 100 to about 900 parts by weight of the solvent (C), based on about 100 parts by weight of the alkali soluble resin (A).

Another embodiment provides a photosensitive resin film prepared using the positive photosensitive resin composition.

Yet another embodiment provides a semiconductor device including the photosensitive resin film.

Other embodiments are described in the detailed description.

The positive photosensitive resin composition can have improved photosensitivity, a high residue removal rate at exposed parts, and excellent etching resistance and heat resistance, and may be used as a protective layer of a semiconductor circuit or a pixel crystal layer of an organic light emitting diode (OLED) display.

DETAILED DESCRIPTION

As used herein, when a specific definition is not otherwise provided, the term “substituted” may refer to one substituted with at least a substituent including halogen (—F, —Cl, —Br, or —I), a hydroxy group, a nitro group, a cyano group, an amino group (NH2, NH(R200), or N(R201)(R202), wherein R200, R201and R202are the same or different and are each independently C1 to C10 alkyl), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, a substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic, or a combination thereof in place of at least one of hydrogen of a functional group.

As used herein, when a specific definition is not otherwise provided, the term “alkyl” may refer to C1 to C30 alkyl, for example C1 to C15 alkyl, the term “cycloalkyl” may refer to C3 to C30 cycloalkyl, for example C3 to C18 cycloalkyl, the term “alkoxy” may refer to C1 to C30 alkoxy, for example C1 to C18 alkoxy, the term “aryl” may refer to C6 to C30 aryl, for example C6 to C18 aryl, the term “alkenyl” may refer to C2 to C30 alkenyl, for example C2 to C18 alkenyl, the term “alkylene” may refer to C1 to C30 alkylene, for example C1 to C18 alkylene, and the term “arylene” may refer to C6 to C30 arylene, for example C6 to C16 arylene.

As used herein, when a specific definition is not otherwise provided, the term “combination” refers to mixing or copolymerization. Also, the term “copolymerization” refers to block copolymerization or random copolymerization, and the term “copolymer” refers to a block copolymer or a random copolymer.

Also, “*” refers to a linking part between the same or different atoms, or chemical formulae.

The positive photosensitive resin composition according to one embodiment includes (A) an alkali soluble resin, (B) a photosensitive diazoquinone compound, and (C) a solvent.

Hereinafter, each component is described in detail.

The alkali soluble resin may be prepared from a phosphorous-containing diamine represented by the following Chemical Formula 1.

In Chemical Formula 1, R′ and R″ may be the same or different and are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C3 to C20 cycloalkenyl, substituted or unsubstituted C3 to C20 cycloalkynyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkenyl, substituted or unsubstituted C2 to C20 heterocycloalkynyl, or substituted or unsubstituted C6 to C30 aryl.

In Chemical Formula 1, R is substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C3 to C20 cycloalkenyl, substituted or unsubstituted C3 to C20 cycloalkynyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkenyl, substituted or unsubstituted C2 to C20 heterocycloalkynyl, or substituted or unsubstituted C6 to C30 aryl. In exemplary embodiments, R can be substituted or unsubstituted C1 to C20 alkyl or substituted or unsubstituted C6 to C30 aryl.

In Chemical Formula 1, n′ and n″ are the same or different and are each independently integers of 0 to 3.

An hydroxyl group of the above Chemical Formula 1 is a reactive curable functional group, and an amino group is reacted during polymerization to provide polyhydroxyamide as a polybenzoxazole precursor. In addition, the hydroxy group and the amino group exist at an ortho position relative to each other and may produce a cyclic benzoxazole structure through a ring-closing reaction during a curing process.

When the phosphorous-containing diamine represented by the above Chemical Formula 1 is used to prepare an alkali soluble resin, in particular, a polybenzoxazole precursor, the prepared positive photosensitive resin composition can have excellent photosensitivity, a high residue removal rate at exposed parts during the pattern forming process, and excellent etching resistance and heat resistance.

The phosphorous-containing diamine may include a compound represented by the following Chemical Formula 2, Chemical Formula 3 or a combination thereof.

The alkali soluble resin may use a polybenzoxazole precursor including a repeating unit represented by the following Chemical Formula 4 prepared from the phosphorous-containing diamine.

In Chemical Formula 4, X1is a residual group derived from a phosphorous-containing diamine represented by the above Chemical Formula 1.

In Chemical Formula 4, Y1is a substituted or unsubstituted C6 to C30 aromatic organic group, substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group. In one embodiment, Y1may be a residual group of dicarboxylic acid or a residual group of a dicarboxylic acid derivative.

Examples of the dicarboxylic acid may include without limitation Y1(COOH)2(wherein Y1is the same as Y1of the above Chemical Formula 6).

Examples of the dicarboxylic acid derivative may include without limitation carbonyl halide derivatives of Y1(COOH)2or active compounds of an active ester derivative obtained by reacting Y1(COOH)2and 1-hydroxy-1,2,3-benzotriazole.

Examples of Y1may include functional groups represented by the following Chemical Formulae 5 to 7, and combinations thereof, but is not limited thereto.

In Chemical Formulae 5 to 7, R10to R13are the same or different and are each independently hydrogen or substituted or unsubstituted C1 to C30 alkyl, n4, n6, and n7are the same or different and are each independently an integer of 0 to 4, and n5is an integer of 0 to 3.

In Chemical Formulae 5 to 7, A2may be a single bond, O, CR4R5, CO, CONH, S, or SO2, wherein R4and R5are the same or different and are each independently hydrogen or substituted or unsubstituted C1 to C30 alkyl, for example C1 to C30 fluoroalkyl.

The alkali soluble resin may be prepared by mixing the phosphorous-containing diamine with aromatic diamine.

Examples of the aromatic diamine may include without limitation a diamine represented by following Chemical Formula 8, Chemical Formula 9, or a combination thereof.

In Chemical Formulae 8 and 9, A is a single bond, —O—, —CO—, —CR4R5—, —SO2—, or —S—, wherein R4and R5are the same or different and are each independently hydrogen or substituted or unsubstituted C1 to C30 alkyl. In one embodiment, A may be —CR4R5—, wherein R4and R5are each C1 to C30 fluoroalkyl.

In Chemical Formulae 8 and 9, R1to R3are the same or different and are each independently hydrogen, substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxy group, or a thiol group.

In Chemical Formulae 8 and 9, n1may be an integer of 0 to 2, and n2and n3are the same or different and are each independently an integer of 0 to 3.

The phosphorous-containing diamine and the aromatic diamine may be mixed in a weight ratio of about 5:95 to about 95:5, for example about 5:95 to about 50:50.

When the phosphorous-containing diamine and the aromatic diamine are mixed in an amount within the above weight ratio range, the prepared positive photosensitive resin composition may have excellent photosensitivity, a high residue removal rate at exposed parts during the pattern forming process, and excellent etching and heat resistances.

The alkali soluble resin may include a polybenzoxazole precursor prepared from the phosphorous-containing diamine and the aromatic diamine.

The polybenzoxazole precursor may include a repeating unit represented by the above Chemical Formula 4 and a repeating unit represented by the above the following Chemical Formula 10.

In Chemical Formula 10, X2is a residual group derived from at least one aromatic diamine represented by the above Chemical Formulae 8 and 9 or a combination thereof. The aromatic diamine is the same as described above.

In Chemical Formula 10, Y2may be a substituted or unsubstituted C6 to C30 aromatic organic group, substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group. Y2is the same as Y1defined in the above Chemical Formula 4.

The alkali soluble resin prepared from the phosphorous-containing diamine represented by the above Chemical Formula 1 may be mixed with at least one alkali soluble resin prepared from the aromatic diamine represented by the above Chemical Formulae 8 and 9 and combinations thereof. Stated differently, the positive photosensitive resin composition can further include (A′) an alkali soluble resin prepared from aromatic diamine, wherein the aromatic diamine comprises a diamine represented by Chemical Formula 8, Chemical Formula 9, or a combination thereof:

wherein in Chemical Formulae 8 and 9,

A is a single bond, —O—, —CO—, —CR4R5—, —SO2—, or —S—, wherein R4and R5are the same or different and are each independently hydrogen or substituted or unsubstituted C1 to C30 alkyl,

R1to R3are the same or different and are each independently hydrogen, substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxy group, or a thiol group,

n1is an integer ranging from 0 to 2, and

n2and n3are the same or different are and are each independently an integer ranging from 0 to 3.

The alkali soluble resin can include the phosphorous-containing diamine (A) and the alkali soluble resin prepared from aromatic diamine (A′) mixed at a weight ratio of about 5:95 to about 95:5.

The alkali soluble resin prepared from the phosphorous-containing diamine and the alkali soluble resin prepared from aromatic diamine may be mixed at a weight ratio of about 5:95 to about 95:5, for example about 5:95 to about 50:50.

When the alkali soluble resin includes the phosphorous-containing diamine (A) and the alkali soluble resin prepared from aromatic diamine (A′) in amounts within the above weight ratio range, a positive photosensitive resin composition having improved photosensitivity, a high residue removal rate at exposed parts excellent etching resistance and heat resistance during pattern forming processes may be obtained.

The alkali soluble resin may have a weight average molecular weight (Mw) of about 3,000 to about 300,000 g/mol, for example about 5,000 to about 20,000 g/mol. When the alkali soluble resin has a weight average molecular weight within the above range, sufficient film residue ratios at non-exposed parts during development using an alkali aqueous solution may be provided, and patterning may be performed efficiently.

The photosensitive diazoquinone compound may be a compound including a 1,2-benzoquinone diazide or 1,2-naphtoquinone diazide structure.

The photosensitive diazoquinone compound may include a compound represented by the following Chemical Formulae 11, 13 to 15, or a combination thereof, but is not limited thereto.

In Chemical Formula 11, R14to R16are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkyl, for example methyl.

In Chemical Formula 11, R17to R19are the same or different and are each independently OQ, wherein Q is hydrogen, a functional group represented by the following Chemical Formula 12a, or a functional group represented by the following Chemical Formula 12b, provided that all Qs are not simultaneously hydrogen.

In Chemical Formula 11, n8to n10are the same or different and are each independently integers of 0 to 3.

In Chemical Formula 13, R20is hydrogen or substituted or unsubstituted C1 to C30 alkyl, R21to R23are the same or different and are each independently OQ, wherein Q is the same as defined in the above Chemical Formula 11, and n11to n13are the same or different and are each independently integers of 0 to 3.

In Chemical Formula 14, A3is CO or CR4R5, wherein R4and R5are the same or different and are each independently substituted or unsubstituted C1 to C30 alkyl.

In Chemical Formula 14, R24to R27are the same or different and are each independently hydrogen, substituted or unsubstituted C1 to C30 alkyl, OQ, or NHQ, wherein Q is the same as defined in Chemical Formula 11.

In Chemical Formula 14, n14to n17are the same or different and are each independently integers ranging from 0 to 4, and n14+n15and n16+n17are the same or different and are each independently integers of 5 or less,

provided that at least one of R24and R25is OQ, and one aromatic ring includes one to three OQs and the other aromatic ring includes one to four OQs.

In Chemical Formula 15,

R28to R35are the same or different and are each independently hydrogen or substituted or unsubstituted C1 to C30 alkyl, n18and n19are the same or different and are each independently integers ranging from 1 to 5, and each Q is the same as defined in Chemical Formula 11.

When the amount of the photosensitive diazoquinone compound is within the above range, the pattern can be well-formed with minimal or no residue from exposure, and film thickness loss during development may be minimized or prevented, which can provide a good pattern.

The positive photosensitive resin composition may include a solvent that is capable of dissolving each component easily.

The solvent may be desirably selected according to a method of forming a photosensitive resin film such as spin coating, slit die coating, and the like.

The positive photosensitive resin composition may include the solvent in an amount of about 100 to about 900 parts by weight, for example about 300 to about 800 parts by weight, based on about 100 parts by weight of the alkali soluble resin. When the solvent is used in an amount within the above range, a sufficiently thick film can be obtained, and good solubility and coating can be provided.

In one embodiment, the solvent may be used so that a solid content of the positive photosensitive resin composition is about 5 to about 50 wt %.

The positive photosensitive resin composition according to one embodiment may further include one or more other additives.

The other additives may include a latent thermal acid generator. Examples of the latent thermal acid generator include without limitation arylsulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, and the like; perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid, trifluorobutanesulfonic acid, and the like; alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, and the like; and the like; and combinations thereof.

The latent thermal acid generator is a catalyst for a dehydration reaction and a cyclization reaction of the polybenzoxazole precursor that is polyamide including a phenolic hxdroxy group, and thus a cyclization reaction may be performed smoothly even if curing temperature is decreased.

In addition, the positive photosensitive resin composition may further include an additive such as a suitable surfactant and/or leveling agent to prevent staining of the film and/or to improve development.

Exemplary processes for forming a pattern using a positive photosensitive resin composition include: coating a positive photosensitive resin composition on a supporting substrate using spin coating, slit coating, inkjet printing, and the like; drying the coated positive photosensitive resin composition to provide a positive photosensitive resin composition layer; exposing the positive photosensitive resin composition layer; developing the positive photosensitive resin composition layer using an alkali aqueous solution to provide a photosensitive resin film; and baking the photosensitive resin film. The conditions of processes to provide a pattern are widely known in this art, so detailed descriptions thereof will be omitted in this specification.

According to another embodiment, a photosensitive resin film prepared using the positive photosensitive resin composition is provided. The photosensitive resin film may be an insulation layer, a buffer layer, or a protective layer.

According to yet another embodiment, a semiconductor device including the photosensitive resin layer is provided. The semiconductor device may be an organic light emitting diode (OLED) or a liquid crystal display (LCD).

The following examples illustrate the present invention in more detail. However, it is understood that the present invention is not limited by these examples.

PREPARATION OF POLYBENZOXAZOLE PRECURSOR

Preparation Example 1

11.0 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide is added to 280 g of N-methyl-2-pyrrolidone (NMP) and dissolved therein in a four-neck flask mounted with an agitator, a temperature controller, a nitrogen gas injector, and a cooler while nitrogen is passed therethrough. When the reactant is completely dissolved, 9.9 g of pyridine is added to the solution. Then, a solution prepared by adding 13.3 g of 4,4′-oxydibenzoylchloride to 142 g of N-methyl-2-pyrrolidone (NMP) is slowly added to the mixture in a dropwise fashion for 30 minutes while the mixture is maintained at a temperature ranging from 0 to 5° C. The resulting mixture is reacted for 1 hour at a temperature ranging from 0 to 5° C. Then, after the temperature of the reactant is increased to room temperature, and the reactant is agitated for 1 hour. Herein, 1.6 g of 5-norbornene-2,3-dicarboxyl anhydride is added to the agitated reactant, and the mixture is agitated at 70° C. for 24 hours. The reaction mixture is precipitated in water/methanol=10/1 (a volume ratio). The precipitate is filtered, sufficiently cleaned with water, and dried at 80° C. under vacuum for greater than or equal to 24 hours, obtaining a polybenzoxazole precursor having a weight average molecular weight of 8,100 g/mol.

Preparation Example 2

The polybenzoxazole precursor is prepared according to the same method as Preparation Example 1 except for using 0.6 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide and 19.6 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 11.0 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 9,500 g/mol.

Preparation Example 3

The polybenzoxazole precursor is prepared according to the same method as Preparation Example 1 except for using 2.8 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide and 15.5 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 11.0 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 9,400 g/mol.

Preparation Example 4

The polybenzoxazole precursor is prepared according to the same method as Preparation Example 1 except for using 5.5 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide and 10.3 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 11.0 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 9,500 g/mol.

Preparation Example 5

The polybenzoxazole precursor is prepared according to the same method as Preparation Example 1 except for using 8.3 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide and 5.2 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 11.0 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 8,700 g/mol.

Preparation Example 6

The polybenzoxazole precursor is prepared according to the same method as Preparation Example 1 except for using 8.3 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide and 5.2 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 11.0 g of bis(3-amino-4-hydroxyphenyl)(phenyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 8,600 g/mol.

Preparation Example 7

9.5 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide is added to 280 g of N-methyl-2-pyrrolidone (NMP) and dissolved therein in a four-neck flask mounted with an agitator, a temperature controller, a nitrogen gas injector, and a cooler while nitrogen is passed therethrough. When the dissolution is complete, 9.9 g of pyridine is added to the solution. While the temperature of the mixture is maintained at a temperature ranging from 0 to 5° C., a solution prepared by adding 13.3 g of 4,4′-oxydibenzoyl chloride to 142 g of N-methyl-2-pyrrolidone (NMP) is slowly added thereto in a dropwise fashion for 30 minutes. The mixture is reacted for 1 hour at a temperature ranging from 0 to 5° C., and after its temperature is increased up to room temperature, the reactant is agitated for 1 hour. Then, 1.6 g of 5-norbornene-2,3-dicarboxyl anhydride is added to the agitated reactant. The mixture is agitated at 70° C. for 24 hours. The reaction mixture is precipitated in water/methanol=10/1 (a volume ratio). The precipitate is filtered, sufficiently cleaned with water, and dried at 80° C. under vacuum for greater than or equal to 24 hours, obtaining a polybenzoxazole precursor having a weight average molecular weight of 8,000 g/mol.

Preparation Example 8

A polybenzoxazole precursor is prepared according to the same method as Preparation Example 7 except for using 0.5 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide and 19.6 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 9.5 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 9,400 g/mol.

Preparation Example 9

A polybenzoxazole precursor is prepared according to the same method as Preparation Example 7 except for using 2.4 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide and 15.5 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 9.5 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 9,300 g/mol.

Preparation Example 10

A polybenzoxazole precursor is prepared according to the same method as Preparation Example 7 except for using 4.8 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide and 10.3 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 9.5 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 8,900 g/mol.

Preparation Example 11

A polybenzoxazole precursor is prepared according to the same method as Preparation Example 7 except for using 7.1 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide and 5.2 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 9.5 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 8,500 g/mol.

Preparation Example 12

A polybenzoxazole precursor is prepared according to the same method as Preparation Example 7 except for using 9.0 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide and 1.0 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane instead of 9.5 g of bis(3-amino-4-hydroxyphenyl)(ethyl)phosphine oxide. Herein, the polybenzoxazole precursor has a weight average molecular weight of 8,400 g/mol.

Preparation Example 13

20.6 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is added to 280 g of N-methyl-2-pyrrolidone (NMP) and dissolved therein in a four-neck flask mounted with an agitator, a temperature controller, a nitrogen gas injector, and a cooler while passing nitrogen therethrough. When the dissolution is complete, 9.9 g of pyridine is added to the solution. The mixture is maintained at a temperature ranging from 0 to 5° C., a solution prepared by dissolving 13.3 g of 4,4′-oxydibenzoyl chloride to 142 g of N-methyl-2-pyrrolidone (NMP) is slowly added thereto for 30 minutes in a dropwise fashion. The resulting mixture is reacted for 1 hour at a temperature ranging from 0 to 5° C. Then, the reactant is agitated for one hour after increasing its temperature up to room temperature. Then, 1.6 g of 5-norbornene-2,3-dicarboxyl anhydride is added to the agitated reactant, and the mixture is agitated at 70° C. for 24 hours. The reaction mixture is precipitated in water/methanol=10/1 (a volume ratio). The precipitate is filtered, sufficiently cleaned with water, and dried at 80° C. under vacuum for greater than or equal to 24 hours, obtaining a polybenzoxazole precursor having a weight average molecular weight of 10,200 g/mol.

PREPARATION of POSITIVE PHOTOSENSITIVE RESIN COMPOSITION

10 g of the polybenzoxazole precursor according to Preparation Example 1 is added to 35.0 g of γ-butyrolactone (GBL) and dissolved therein, and 1 g of photosensitive diazoquinone represented by the following Chemical Formula 16, 0.02 g of trimethoxy[3-(phenylamino)propyl]silane represented by the following Chemical Formula 17, and 0.75 g of a phenol compound represented by the following Chemical Formula 18 are added thereto and dissolved therein. The solution is filtered using a 0.45 μm fluorine resin filter, preparing a positive photosensitive resin composition.

Examples 2 To 12

A positive photosensitive resin composition is prepared according to the same method as Example 1 except for using 10 g of each polybenzoxazole precursor according to Preparation Examples 2 to 12 instead of 10 g of the polybenzoxazole precursor according to Preparation Example 1.

A positive photosensitive resin composition is prepared according to the same method as Example 1 except for using 0.5 g of the polybenzoxazole precursor according to Preparation Example 1 and 9.5 g of the polybenzoxazole precursor according to Preparation Example 13 instead of 10 g of the polybenzoxazole precursor according to Preparation Example 1.

A positive photosensitive resin composition is prepared according to the same method as Example 1 except for using 5 g of the polybenzoxazole precursor according to Preparation Example 1 and 5 g of the polybenzoxazole precursor according to Preparation Example 13 instead of 10 g of the polybenzoxazole precursor according to Preparation Example 1.

A positive photosensitive resin composition is prepared according to the same method as Example 1 except for using 9.5 g of the polybenzoxazole precursor according to Preparation Example 1 and 0.5 g of the polybenzoxazole precursor according to Preparation Example 13 instead of 10 g of the polybenzoxazole precursor according to Preparation Example 1.

A positive photosensitive resin composition is prepared according to the same method as Example 1 except for using 0.5 g of the polybenzoxazole precursor according to Preparation Example 7 and 9.5 g of the polybenzoxazole precursor according to Preparation Example 13 instead of 10 g of the polybenzoxazole precursor according to Preparation Example 7.

A positive photosensitive resin composition is prepared according to the same method as Example 1 except for using 5 g of the polybenzoxazole precursor according to Preparation Example 7 and 5 g of the polybenzoxazole precursor according to Preparation Example 13 instead of 10 g of the polybenzoxazole precursor according to Preparation Example 7.

A positive photosensitive resin composition is prepared according to the same method as Example 1 except for using 9.5 g of the polybenzoxazole precursor according to Preparation Example 7 and 0.5 g of the polybenzoxazole precursor according to Preparation Example 13 instead of 10 g of the polybenzoxazole precursor according to Preparation Example 7.

Comparative Example 1

A positive photosensitive resin composition is prepared according to the same method as Example 1 except for using the polybenzoxazole precursor according to Preparation Example 13 instead of 10 g of the polybenzoxazole precursor according to Preparation Example 1.

Evaluation 1: Thickness Change

Each positive photosensitive resin composition prepared from Examples 1 to 18 and Comparative Example 1 is coated on a 8-inch wafer using a spin coater manufactured by Mikasa (1H-DX2), and then heated on a hot plate to 130° C. for 2 minutes to provide a polybenzoxazole precursor film.

The polybenzoxazole precursor films are exposed through a mask having various sized patterns by an I-line stepper (NSR i10C) manufactured by Japan Nikon, and the exposed part is dissolved and removed in a 2.38% tetramethyl ammonium hydroxide aqueous solution at a room temperature for 40 seconds, 2 puddles, and washed with pure water for 30 seconds. Subsequently, the obtained pattern is cured in an electric furnace under an oxygen concentration of less than or equal to 1000 ppm at 150° C. for 30 minutes and additionally at 320° C. for 30 minutes to provide a patterned film.

Herein, the films are measured for thickness changes after the coating, development, curing, and etching steps using ST4000-DLX equipment (KMAC Corp.), and the results are provided in the following Table 1.

Evaluation 2: Sensitivity

The films are evaluated for sensitivity by measuring the exposure time taken to form a 10 μm L/S pattern having a line width of 1:1 after the exposure and development and using this exposure time as an optimal exposure time. The results are provided in the following Table 1.

Evaluation 3: 5% Weight Decrease Temperature

Dry etching to fabricate the films in Evaluation 1 is performed using a mixed gas of CHF3/CF4, and the films are measured for 5% weight decrease temperature using a thermal weight analyzer (TGA), while the temperature of the cured thin films is increased by 10° C. per minute under nitrogen. The results are provided in the following Table 1.

Based on Table 1, the films of Examples 1 to 18 including an alkali soluble resin prepared from a phosphorous-containing diamine according to one embodiment can have excellent photosensitivity, a high residue removal rate in exposed parts, and excellent etching and heat resistances compared with the film including an alkali soluble resin prepared from aromatic diamine according to Comparative Example 1. Accordingly, the films according to Examples 1 to 18 may be usefully applied as a semiconductor circuit protective layer or a pixel crystal layer for an organic light emitting diode (OLED) display.