Patent Application
20160160074
This application claims the priority benefit of Taiwan application serial no. 103142138, filed on Dec. 4, 2014. The entirety of the above-mentioned patent application is hereby incorporated by reference herein and made a part of this specification.
The disclosure is related to a photoimprinting resin composition solution, a photoimprinting resin thin film, and a patterning method.
With the vigorous development of the integrated circuit, the reduction in size and the integration of elements are inevitable trends, and the active development of those characteristics is an important topic of various industries. The etching process plays an important role in the integrated circuit manufacturing process. However, in the conventional lithography and etching process, a photoresist is manufactured into an etch mask via a lithography method, where the dimension and the aspect ratio of the structure are limited by optics. Therefore, bottleneck may occur when a micro-nano structure having a high aspect ratio is etched. Moreover, conventional lithography and etching techniques also have the disadvantage of a costly exposure machine.
In comparison to the conventional lithography process, the photoimprinting method has the advantage of faster production speed, and at the same time, due to the demand for larger substrate dimension and a refined pattern, adjustment to the machine of the photoimprinting method is also more flexible. Therefore, the photoimprinting method has the potential to become the main technique of the etching process. It should be mentioned that, the photoimprint resin used in the photoimprinting method is a key material in the process, and has a certain influence over the imprint forming quality, reducing imprint residue, and production yield.
A photoimprinting resin composition solution of the disclosure includes a monomer or a polymer having an epoxy group, a cationic photopolymerization initiator, a thermoplastic resin, and a solvent. The weight-average molecular weight of the thermoplastic resin is 500 to 50000, and the thermoplastic resin does not react with the monomer or the polymer having an epoxy group and the cationic photopolymerization initiator.
A patterning method of the disclosure includes preparing a photoimprinting resin composition solution, and then coating the photoimprinting resin composition solution on a substrate. Then, a pre-bake process is performed to remove the solvent in the photoimprinting resin composition solution so as to form a photoimprinting resin thin film. Then, an imprinting process is performed on the photoimprinting resin thin film via an imprint mold to pattern the photoimprinting resin thin film. Then, an irradiation step is performed to cure the patterned photoimprinting resin thin film. Lastly, the imprint mold is removed, and then the substrate is patterned by using the patterned photoimprinting resin thin film as an etch mask.
A photoimprinting resin thin film of the disclosure includes a monomer or a polymer having an epoxy group, a cationic photopolymerization initiator, and a thermoplastic resin. The weight-average molecular weight of the thermoplastic resin is 500 to 50000, and the thermoplastic resin does not react with the monomer or the polymer having an epoxy group and the cationic photopolymerization initiator.
To make the above features and advantages of the disclosure more comprehensible, several embodiments accompanied with drawings are described in detail as follows.
A photoimprinting resin composition solution of an embodiment of the disclosure can include a monomer or a polymer having an epoxy group, a cationic photopolymerization initiator, a thermoplastic resin, and a solvent. In particular, the thermoplastic resin does not react with the monomer or the polymer having an epoxy group and the cationic photopolymerization initiator. Each component of the photoimprinting resin composition solution of an embodiment of the disclosure is described in detail below.
The weight-average molecular weight of the thermoplastic resin is 500 to 50000, and the thermoplastic resin does not react with the monomer or the polymer having an epoxy group and the cationic photopolymerization initiator. In the present embodiment, the thermoplastic resin is, for instance, a phenol resin, polystyrene, polyacrylate, polycarbonate, or a cyclic olefin polymer. The phenol resin can include a structure shown in formula 1:
wherein R is a hydrogen atom or a methyl group, and n is 4 to 400.
The monomer or the polymer having an epoxy group can be one or a plurality of different monomers or polymers having an epoxy group. That is, the photoimprinting resin composition solution can contain one monomer or polymer having an epoxy group, and can also contain a plurality of different monomers or polymers having an epoxy group. In the present embodiment, the monomer having an epoxy group can include 1,4-cyclohexanedimethanol diglycidyl ether, bisphenol A diglycidyl ether, bis[4-(glycidyloxy)phenyl]methane, 1,4-butanediol diglycidyl ether, 1,2,7,8-diepoxyoctane, diglycidyl 1,2-cyclohexanedicarboxylate, N,N-diglycidyl-4-glycidyloxyaniline, 4,4′-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, α-pinene oxide, 3-(1H,1H,5H-octafluoropentyloxy)-1,2-epoxypropane, or trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane. The polymer having an epoxy group can include poly[(phenyl glycidyl ether)-co-formaldehyde] or poly[(o-cresyl glycidyl ether)-co-formaldehyde]. The monomer or the polymer having an epoxy group can reduce the imprint temperature of the imprinting process.
The cationic photopolymerization initiator can include triarylsulfonium hexafluoroantimonate salt, triarylsulfonium hexafluorophosphate salt, diaryliodonium salt, or ferrocenium salt. In the present embodiment, a weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution is used for the cationic photopolymerization initiator. The cationic photopolymerization initiator can generate crosslinking and curing to the monomer or the polymer having an epoxy group in the formed photoimprinting resin thin film via an irradiation step. As a result, not only can the issue of a brittle imprint structure be alleviated, the etch resistance thereof can also be increased.
The solvent can include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol propyl ether, anisole, or propylene carbonate. In the present embodiment, via the selection and the mixing of the solvent, the adhesion and the coating properties of the photoimprinting resin composition solution can be adjusted.
In the photoimprinting resin composition solution of the present embodiment, based on 100 parts by weight of the thermoplastic resin, the content of the monomer or the polymer having an epoxy group is 10 parts by weight to 500 parts by weight, the content of the cationic photopolymerization initiator is 1 part by weight to 50 parts by weight, and the content of the solvent is 50 parts by weight to 5000 parts by weight. In an embodiment, based on 100 parts by weight of the thermoplastic resin, the content of the monomer or the polymer having an epoxy group is 40 parts by weight to 400 parts by weight, the content of the cationic photopolymerization initiator is 5 part by weight to 40 parts by weight, and the content of the solvent is 100 parts by weight to 3000 parts by weight. In particular, based on 100 parts by weight of the thermoplastic resin, the content of the monomer or the polymer having an epoxy group is 80 parts by weight to 250 parts by weight, the content of the cationic photopolymerization initiator is 10 part by weight to 25 parts by weight, and the content of the solvent is 300 parts by weight to 1000 parts by weight.
According to another embodiment of the disclosure, in addition to including a solvent, a monomer or a polymer having an epoxy group, a cationic photopolymerization initiator, and a thermoplastic resin, the photoimprinting resin composition solution can further include an additive. The additive can include a photoacid generator, a surfactant, a polyol, or a combination thereof. In the present embodiment, by adding a photoacid generator, the peelability of the formed photoimprinting resin thin film can be increased; by adding a surfactant, the coating properties of the photoimprinting resin composition solution and the mold release properties of the formed photoimprinting resin thin film can be adjusted; by adding a polyol, the curing properties of the formed photoimprinting resin thin film in the irradiation step can be adjusted.
Referring to
Referring further to
Then, referring to
Based on the above, since a pre-bake process is performed to remove the solvent in the step of
Referring to
Then, referring to
Referring to
In the following, experimental examples are listed to describe in detail the photoimprinting resin composition solution provided in the above embodiments and characteristics thereof when applied in a patterning method. However, the following experimental examples are not intended to limit the disclosure.
3 g of novolak solution A, 1 g of 1,4-cyclohexanedimethanol diglycidyl ether, and 0.16 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, and the phenol resin is acresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000. The patterning method was performed via the photoimprinting resin composition solution. In particular, a pre-bake process was performed under a temperature of 120° C. for 300 s, the imprinting process was performed under a temperature of 80° C. with a pressure of 2.3 Kgf/cm2 for 60 s, the irradiation step was performed by an UV exposure dose of 900 mj/cm2, and the imprint mold was removed under a temperature of 70° C.
3 g of novolak solution A, 0.2 g of 1,4-cyclohexanedimethanol diglycidyl ether, and 0.096 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, and the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000. The patterning method was performed via the photoimprinting resin composition solution. In particular, a pre-bake process was performed under a temperature of 120° C. for 300 s, the imprinting process was performed under a temperature of 80° C. with a pressure of 2.3 Kgf/cm2 for 60 s, the irradiation step was performed by an UV exposure dose of 900 mj/cm2, and the imprint mold was removed under a temperature of 70° C.
3 g of novolak solution A, 0.5 g of 1,4-cyclohexanedimethanol diglycidyl ether, and 0.12 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, and the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000. The patterning method was performed via the photoimprinting resin composition solution. In particular, a pre-bake process was performed under a temperature of 120° C. for 300 s, the imprinting process was performed under a temperature of 80° C. with a pressure of 2.3 Kgf/cm2 for 60 s, the irradiation step was performed by an UV exposure dose of 900 mj/cm2, and the imprint mold was removed under a temperature of 70° C.
3 g of novolak solution A was used to perform a patterning method. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, and the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000. In particular, a pre-bake process was performed under a temperature of 120° C. for 300 s, the imprinting process was performed under a temperature of 80° C. with a pressure of 2.3 Kgf/cm2 for 60 s, the irradiation step was performed by an UV exposure dose of 900 mj/cm2, and the imprint mold was removed under a temperature of 70° C.
Then, evaluations of imprint formability and mold release effect were performed on the photoimprinting resin thin films formed by the photoimprinting resin composition solutions of example 1 to example 3 in the patterning method and the photoimprinting resin thin film of the comparative example formed in the patterning method, and each evaluation result is shown in Table 1 below.
It can be known from Table 1 that, in the comparative example, only novolak solution A is used as the component of the photoimprinting resin, the imprint pattern formability of the formed photoimprinting resin thin film is poor, and the imprinting resin fracture sticks to the mold. In comparison, in addition to novolak solution A, 1,4-cyclohexanedimethanol diglycidyl ether and triarylsulfonium hexafluoroantimonate are further added in the photoimprinting resin composition solutions of example 1 to example 3. It can be known from Table 1 that, the imprint pattern formability of the photoimprinting resin thin films formed by the photoimprinting resin composition solutions of example 1 to example 3 is good, and mold release thereof is complete. In comparison to the photoimprinting resin thin film formed by the solution of the comparative example, since the monomer having an epoxy group and the cationic photopolymerization initiator are added in the photoimprinting resin composition solutions of example 1 to example 3, the imprint pattern formability of the formed photoimprinting resin thin films can be increased, and mold release property thereof can be improved.
3 g of novolak solution A, 1 g of 1,4-cyclohexanedimethanol diglycidyl ether, 0.16 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 0.6 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000.
3 g of novolak solution A, 0.5 g of 1,4-cyclohexanedimethanol diglycidyl ether, 0.12 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 0.6 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000.
3 g of novolak solution A, 0.8 g of bisphenol A diglycidyl ether, 0.18 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 0.6 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000.
3 g of novolak solution A, 0.5 g of bisphenol A diglycidyl ether, 0.12 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 0.6 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000.
Then, the steps of
It can be known from Table 2 that, in example 4 to example 7, different types of monomers having an epoxy group are respectively added, and different amounts thereof are added. Specifically, in example 4, 1 g of 1,4-cyclohexanedimethanol diglycidyl ether is added, and an imprinting process can be performed on the formed photoimprinting resin thin film under room temperature. In example 5, 0.5 g of 1,4-cyclohexanedimethanol diglycidyl ether is added, and an imprinting process can be performed on the formed photoimprinting resin thin film under a temperature of ≧50° C. In example 6, 0.8 g of bisphenol A diglycidyl ether is added, and an imprinting process can be performed on the formed photoimprinting resin thin film under a temperature of ≧60° C. In example 7, 0.5 g of bisphenol A diglycidyl ether is added, and an imprinting process can be performed on the formed photoimprinting resin thin film under a temperature of ≧70° C. It can therefore be known that, when preparing the photoimprinting resin composition solution of the disclosure, the imprint temperature of the photoimprinting resin thin film can be adjusted by adjusting the type and the amount of the monomer having an epoxy group. As a result, the patterning method of the disclosure can be performed via a room temperature imprinting process or a heating imprinting process.
18 g of novolak solution A, 3 g of 1,4-cyclohexanedimethanol diglycidyl ether, 0.72 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 6 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000.
15 g of novolak solution A, 2.5 g of bisphenol A diglycidyl ether, 0.6 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 7.5 g of PGMEA were mixed to fonn a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000.
9 g of novolak solution A, 1.2 g of bisphenol A diglycidyl ether, 0.36 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 3.75 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000.
9 g of novolak solution A, 1.8 g of 1,4-cyclohexanedimethanol diglycidyl ether, 0.38 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 5.25 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000.
9 g of novolak solution B, 2.4 g of bisphenol A diglycidyl ether, 0.63 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 12 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution B is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 35 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2500.
9 g of novolak solution B, 2.15 g of bisphenol A diglycidyl ether, 0.62 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 12 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution B is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 35 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2500.
9 g of novolak solution A, 0.5 g of 1,4-cyclohexanedimethanol diglycidyl ether, 1.8 g of poly[(phenyl glycidyl ether)-co-formaldehyde], 0.51 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 5.5 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution A is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 28 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2000.
15 g of novolak solution B, 2 g of 1,4-cyclohexanedimethanol diglycidyl ether, 4.45 g of bisphenol A diglycidyl ether, 1.52 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 11.2 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution B is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 35 wt %, the phenol resin is acresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2500.
15.4 g of novolak solution B, 1.2 g of bisphenol A diglycidyl ether, 4.92 g of poly[(phenyl glycidyl ether)-co-formaldehyde], 1.37 g of weight concentration 50% triarylsulfonium hexafluoroantimonate propylene carbonate solution, and 8.9 g of PGMEA were mixed to form a photoimprinting resin composition solution. The novolak solution B is a phenol resin solution with PGMEA as the solvent, wherein the content of the phenol resin is 35 wt %, the phenol resin is a cresol/phenol resin obtained by polymerizing formaldehyde, dimethylphenol, and methyl phenol, and the weight-average molecular weight thereof is about 2500.
The commercial product epoxy imprint resin and the photoimprinting resin composition solutions of example 8 to example 16 were applied in the processing steps of
It can be known from Table 3 that, the etch rate of the commercial product epoxy imprint resin is 165 nm/min, and the etch rates of the photoimprinting resin thin films of example 8 to example 16 are all lower than 165 nm/min. Therefore, the etch rates of the photoimprinting resin thin films of example 8 to example 16 are slower. That is, the photoimprinting resin thin films formed by the photoimprinting resin composition solutions of example 8 to example 16 have superior etch resistance.
Based on the above, since the photoimprinting resin composition solution provided in the disclosure includes a monomer or a polymer having an epoxy group, the imprint temperature of the formed photoimprinting resin thin film can be reduced. Moreover, since the photoimprinting resin composition solution provided in the disclosure also includes a cationic photopolymerization initiator, crosslinking and curing can be generated to the monomer or the polymer having an epoxy group in the formed photoimprinting resin thin film via an irradiation step. As a result, not only can the issue of a brittle imprint structure be alleviated, the etch resistance thereof can also be increased. Moreover, when applied in a lithography and etching process of a semiconductor or metal oxide, the photoimprinting resin composition solution of the disclosure further has the advantages of lower investment in equipment and simplified process.
Although the disclosure has been described with reference to the above embodiments, it will be apparent to one of the ordinary skill in the art that modifications and variations to the described embodiments may be made without departing from the spirit and scope of the disclosure. Accordingly, the scope of the disclosure will be defined by the attached claims not by the above detailed descriptions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 103142138 | Dec 2014 | TW | national |
