WO2022012077A1

WO2022012077A1 - Low-dielectric intrinsic negative photosensitive polyimide material and preparation method therefor

Info

Publication number: WO2022012077A1
Application number: PCT/CN2021/082190
Authority: WO
Inventors: 闵永刚; 朋小康; 廖松义; 黄兴文; 张诗洋; 刘荣涛; 赵晨; 刘屹东
Original assignee: 广东工业大学; 东莞华南设计创新院
Priority date: 2020-07-14
Filing date: 2021-03-22
Publication date: 2022-01-20
Also published as: CN111995752A

Abstract

A low-dielectric intrinsic negative photosensitive polyimide material and a preparation method therefor. The preparation method comprises the following steps: dissolving a first diamine monomer, a second diamine monomer, and dianhydride monomers in an organic solvent, wherein the dianhydride monomers are added in batches; obtaining a polyamide acid solution by means of reaction for a certain period of time; spin-coating the polyamide acid solution to obtain a polyamide acid film; and then performing gradient imidization treatment in a preset temperature range to obtain the low-dielectric intrinsic negative photosensitive polyimide material. The preparation method achieves the purpose of self-sensitization by introducing a diyne group as a light sensing source, and the obtained photosensitive polyimide material has remarkable mechanical properties and thermal properties. In addition, introducing a large amount of fluorine into the photosensitive polyimide can effectively reduce the dielectric constant and water absorption of the material to further facilitate use. The preparation method is simple and can be used for forming a film material having a uniform and controllable thickness.

Description

A kind of low dielectric intrinsic type negative photosensitive polyimide material and preparation method thereof

technical field

The invention relates to the field of photosensitive polyimide materials, in particular to a low dielectric intrinsic type negative photosensitive polyimide material and a preparation method thereof.

Background technique

Compared with traditional photoresist, photosensitive polyimide (PSPI) has good dielectric properties, so it does not need to be coated with a photo-blocker that only acts as a working medium during use, which can greatly shorten the time. process, improve production efficiency, has been widely used in the field of integrated circuit packaging. At present, most photosensitive polyimides focus on chemical amplification systems and doping of photoinitiators. Although the photosensitivity and resolution are high, due to the high molecular structure of polyimide, the removal of small molecule auxiliary residues is difficult. There will be some obstacles, which will affect the performance of electronic components, and the doping of small molecular impurities will greatly affect the mechanical and thermal properties of polyimide itself. Therefore, the development of high-performance intrinsic photosensitive polyimide is a major research problem.

SUMMARY OF THE INVENTION

In order to solve the technical problem that the existing polyimide is unfavorable to use, the present invention provides a low-dielectric intrinsic type negative photosensitive polyimide material and a preparation method thereof.

The invention provides a preparation method of a low dielectric intrinsic type negative photosensitive polyimide material, which comprises the following steps: mixing a first diamine monomer, a second diamine monomer and a dibasic anhydride monomer Dissolving in an organic solvent, wherein dibasic anhydride monomers are added in batches; reacting for a certain time to obtain a polyamic acid solution; spin-coating the polyamic acid solution to obtain a polyamic acid film; The amination treatment obtains a low-dielectric intrinsic type negative photosensitive polyimide material.

Further, the ratio of the sum of the molar mass of the first diamine monomer and the second diamine monomer to the molar mass of the dibasic anhydride monomer is 1: (1-1.2); The molar ratio of the amine monomer and the second diamine monomer is 1: (1-9); the mass ratio of the first diamine monomer, the second diamine monomer and the dibasic anhydride monomer is The ratio of the mass to the organic solvent is (0.5-2.5):10.

Further, the organic solvent is one or more of N,N-dimethylacetamide, N,N-dimethylformamide or N-methylpyrrolidone.

Further, the described dibasic anhydride monomer is one or more of 6FDA, 6FXDA, PFPDA, 3FDA, 3FXDA, 3FX3FXDA, and its molecular structural formula is as follows:

Further, the described first diamine monomer is more than one of p-BDDA, m-BDDA or o-BDDA, and its molecular structural formula is as follows:

Further, the second diamine monomer is more than one of TFMOB, 3,3'-6FDAm, 3FDAm, TFMB, 4,4'-6FDAm or BDAF, and its molecular structure is as follows:

Further, the gradient imidization temperature range is 100-400°C.

On the other hand, the present invention also provides a low-dielectric intrinsic type negative photosensitive polyimide material, and the low-dielectric intrinsic type negative photosensitive polyimide material is prepared by the preparation method.

The beneficial effects of the present invention are: in the embodiment of the present invention, a diacetylenic group is introduced as a light-sensing light source, on the one hand, the purpose of self-sensitization is achieved, and on the other hand, the prepared photosensitive polyimide material has considerable mechanical properties and thermal properties. . In addition, introducing a large amount of fluorine element into the photosensitive polyimide can effectively reduce the dielectric constant and water absorption rate of the material, and is more convenient to use; the preparation method of the invention is simple, and can form a film material with uniform and controllable thickness.

detailed description

The following describes in detail the embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary, and are intended to explain the present invention and should not be construed as limiting the present invention.

In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", " Rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", etc. The relationship is based on the orientation or positional relationship shown in the drawings, only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore It should not be construed as a limitation of the present invention.

In addition, the terms "first" and "second" are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implying the number of indicated technical features. Thus, a feature defined as "first" or "second" may expressly or implicitly include one or more of that feature. In the description of the present invention, "plurality" means two or more, unless otherwise expressly and specifically defined.

In the present invention, unless otherwise expressly specified and limited, terms such as "installation", "connection", "connection", "fixation" and other terms should be understood in a broad sense, for example, it may be a fixed connection or a detachable connection , or integrally connected; it can be a mechanical connection or an electrical connection; it can be a direct connection, or an indirect connection through an intermediate medium, or the internal communication between the two components. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations.

In the present invention, unless otherwise expressly specified and limited, a first feature "on" or "under" a second feature may include the first and second features in direct contact, or may include the first and second features Not directly but through additional features between them. Also, the first feature being "above", "over" and "above" the second feature includes the first feature being directly above and obliquely above the second feature, or simply means that the first feature is level higher than the second feature. The first feature is "below", "below" and "below" the second feature includes the first feature being directly below and diagonally below the second feature, or simply means that the first feature has a lower level than the second feature.

The present invention will be further described in detail below through specific embodiments in conjunction with the accompanying drawings.

In the embodiment of the present invention, a diacetylenic group is introduced as a photosensitive light source, on the one hand, the purpose of self-sensitization is achieved, and on the other hand, the prepared photosensitive polyimide material has considerable mechanical properties and thermal properties. In addition, introducing a large amount of fluorine element into the photosensitive polyimide can effectively reduce the dielectric constant and water absorption rate of the material, and is more convenient to use; the preparation method of the invention is simple, and can form a film material with uniform and controllable thickness.

The application of the low dielectric intrinsic type negative photosensitive polyimide material in the fields of chip packaging, integrated circuit etching and the like.

In an optional embodiment, the ratio of the sum of the molar mass of the first diamine monomer and the second diamine monomer to the molar mass of the dibasic anhydride monomer is 1: (1-1.2); The molar ratio of the first diamine monomer and the second diamine monomer is 1: (1-9); the first diamine monomer, the second diamine monomer and the dibasic anhydride The ratio of the sum of the mass of the monomers to the mass of the organic solvent is (0.5-2.5):10.

In an optional embodiment, the organic solvent is one or more of N,N-dimethylacetamide, N,N-dimethylformamide or N-methylpyrrolidone.

In an optional embodiment, the described dibasic anhydride monomer is one or more of 6FDA, 6FXDA, PFPDA, 3FDA, 3FXDA, 3FX3FXDA, and its molecular structural formula is as follows:

In an optional embodiment, the first diamine monomer is one or more of p-BDDA, m-BDDA or o-BDDA, and its molecular structure is as follows:

In an optional embodiment, the second diamine monomer is one or more of TFMOB, 3,3'-6FDAm, 3FDAm, TFMB, 4,4'-6FDAm or BDAF, and its molecular structure is as follows shown:

In an optional embodiment, the gradient imidization temperature ranges from 100 to 400°C.

Specific examples are as follows:

Example 1

5mmol 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 5mmol 1,4-bis(4-aminophenyl)butadiyne (p-BDDA) and 10mmol Hexafluorodianhydride (6FDA) was successively dissolved in 40mL of N,N-dimethylacetamide solvent (hexafluorodianhydride was added in batches), and the photosensitive polyamic acid (PSPAA) solution was obtained by stirring and reacting at room temperature in a nitrogen atmosphere; The PSPAA solution is spin-coated to obtain a PSPAA film, which is then subjected to gradient imidization at 100°C, 200°C, 300°C, 350°C, and 400°C to obtain a low-dielectric intrinsic type negative photosensitive polyimide material.

The average thickness of the photosensitive polyimide material obtained above is 10 μm, the dielectric constant is 2.73@1MHz, and the water absorption rate is 0.62%. The i-line exposure sensitivity of this PSPAA solution is 260mJ/cm2, which can be formed by i-line exposure and development The negative photolithography pattern with a resolution of 10 μm has considerable application prospects in the field of chip packaging and photoresist.

Example 2

2.5mmol 2,2-bis(4-aminophenyl)hexafluoropropane (4,4'-6FDAm), 7.5mmol 1,4-bis(3-aminophenyl)butadiyne (m-BDDA) and 10mmol 1,3-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (PFPDA) was successively dissolved in 40 mL of N,N-dimethylformamide solvent (dianhydride was added in batches), and the dianhydride was added in argon atmosphere. , and stirring at room temperature to obtain a photosensitive polyamic acid (PSPAA) solution; spin coating the PSPAA solution to obtain a PSPAA film, and then undergo gradient imidization at 100 °C, 200 °C, 300 °C, 350 °C, and 400 °C to obtain Low dielectric intrinsic type negative photosensitive polyimide material.

The average thickness of the photosensitive polyimide material obtained above is 10 μm, the dielectric constant is 3.05@1MHz, and the water absorption rate is 0.75%. The i-line exposure sensitivity of this PSPAA solution is 215mJ/cm2, which can be formed by i-line exposure and development. Negative-tone lithography pattern with 8 μm resolution.

Example 3

7.5mmol 2,2-bis(3-aminophenyl)hexafluoropropane (3,3'-6FDAm), 2.5mmol 1,4-bis(2-aminophenyl)butadiyne (o-BDDA) and 10mmol 4,4'-(1-phenyl-2,2,2-trifluoroethylidene) diphthalic anhydride (3FDA) was successively dissolved in 40 mL of N-methylpyrrolidone solvent (dianhydride was added in batches), The photosensitive polyamic acid (PSPAA) solution was obtained by stirring the reaction in an argon atmosphere at room temperature; the PSPAA solution was spin-coated to obtain a PSPAA film, and then the PSPAA film was subjected to a gradient of 100°C, 200°C, 300°C, 350°C, and 400°C. After calcination, a low-dielectric intrinsic type negative photosensitive polyimide material is obtained.

The average thickness of the photosensitive polyimide material obtained above is 10μm, the dielectric constant is 2.55@1MHz, and the water absorption rate is 0.51%. The i-line exposure sensitivity of this PSPAA solution is 310mJ/cm2, which can be formed by i-line exposure and development. Negative-tone lithography patterns with a resolution of 10 μm.

In the description of this specification, reference is made to the description of the terms "one embodiment", "some embodiments", "one embodiment", "some embodiments", "example", "specific example", or "some examples", etc. It is intended that a particular feature, structure, material or characteristic described in connection with this embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The above content is a further detailed description of the present invention in conjunction with specific embodiments, and it cannot be considered that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art to which the present invention pertains, some simple deductions or substitutions can be made without departing from the concept of the present invention.

Claims

A method for preparing a low-dielectric intrinsic type negative photosensitive polyimide material, characterized by comprising the following steps: mixing a first diamine monomer, a second diamine monomer and a dibasic anhydride monomer Dissolving in an organic solvent, wherein dibasic anhydride monomers are added in batches; reacting for a certain time to obtain a polyamic acid solution; spin-coating the polyamic acid solution to obtain a polyamic acid film; The amination treatment obtains a low-dielectric intrinsic type negative photosensitive polyimide material.
The method for preparing a low-dielectric intrinsic type negative photosensitive polyimide material according to claim 1, wherein the molar mass of the first diamine monomer and the second diamine monomer is a The molar mass ratio of the sum to the dibasic anhydride monomer is 1:(1～1.2); the molar ratio of the first diamine monomer and the second diamine monomer is 1:(1～9); The ratio of the sum of the mass of the first diamine monomer, the second diamine monomer and the dibasic anhydride monomer to the mass of the organic solvent is (0.5-2.5):10.
The method for preparing a low-dielectric intrinsic type negative photosensitive polyimide material according to claim 1, wherein the organic solvent is N,N-dimethylacetamide, N,N-dimethicone One or more of methylformamide or N-methylpyrrolidone.
The method for preparing a low-dielectric intrinsic type negative photosensitive polyimide material according to claim 1, wherein the dibasic anhydride monomer is 6FDA, 6FXDA, PFPDA, 3FDA, 3FXDA, One or more of 3FX3FXDA, its molecular structure is as follows:
The method for preparing a low-dielectric intrinsic type negative photosensitive polyimide material according to claim 1, wherein the first diamine monomer is p-BDDA, m-BDDA or o- More than one of BDDA, its molecular structure is as follows:
The method for preparing a low dielectric intrinsic type negative photosensitive polyimide material according to claim 1, wherein the second diamine monomer is TFMOB, 3,3'-6FDAm, 3FDAm , more than one of TFMB, 4,4'-6FDAm or BDAF, and its molecular structure is as follows:
The method for preparing a low-dielectric intrinsic type negative photosensitive polyimide material according to claim 1, wherein the gradient imidization temperature ranges from 100 to 400°C.
A low-dielectric intrinsic type negative photosensitive polyimide material, characterized in that the low-dielectric intrinsic type negative photosensitive polyimide material is prepared according to any one of claims 1 to 7 method produced.