WO2024109119A1 - 用于光刻图案化的全碳氢低介电损耗光敏树脂的制备及应用 - Google Patents

用于光刻图案化的全碳氢低介电损耗光敏树脂的制备及应用 Download PDF

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WO2024109119A1
WO2024109119A1 PCT/CN2023/108030 CN2023108030W WO2024109119A1 WO 2024109119 A1 WO2024109119 A1 WO 2024109119A1 CN 2023108030 W CN2023108030 W CN 2023108030W WO 2024109119 A1 WO2024109119 A1 WO 2024109119A1
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vinylphenyl
benzocyclobutenyl
photosensitive
photosensitive resin
ethylene
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PCT/CN2023/108030
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English (en)
French (fr)
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杨军校
杜翰林
邓跃霆
马佳俊
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西南科技大学
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Publication of WO2024109119A1 publication Critical patent/WO2024109119A1/zh

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the integrated circuit materials industry is located at the upstream of the integrated circuit industry chain. It is the foundation of the entire industry and the basis for the development of the integrated circuit industry. The quality of materials directly affects the performance of integrated circuit products. However, the domestic integrated circuit materials industry's independent controllable capabilities and international competitiveness are far from sufficient, especially independent products are still concentrated in the middle and low-end, and high-end products are heavily dependent on imports. With the rapid development of the microelectronics industry, the corresponding electronic devices and integrated circuits are developing in the direction of miniaturization, high speed, and high density, requiring dielectric materials with lower dielectric constants and loss factors to accommodate more metal wires in narrower intervals.
  • UV curing is a low-cost, environmentally friendly polymer material curing technology that can cure to form a three-dimensional network structure in a short time. Since the mid-20th century, UV curing technology has made great progress and has been widely used in many fields.
  • the core of UV curing is photoresist. In the integrated circuit manufacturing process, photochemical reactions occur in the exposed area of the photoresist, resulting in solubility differences between the exposed area and the non-exposed area in the developer.
  • the resulting photolithography pattern can be used as a dielectric insulating layer for integrated circuits.
  • Organic polymer materials exhibit excellent performance due to their structural characteristics. Since the lateral diffusion of macromolecules is suppressed, the patterns of polymers usually have higher resolution.
  • Benzocyclobutene (BCB) groups can be cross-linked and cured by heating without producing small molecules (as shown in Figure 1), which has little effect on the performance of the resin.
  • Photosensitive resins prepared with benzocyclobutene as the base material have the advantages of low dielectric constant, low dielectric loss, low moisture absorption rate, and high thermal stability, and have important application value in microelectronic packaging.
  • photosensitive resins with all-carbon hydrogen structures have low chemical conductivity under external electric field conditions. The advantages of chemical polarity and low polarizability are beneficial to reducing the dielectric constant.
  • the film under the mask was irradiated with ultraviolet light, and a pattern with a minimum feature size of 5 microns was obtained after development.
  • the thermal stability of the photosensitive resin is low, and it is difficult to meet the high heat resistance requirements in the process of electronic device manufacturing.
  • CYCLOTENE 4000 Series photosensitive resin developed by DOW Chemical Company shows good comprehensive performance, but its high dielectric constant (Dk: 2.65) and dielectric loss (Df: 0.005-0.008) due to the high polarity Si-O bonds limit its application in high-frequency fields.
  • the present invention relates to the preparation of a photosensitive resin system of a 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene monomer and a polymer thereof, a composite photoinitiator system and a solvent.
  • the photosensitive resin system can be used for the structural expansion of a benzocyclobutene photosensitive resin.
  • the benzocyclobutene structure has relatively strong rigidity, so that the mechanical properties and thermal stability of the material are improved and enhanced. Due to the introduction of double bonds, the synthesized polymer has relatively more photocrosslinking sites and can be photocured under ultraviolet light.
  • the polymer after photo/thermal curing has a high degree of crosslinking, excellent mechanical properties, chemical stability and thermal stability, and relatively low dielectric constant and dielectric loss, and can be applied to the field of microelectronics, and provides a reference for the cross-integration of multiple patterning and microelectronics related fields.
  • An object of the present invention is to solve at least the above-mentioned problems and/or disadvantages and to provide at least the advantages which will be described hereinafter.
  • a method for preparing a full carbon hydrogen low dielectric loss photosensitive resin for photolithography patterning wherein a photosensitive solution is prepared from 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene monomer, 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene polymer, a photoinitiator system and an organic solvent, and a photosensitive film is prepared from the photosensitive solution, i.e., a full carbon hydrogen low dielectric loss photosensitive resin for photolithography patterning;
  • the 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene polymer is a 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene homopolymer, and its structural formula is:
  • n 1 ⁇ 1000.
  • the 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene polymer is a copolymer of 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene and styrene, and its structural formula is:
  • n 1 ⁇ 1000
  • m 1 ⁇ 1000.
  • the 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene homopolymer is replaced by a copolymer of 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene and divinylbenzene, the structural formula of which is:
  • n 1 ⁇ 1000
  • m 1 ⁇ 1000.
  • the photoinitiator system is one or more of 2,6-bis-(4-azidobenzylidene)cyclohexanone, 3,3'-carbonylbis(7-diethylaminocoumarin), benzophenone and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide;
  • the organic solvent is one or more of toluene and chloroform.
  • the amount of the 2,6-bis-(4-azidobenzylidene)cyclohexanone is 1 to 10% of the mass of the 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene polymer; the amount of the 3,3'-carbonylbis(7-diethylaminocoumarin) is 0.1 to 5% of the mass of the 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene polymer; the amount of the 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene monomer is 10 to 20% of the mass of the 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene polymer; the mass volume ratio of the 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene polymer to the organic solvent is 1 g:3 to 10 mL;
  • the process of preparing a photosensitive film by using a photosensitive solution is as follows: drop the photosensitive solution on a glass sheet or a silicon sheet for spin coating at a speed of 2500 to 5000 rpm for 30 to 60 seconds to obtain a photosensitive film, and then dry it;
  • the process of preparing the photosensitive solution is carried out under light protection.
  • the present invention also provides an application of a full carbon hydrogen low dielectric loss photosensitive resin for photolithography patterning prepared by the preparation method as described above in photolithography patterning, using a 365nm UV-LED point light source to expose the photosensitive film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, and the unexposed area is soluble in a developer; after development with a developer, a pattern consistent with the photomask is obtained; finally, the photocured film is heat-treated to obtain a film with a high cross-linking density. Through the light/heat double cross-linking process, the obtained film has a high thermal stability. At the same time, during the heat treatment process, the unreacted photoinitiator will be thermally decomposed and will not affect the dielectric properties of the film.
  • the developer is cyclohexanone and petroleum ether in a volume ratio of 2 to 6:1;
  • the programmed heating and cooling process is: keeping warm at 150-170°C for 0.5-1.5 hours, keeping warm at 175-190°C for 0.5-1.5 hours, keeping warm at 195-205°C for 1-3 hours, keeping warm at 210-220°C for 1-3 hours, keeping warm at 225-235°C for 1-3 hours, keeping warm at 210-220°C for 0.5-1.5 hours, keeping warm at 195-205°C for 0.5-1.5 hours, keeping warm at 175-190°C for 0.5-1.5 hours, keeping warm at 150-170°C for 0.5-1.5 hours, and cooling naturally.
  • the 1-(4-vinylphenyl)-2-(4-benzocyclobutene)ethylene monomer and polymer thereof of the present invention are all-carbon hydrogen structures, and the molecular weight of such polymers is 6,000 to 200,000. Under the condition of an applied electric field, the all-carbon hydrogen structure has the advantages of low chemical polarity and low polarizability, which is beneficial to reducing dielectric loss. Due to the introduction of benzocyclobutene groups, cross-linking and curing can be carried out by heating, without small molecule release, and the cross-linking density is large, so it has good heat resistance and mechanical properties. The monomer and polymer are blended and added into a photosensitive system, so that the photosensitive system has good film-forming properties and photosensitivity, which is beneficial to the generation of light patterning.
  • the pattern obtained after photocuring of the photosensitive system of the present invention has high clarity, and the obtained film has high thermal stability through the light/heat double cross-linking process; at the same time, during the heat treatment process, the unreacted photoinitiator will thermally decompose and will not affect the dielectric properties of the film; the all-hydrocarbon benzocyclobutene photosensitive resin provided by the present invention has relatively excellent dielectric properties (10GHz, Dk: 2.4, Df: 0.001 ⁇ 0.002), mechanical properties (Young’s modulus: 5.58GPa), heat resistance (T5%: 420°C) and chemical stability, and is expected to be applied in the field of microelectronics.
  • the all-carbon hydrogen photosensitive resin of the present invention can cross-link the double bonds in the polymer chain through photocuring. It is insoluble in the developing solution, so a pattern with neat edges and high precision is obtained.
  • the currently used all-carbon hydrogen photosensitive resin faces the problem of insufficient thermal stability, so the benzocyclobutene group is introduced to form a light/heat double cross-linking structure through thermal cross-linking curing of benzocyclobutene, which improves the thermal stability of the all-carbon hydrogen photosensitive resin. At the same time, the pattern will not deform during the heat treatment process.
  • FIG1 is a 1 H NMR spectrum of P-DVB-S-BCB prepared in Example 1;
  • FIG2 is an infrared FTIR spectrum of the material prepared in Example 1;
  • FIG3 is a thermogravimetric curve of the material prepared in Example 1;
  • FIG4 is a thermogravimetric curve of the material prepared in Example 1.
  • FIG5 is a dielectric constant of the material prepared in Example 1;
  • FIG6 is a diagram showing the dielectric loss of the material prepared in Example 1.
  • FIG7 is a graph of Young's modulus of the material prepared in Example 1.
  • FIG8 is a nanoindentation image of the material prepared in Example 1.
  • FIG9 is a microscope image of the light-cured material (UV cured film) of Example 1;
  • Figure 10 is a microscope image of the material (UV/Thermal cured film) after light curing and heat treatment in Example 1.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • UV cured film was subjected to a programmed temperature rising process, the temperature rising process was 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour and natural cooling to obtain a film with high cross-linking density (UV/Thermal cured film).
  • the structure and purity of P-DVB-S-BCB were determined by the number of proton hydrogens and the peak integrated area, indicating that the polymer P-DVB-S-BCB was successfully prepared.
  • FIG3 is a thermogravimetric curve of the material prepared in Example 1; it can be seen that the decomposition temperatures of the UV-curable and UV/thermal-curable polymers at 5% weight loss (T 5 %) are 415° C. and 420° C., respectively, and they have high thermal stability.
  • Figure 4 is the thermogravimetric curve of the material prepared in Example 1; the thermal curing process of the polymer film is inferred by measuring the thermal decomposition temperature of the polymer film; the thermogravimetric curves of the polymer films after different treatments, the sample after UV curing begins to decompose above 110°C, and a thermogravimetric stage appears at around 200°C, showing a gradually decreasing curve on the TGA graph. This is because BAC begins to decompose at 120°C and the aziridine group begins to decompose at around 200°C.
  • FIG5 is a dielectric constant of the material prepared in Example 1, which reflects the dielectric properties or polarization properties of the material under the action of an electrostatic field; the dielectric constants of the cured DVB-S-BCB and the cured P-DVB-S-BCB at a frequency of 10 MHz are 2.54 and 2.55, respectively, and the low dielectric properties are good;
  • FIG6 is the dielectric loss of the material prepared in Example 1, which reflects the phenomenon that the dielectric itself is heated due to the consumption of part of the electric energy in the alternating electric field.
  • the dielectric loss of the cured DVB-S-BCB and the cured P-DVB-S-BCB at a frequency of 10 MHz are 1.40 ⁇ 10 -3 and 1.56 ⁇ 10 -3 respectively, which have low loss performance.
  • FIG7 is a graph of the Young's modulus of the material prepared in Example 1; it can be seen that the Young's modulus of the P-DVB-S-BCB film after light/heat curing reaches 5.58 GPa, which has good mechanical properties;
  • FIG8 is a nanoindentation image of the material prepared in Example 1; it can be seen that the hardness of the P-DVB-S-BCB film after light/heat curing is 0.5 GPa, which has good performance in the field of photosensitive resins.
  • FIG9 is a microscopic image of the UV cured film of Example 1.
  • the image was taken using an optical microscope.
  • the pattern is a 40-micron polygonal pattern with connected corner lines.
  • the microscopic image shows that the obtained pattern has a high degree of fineness and that the patterning performance of this photosensitive resin is good.
  • Figure 10 is a microscopic image of the material (UV/Thermal cured film) after light curing and heat treatment in Example 1; the microscopic image shows that the pattern of this photosensitive resin will not be deformed after heat treatment and still retains excellent patterning performance. At the same time, through the light/heat double cross-linking process, the obtained film has higher thermal stability.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • DVB-BCB (1 g, 4.3 mmol) and styrene (0.45 g, 4.3 mmol) were added to a 50 ml dry flask, and then appropriate dry tetrahydrofuran was added as a solvent, and n-butyl lithium was used as an initiator.
  • the photosensitive solution was dropped onto a glass sheet for spin coating at a speed of 3000 rpm for 40 seconds to obtain a photosensitive film, which was then placed in an oven at 80°C for 10 minutes.
  • a 365nm UV-LED point light source was used to expose the photosensitive film through a photomask.
  • the exposed area was cross-linked and cured and difficult to dissolve in the developer, while the unexposed area was soluble in the developer.
  • a pattern consistent with the photomask was obtained.
  • the photocured film was subjected to a programmed temperature rise process, which was 160°C for 1 hour, 180°C for 1 hour, and 200°C for 2 hours.
  • the film was heated at 215°C for 2 hours, at 230°C for 2 hours, at 215°C for 1 hour, at 200°C for 1 hour, at 180°C for 1 hour, at 160°C for 1 hour and cooled naturally to obtain a film with high cross-linking density.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the photocured film was subjected to a programmed temperature rise process, which was 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a high cross-linking density. film.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating at a speed of 3000 rpm for 40 seconds to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes.
  • a 365nm UV-LED point light source is used to expose the film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer.
  • the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.
  • the photoinitiator can be replaced by a composite system of 2,6-bis-(4-azidobenzylidene)cyclohexanone and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, a composite system of 2,6-bis-(4-azidobenzylidene)cyclohexanone and benzophenone, and a composite system of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and benzophenone.
  • the 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene homopolymer can be replaced by a copolymer of 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene and styrene and a copolymer of 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene and divinylbenzene.
  • Figure 11 is the reaction process and mechanism of the present invention.
  • the reaction mechanism of the present invention is:
  • the photoinitiator 2,6-bis-(4-azidobenzylidene) cyclohexanone forms nitrene radicals under ultraviolet light, and the nitrene radicals react with double bonds to form a three-membered nitrogen heterocyclic structure for crosslinking.
  • the benzocyclobutene four-membered ring opens at high temperature to form an o-dimethylquinone intermediate, which undergoes a Diels-Alder reaction with each other to form an eight-membered ring structure or a Diels-Alder reaction with a double bond to form a six-membered ring.

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Abstract

一种用于光刻图案化的全碳氢低介电损耗光敏树脂的制备及应用，由1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体、1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物、光引发体系和有机溶剂配制形成光敏溶液，通过光敏溶液制备光敏薄膜，即用于光刻图案化的全碳氢低介电损耗光敏树脂；使用365nm的UV-LED点光源通过光掩膜版对光敏薄膜进行曝光，曝光的区域交联固化而难溶于显影液，未曝光的区域则可溶于显影液；经过显影液显影得到与光掩膜版一致的图案；最后对光固化后的薄膜进行热处理，得到高交联密度的薄膜。全碳氢苯并环丁烯光敏树脂具有比较优异的介电性能、机械性能、耐热性以及化学稳定性。

Description

用于光刻图案化的全碳氢低介电损耗光敏树脂的制备及应用 技术领域
本发明属于光刻图案化材料制备技术领域，具体涉及一种用于光刻图案化的全碳氢低介电损耗光敏树脂的制备及应用。
背景技术
集成电路材料产业位于集成电路产业链上游，是整个行业的根基，是发展集成电路产业的基础，材料的品质直接影响集成电路产品性能。然而，国内集成电路材料行业的自主可控能力及国际竞争力远远不足，特别是自主产品尚集中在中低端，高端产品严重依赖进口。随着微电子工业的快速发展，相应的电子器件和集成电路正朝着小型化、高速化、高密度方向发展，需要更低介电常数和损耗因子的介质材料，以满足在更窄的间隔上容纳更多的金属线。2021年3月发布的《国民经济和社会发展第十四个五年规划和2035远景目标纲要》中明确提出光刻胶等迫切的国家需求：“加快茂金属聚烯烃等高性能树脂和集成电路用光刻胶等电子高纯材料关键技术突破。”
紫外光固化是一种低成本、环保的聚合物材料固化技术，可在短时间内固化形成三维网络结构。自20世纪中叶以来，UV固化技术取得了长足的进步，在许多领域得到了广泛的应用。紫外光固化的核心是光刻胶。在集成电路制造过程中，光化学反应发生在光刻胶的曝光区域，导致曝光区域与非曝光区域在显影液中出现溶解度差异，由此产生的光刻图案可以用作集成电路的介质绝缘层。有机高分子材料由于其结构特点而表现出优异的性能，由于大分子的横向扩散被抑制，高分子聚合物的图案通常具有较高的分辨率。
苯并环丁烯(BCB)基团可以通过加热交联固化，不会产生小分子(如图1)，对树脂的性能影响较小。以苯并环丁烯为基材制备的光敏树脂具有介电常数低、介电损耗小、吸湿率低、热稳定性高等优点，在微电子封装中具有重要的应用价值。另一方面，全碳氢结构的光敏树脂在外加电场条件下具有低化 学极性和低极化率的优点，有利于降低介电常数。
Burgoon等人报道了两种全碳氢结构的聚合物(ACS Applied Polymer Materials,2020,2(5),1819-1826)。分别通过5-丁烯基-2-降冰片烯自身或与5-癸基-2-降冰片烯的共烯烃交换反应，得到两种侧链含有乙烯基双键的全碳氢树脂。在这两种聚合物中加入光交联剂2,6-双-(4-叠氮苯亚甲基)-4-乙基环己酮和溶剂配置成光敏溶液，然后将光敏溶液旋涂形成光敏薄膜，通过紫外光照射掩膜版下的薄膜，经显影后得到最小特征尺寸为5微米的图案。但该光敏树脂的热稳定性较低，难以满足电子器件制作过程中的高耐热性要求。
DOW化学公司开发的CYCLOTENE 4000Series光敏树脂显示了良好的综合性能，但其因含有较高极性的Si-O键而显示出较高的介电常数(Dk:2.65)和介电损耗(Df:0.005-0.008)限制了其在高频领域的应用。
发明内容
本发明涉及一种1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体及其聚合物、复配光引发体系和溶剂的光敏树脂体系的配制，该光敏树脂体系可用于苯并环丁烯光敏树脂的结构扩展，苯并环丁烯结构具有比较强的刚性，使材料的力学性能和热稳定性得到改善和提高；由于双键的引入，合成的聚合物具有比较多的光交联位点，可在紫外光照射下光固化。光/热固化后的聚合物交联度高，机械性能、化学稳定性和热稳定性优异，同时具有比较低的介电常数和介电损耗，可应用于微电子领域，同时为多个图案化与微电子相关领域的交叉融合提供借鉴。
本发明的一个目的是解决至少上述问题和/或缺陷，并提供至少后面将说明的优点。
为了实现根据本发明的这些目的和其它优点，提供了一种用于光刻图案化的全碳氢低介电损耗光敏树脂的制备方法，由1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体、1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物、光引发体系和有机溶剂配制形成光敏溶液，通过光敏溶液制备光敏薄膜，即用于光刻图案化的全碳氢低介电损耗光敏树脂；
其中，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体的结构式为：
优选的是，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯均聚物，其结构式为：
其中，n＝1～1000。
优选的是，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与烯烃的共聚物；所述烯烃为苯乙烯、二乙烯基苯中的任意一种。
优选的是，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与苯乙烯的共聚物，其结构式为：
其中，n＝1～1000，m＝1～1000。
优选的是，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯均聚物替换为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与二乙烯基苯的共聚物，其结构式为：
其中，n＝1～1000，m＝1～1000。
优选的是，所述光引发体系为2,6-双-(4-叠氮苯亚甲基)环己酮、3,3'-羰基双(7-二乙胺香豆素)、二苯甲酮和二苯基(2,4,6-三甲基苯甲酰基)氧化膦中的一种或几种；
其中，所述2,6-双-(4-叠氮苯亚甲基)环己酮的结构式为：
所述3,3'-羰基双(7-二乙胺香豆素)的结构式为：
优选的是，所述有机溶剂为甲苯、三氯甲烷中的一种或几种。
优选的是，所述2,6-双-(4-叠氮苯亚甲基)环己酮的用量为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物质量的1～10％；所述3,3'-羰基双(7-二乙胺香豆素)的用量为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物质量的0.1～5％；所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体的用量为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物质量的10～20％；所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物与有机溶剂的质量体积比为1g:3～10mL；
通过光敏溶液制备光敏薄膜的过程为：将光敏溶液滴在玻璃片或硅片上进行旋涂，转速为2500～5000rpm，旋转30～60s，得到光敏薄膜，烘干；
所述配制形成光敏溶液的过程中进行超声溶解；
所述配制形成光敏溶液的过程中在避光下进行。
本发明还提供一种如上所述的制备方法制备的用于光刻图案化的全碳氢低介电损耗光敏树脂在光刻图案化中的应用，使用365nm的UV-LED点光源通过光掩膜版对光敏薄膜进行曝光，曝光的区域交联固化而难溶于显影液，未曝光的区域则可溶于显影液；经过显影液显影得到与光掩膜版一致的图案；最后对光固化后的薄膜进行热处理，得到高交联密度的薄膜。通过光/热双交联过程，所得的薄膜具有较高的热稳定性。同时在热处理过程中，未反应的光引发剂会热分解，不会影响薄膜的介电性能。
优选的是，所述显影液为体积比为2～6:1的环己酮：和石油醚；
所述程序升温、降温的过程为150～170℃保温0.5～1.5小时、175～190℃保温0.5～1.5小时、195～205℃保温1～3小时、210～220℃保温1～3小时、225～235℃保温1～3小时、210～220℃保温0.5～1.5小时、195～205℃保温0.5～1.5小时、175～190℃保温0.5～1.5小时、150～170℃保温0.5～1.5小时、自然降温。
本发明的1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体及其聚合物为全碳氢结构，该类聚合物的分子量为6千～20万。在在外加电场条件下，全碳氢结构具有低化学极性和低极化率的优点，有利于降低介电损耗。由于引入苯并环丁烯基团，能够通过加热发生交联固化，无小分子释放，交联密度大，因此其具有良好的耐热性能及力学性能。将单体与聚合物共混加入光敏体系中，使得该光敏体系具有良好的成膜性能和光敏性能，这有益于光图案化的产生。
本发明至少包括以下有益效果：
本发明的光敏体系光固化后所得的图案具有较高的清晰度，通过光/热双交联过程，所得的薄膜具有较高的热稳定性；同时在热处理过程中，未反应的光引发剂会热分解，不会影响薄膜的介电性能；本发明提供的全碳氢苯并环丁烯光敏树脂，具有比较优异的介电性能(10GHz，Dk:2.4，Df：0.001～0.002)、机械性能(Young’s modulus:5.58GPa)、耐热性(T5％:420℃)以及化学稳定性，有望应用于微电子领域。
本发明所述的全碳氢光敏树脂能通过光固化使聚合物链中的双键交联而 不溶于显影溶液，因此得到边缘整齐、精度较高的图案。而目前所使用的全碳氢光敏树脂面临着热稳定性不足的问题，因此引入苯并环丁烯基团，通过苯并环丁烯的热交联固化来形成光/热双交联结构，提高了全碳氢光敏树脂的热稳定性，同时，图案在热处理过程中不会发生变形。
本发明的其它优点、目标和特征将部分通过下面的说明体现，部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明：
图1为实施例1制备的P-DVB-S-BCB的1H NMR谱图；
图2为实施例1制备的材料的红外FTIR谱图；
图3为实施例1制备的材料的热重曲线；
图4为实施例1制备的材料的热重曲线；
图5为实施例1制备的材料的介电常数；
图6为实施例1制备的材料的介电损耗；
图7为实施例1制备的材料的杨氏模量图；
图8为实施例1制备的材料的纳米压痕图；
图9为实施例1光固化后的材料(UV cured film)的显微镜图；
图10为实施例1光固化并热处理后的材料(UV/Thermal cured film)的显微镜图。
具体实施方式：
下面结合附图对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
应当理解，本文所使用的诸如“具有”、“包含”以及“包括”术语并不排除一个或多个其它元件或其组合的存在或添加。
实施例1：
在50ml干燥烧瓶中加入1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体DVB-BCB(1g，4.3mmol)，再加入适当的干燥四氢呋喃作为溶剂，以正丁基锂作为引发剂，在-78℃反应7h，加入10ml甲醇终止反应，得到黄色液体； 将混合物滴加到甲醇中，产生白色沉淀，分离，固体真空干燥，得到收率为90％的1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯均聚物；其结构式为：
其中，n＝100；
称量0.1g 1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯均聚物(M＝2.1W)(P-DVB-S-BCB)加入到3mL棕色样品瓶中，称量加入0.005g光引发剂2,6-双-(4-叠氮苯亚甲基)环己酮(BAC)、0.001g 3,3'-羰基双(7-二乙胺香豆素)和均聚物10％质量分数的1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体(DVB-S-BCB)，然后在棕色样品瓶中加入溶剂甲苯0.4mL和三氯甲烷0.2mL，超声溶解，得到光敏溶液；
将光敏溶液滴在玻璃片上进行旋涂，转速为3000rpm，旋转40s，得到光敏薄膜(Uncured film)，将其放入80℃的烘箱中烘10分钟；待溶剂挥干后，使用365nm的UV-LED点光源通过光掩膜版对光敏薄膜进行曝光，曝光的区域交联固化而难溶于显影液，未曝光的区域则可溶于显影液；经过显影液(环己酮：石油醚＝4:1)显影得到与光掩膜版一致的图案(UV cured film)；最后对光固化后的薄膜进行程序升温过程，该升温过程为160℃保温1小时、180℃保温1小时、200℃保温2小时、215℃保温2小时、230℃保温2小时、215℃保温1小时、200℃保温1小时、180℃保温1小时、160℃保温1小时、自然降温，得到高交联密度的薄膜(UV/Thermal cured film)。
图1为实施例1制备的P-DVB-S-BCB的1H NMR谱图；1H NMR(600MHz，Chloroform-d)δ3.17(d,J＝2.3Hz,4H),7.05–6.98(m,2H),1.26(md,J＝9.0Hz,1H),1.54(s,J＝12.1Hz,2H),2.67(m,J＝5.9Hz,2H)。由质子氢的数目和峰积分面积确定P-DVB-S-BCB的结构和纯度，可知成功制备聚合物P-DVB-S-BCB。
图2为实施例1制备的材料的红外FTIR谱图；通过分子吸收基团的振动 峰确定分子结构和光固化反应基团；960cm-1处有＝C-h键的面外弯曲振动吸收峰，苯基之间的乙烯基具有反式双取代结构；1472cm-1处是环丁烯的C-H摇摆振动吸收峰；1489cm-1处是环己烯的振动吸收峰，可能是由于邻二甲苯之间的偶联反应生成的环己烷结构，以及邻二甲苯与乙烯基之间的Diels-Alder反应生成的环己烯结构；2110cm-1处是偶氮基的振动吸收峰，当偶氮发生分解，峰会降低。
图3为实施例1制备的材料的热重曲线；可知UV固化和UV/热固化聚合物在失重5％(T5％)时的分解温度分别为415℃和420℃，具有较高的热稳定性。
图4为实施例1制备的材料的热重曲线；通过测定聚合物薄膜的热分解温度推测其热固化过程；不同处理后的聚合物薄膜的热失重曲线，UV固化后的样品在110℃以上开始分解，在200℃左右出现热失重阶段，在TGA图上呈逐渐下降曲线，这是由于BAC在120℃开始分解，氮丙啶基在200℃左右开始分解。
图5为实施例1制备的材料的介电常数；反映材料静电场作用下介电性质或极化性质；固化的DVB-S-BCB和固化的P-DVB-S-BCB在10Mhz频率下的介电常数分别为2.54和2.55，低介电性能良好；
图6为实施例1制备的材料的介电损耗；反映电介质在交变电场中、由于消耗部分电能而使电介质本身发热的现象大小；固化的DVB-S-BCB和固化的P-DVB-S-BCB在10Mhz频率下的介电损耗分别为1.40×10-3和1.56×10-3，具有低损耗性能；
图7为实施例1制备的材料的杨氏模量图；可知光/热固化后的P-DVB-S-BCB薄膜的杨氏模量达到5.58GPa，具有良好的力学性能；
图8为实施例1制备的材料的纳米压痕图；可知光/热固化后的P-DVB-S-BCB薄膜的硬度为0.5GPa，在光敏树脂领域内具有不错的性能。
图9为实施例1光固化后的材料(UV cured film)的显微镜图；该图片是使用光学显微镜所拍摄的，其中的图案是40微米带有拐角线条相连的多边形图案，从该显微图片可以说明得到的图案精细度较高，此种光敏树脂的图案化性能较好。
图10为实施例1光固化并热处理后的材料(UV/Thermal cured film)的显微镜图；该显微图片说明此种光敏树脂的图案经过热处理后不会发生变形，仍然保留了优异的图案化性能，同时通过光/热双交联过程，所得的薄膜具有更高的热稳定性。
实施例2：
在50ml干燥烧瓶中加入DVB-BCB(1g，4.3mmol)和苯乙烯(0.45g，4.3mmol)，再加入适当的干燥四氢呋喃作为溶剂，以正丁基锂作为引发剂，在-78℃反应7h，加入10ml甲醇终止反应，得到黄色液体；将混合物滴加到甲醇中，产生白色沉淀，分离，固体真空干燥，得到收率为84％的1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与苯乙烯的共聚物；其结构式为：
其中，n＝50，m＝50；
称量0.1g 1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与苯乙烯的共聚物(M＝1.5W)加入到3mL棕色样品瓶中，称量加入0.005g光引发剂2,6-双-(4-叠氮苯亚甲基)环己酮(BAC)、0.001g 3,3'-羰基双(7-二乙胺香豆素)和共聚物10％质量分数的1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体，然后在棕色样品瓶中加入溶剂甲苯0.4mL和三氯甲烷0.2mL，超声溶解，得到光敏溶液；
将光敏溶液滴在玻璃片上进行旋涂，转速为3000rpm，旋转40s，得到光敏薄膜，将其放入80℃的烘箱中烘10分钟；待溶剂挥干后，使用365nm的UV-LED点光源通过光掩膜版对光敏薄膜进行曝光，曝光的区域交联固化而难溶于显影液，未曝光的区域则可溶于显影液；经过显影液(环己酮：石油醚＝4:1)显影得到与光掩膜版一致的图案；最后对光固化后的薄膜进行程序升温过程，该升温过程为160℃保温1小时、180℃保温1小时、200℃保温2小 时、215℃保温2小时、230℃保温2小时、215℃保温1小时、200℃保温1小时、180℃保温1小时、160℃保温1小时、自然降温，得到高交联密度的薄膜。
实施例3：
在50ml干燥烧瓶中加入DVB-BCB(1g，4.3mmol)和二乙烯基苯(0.56g，4.3mmol)，再加入适当的干燥四氢呋喃作为溶剂，以正丁基锂作为引发剂，在-78℃反应7h，加入10ml甲醇终止反应，得到黄色液体。将混合物滴加到甲醇中，产生白色沉淀，分离，固体真空干燥，得到收率为75％的1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与二乙烯基苯的共聚物；其结构式为：
其中，n＝50，m＝50；
称量0.1g 1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与二乙烯基苯的共聚物(M＝2.6W)加入到3mL棕色样品瓶中，称量加入0.005g光引发剂2,6-双-(4-叠氮苯亚甲基)环己酮(BAC)、0.001g 3,3'-羰基双(7-二乙胺香豆素)和共聚物10％质量分数的1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体，然后在棕色样品瓶中加入溶剂甲苯0.4mL和三氯甲烷0.2mL，超声溶解，得到光敏溶液；
将光敏溶液滴在玻璃片上进行旋涂，转速为3000rpm，旋转40s，得到光敏薄膜，将其放入80℃的烘箱中烘10分钟；待溶剂挥干后，使用365nm的UV-LED点光源通过光掩膜版对光敏薄膜进行曝光，曝光的区域交联固化而难溶于显影液，未曝光的区域则可溶于显影液；经过显影液(环己酮：石油醚＝1:1)显影得到与光掩膜版一致的图案。最后对光固化后的薄膜进行程序升温过程，该升温过程为160℃保温1小时、180℃保温1小时、200℃保温2小时、215℃保温2小时、230℃保温2小时、215℃保温1小时、200℃保温1小时、180℃保温1小时、160℃保温1小时、自然降温，得到高交联密度的 薄膜。
实施例4：
称量0.1g 1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯均聚物(M＝1.3W)加入到3mL棕色样品瓶中，称量加入光引发剂0.004g二苯基(2,4,6-三甲基苯甲酰基)氧化膦、0.002g二苯甲酮和均聚物10％质量分数的1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体，然后在棕色样品瓶中加入溶剂甲苯0.4mL和三氯甲烷0.2mL，超声溶解，得到光敏溶液；
将光敏溶液滴在玻璃片或硅片上进行旋涂，转速为3000rpm，旋转40s，得到光敏薄膜，将其放入80℃的烘箱中烘10分钟；待溶剂挥干后，使用365nm的UV-LED点光源通过光掩膜版对薄膜进行曝光，曝光的区域交联固化而难溶于显影液，未曝光的区域则可溶于显影液；经过显影液(环己酮：石油醚＝4:1)显影得到与光掩膜版一致的图案；最后对光固化后的薄膜进行程序升温过程，该升温过程为160℃保温1小时、180℃保温1小时、200℃保温2小时、215℃保温2小时、230℃保温2小时、215℃保温1小时、200℃保温1小时、180℃保温1小时、160℃保温1小时、自然降温，得到高交联密度的薄膜。
上述实施例1～3中，光引发剂可以替换为2,6-双-(4-叠氮苯亚甲基)环己酮与二苯基(2,4,6-三甲基苯甲酰基)氧化膦的复配体系、2,6-双-(4-叠氮苯亚甲基)环己酮与二苯甲酮的复配体系、二苯基(2,4,6-三甲基苯甲酰基)氧化膦与二苯甲酮的复配体系。
上述实施例4中，1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯均聚物可以替换为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与苯乙烯的共聚物和1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与二乙烯基苯的共聚物。
图11为本发明的反应流程及机理：
本发明的反应机理为：
光引发剂2,6-双-(4-叠氮苯亚甲基)环己酮在紫外光照射下形成氮烯自由基，氮烯自由基与双键发生反应形成三元氮杂环结构而交联。在热固化过程中，苯并环丁烯四元环在高温下开环形成邻二甲烯醌中间体，邻二甲烯醌互相发生Diels-Alder反应形成八元环结构或与双键发生Diels-Alder反应形成六 元环结构而交联。通过调节优化光引发剂的量、曝光能量、曝光时间等研究其官能团转化率、光敏动力学等，优化树脂光敏体系。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节和这里示出与描述的图例。

Claims (10)

  1. 一种用于光刻图案化的全碳氢低介电损耗光敏树脂的制备方法，其特征在于，由1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体、1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物、光引发体系和有机溶剂配制形成光敏溶液，通过光敏溶液制备光敏薄膜，即用于光刻图案化的全碳氢低介电损耗光敏树脂；
    其中，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体的结构式为：
  2. 如权利要求1所述的用于光刻图案化的全碳氢低介电损耗光敏树脂的制备方法，其特征在于，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯均聚物，其结构式为：
    其中，n＝1～1000。
  3. 如权利要求1所述的用于光刻图案化的全碳氢低介电损耗光敏树脂的制备方法，其特征在于，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与烯烃的共聚物；所述烯烃为苯乙烯、二乙烯基苯中的任意一种。
  4. 如权利要求1所述的用于光刻图案化的全碳氢低介电损耗光敏树脂的制备方法，其特征在于，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与苯乙烯的共聚物，其结构 式为：
    其中，n＝1～1000，m＝1～1000。
  5. 如权利要求2所述的用于光刻图案化的全碳氢低介电损耗光敏树脂的制备方法，其特征在于，所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯均聚物替换为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯与二乙烯基苯的共聚物，其结构式为：
    其中，n＝1～1000，m＝1～1000。
  6. 如权利要求1所述的用于光刻图案化的全碳氢低介电损耗光敏树脂的制备方法，其特征在于，所述光引发体系为2,6-双-(4-叠氮苯亚甲基)环己酮、3,3'-羰基双(7-二乙胺香豆素)、二苯甲酮和二苯基(2,4,6-三甲基苯甲酰基)氧化膦中的一种或几种；
    其中，所述2,6-双-(4-叠氮苯亚甲基)环己酮的结构式为：
    所述3,3'-羰基双(7-二乙胺香豆素)的结构式为：
  7. 如权利要求1所述的用于光刻图案化的全碳氢低介电损耗光敏树脂的制备方法，其特征在于，所述有机溶剂为甲苯、三氯甲烷中的一种或几种。
  8. 如权利要求6所述的用于光刻图案化的全碳氢低介电损耗光敏树脂的制备方法，其特征在于，
    所述2,6-双-(4-叠氮苯亚甲基)环己酮的用量为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物质量的1～10％；所述3,3'-羰基双(7-二乙胺香豆素)的用量为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物质量的0.1～5％；所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯单体的用量为1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物质量的10～20％；所述1-(4-乙烯基苯基)-2-(4-苯并环丁烯基)乙烯类聚合物与有机溶剂的质量体积比为1g:3～10mL；
    通过光敏溶液制备光敏薄膜的过程为：将光敏溶液滴在玻璃片或硅片上进行旋涂，转速为2500～5000rpm，旋转30～60s，得到光敏薄膜，烘干；
    所述配制形成光敏溶液的过程中进行超声溶解；
    所述配制形成光敏溶液的过程中在避光下进行。
  9. 一种如权利要求1～8任一项所述的制备方法制备的用于光刻图案化的全碳氢低介电损耗光敏树脂在光刻图案化中的应用，其特征在于，使用365nm的UV-LED点光源通过光掩膜版对光敏薄膜进行曝光，曝光的区域交联固化而难溶于显影液，未曝光的区域则可溶于显影液；经过显影液显影得到与光掩膜版一致的图案；最后对光固化后的薄膜进行热处理，得到高交联密度的薄膜。
  10. 如权利要求9所述的用于光刻图案化的全碳氢低介电损耗光敏树脂在光刻图案化中的应用，其特征在于，所述显影液为体积比为2～6:1的环己酮：和石油醚；
    所述热处理的过程为150～170℃保温0.5～1.5小时、175～190℃保温0.5～1.5 小时、195～205℃保温1～3小时、210～220℃保温1～3小时、225～235℃保温1～3小时、210～220℃保温0.5～1.5小时、195～205℃保温0.5～1.5小时、175～190℃保温0.5～1.5小时、150～170℃保温0.5～1.5小时、自然降温。
PCT/CN2023/108030 2022-11-22 2023-07-19 用于光刻图案化的全碳氢低介电损耗光敏树脂的制备及应用 WO2024109119A1 (zh)

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