TWI759378B - Negative photosensitive resin composition, resin film and electronic device - Google Patents
Negative photosensitive resin composition, resin film and electronic device Download PDFInfo
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- C08F220/56—Acrylamide; Methacrylamide
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- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- 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
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- 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
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Abstract
Description
本發明係關於一種負型感光性樹脂組成物、樹脂膜及電子裝置。The present invention relates to a negative photosensitive resin composition, a resin film and an electronic device.
在迄今為止的負型感光性樹脂組成物的領域中,以提高伴隨圖案的微細化而產生之阻劑圖案的精度為目的,正在開發各種技術。作為該種技術,例如可列舉專利文獻1中記載之技術。依該專利文獻1,記載有一種含有[A]聚合物及[B]酸產生物之感放射線性樹脂組成物。並且,記載有如下內容:藉由[A]聚合物具有結構單元(I)及結構單元(II),表示線寬度的不穩定性的小度的LWR(Line Width Roughness(線寬粗糙度))性能及缺陷抑制性優異(專利文獻1的0012段)。 記載有如下內容:其中,記載了結構單元(I)係來自於N-(三級丁氧基羰基甲基)馬來醯亞胺、N-(1-甲基-1-環戊氧基羰基甲基)馬來醯亞胺、或N-(2-乙基-2-金剛烷基氧基羰基甲基)馬來醯亞胺的結構單元。又,記載有如下內容:結構單元(II)係來自於2-降莰烯的結構單元。 [先前技術文獻] [專利文獻]In the field of conventional negative-type photosensitive resin compositions, various techniques have been developed for the purpose of improving the accuracy of the resist pattern produced with the miniaturization of the pattern. As such a technique, the technique described in patent document 1 is mentioned, for example. According to this patent document 1, the radiation sensitive resin composition containing [A] polymer and [B] acid generator is described. In addition, it is described that the LWR (Line Width Roughness) indicating the small degree of instability of the line width is indicated by the fact that the polymer [A] has the structural unit (I) and the structural unit (II). Excellent performance and defect suppression (paragraph 0012 of Patent Document 1). It is described as follows: wherein, it is described that the structural unit (I) is derived from N-(tertiary butoxycarbonylmethyl)maleimide, N-(1-methyl-1-cyclopentyloxycarbonyl Methyl)maleimide, or N-(2-ethyl-2-adamantyloxycarbonylmethyl)maleimide structural unit. Furthermore, it is described that the structural unit (II) is a structural unit derived from 2-norbornene. [Prior Art Literature] [Patent Literature]
專利文獻1:日本特開2015-184458號公報Patent Document 1: Japanese Patent Laid-Open No. 2015-184458
[發明欲解決的問題][Problems to be Solved by Invention]
本發明人製作由負型感光性樹脂組成物形成之樹脂膜,並研究了該樹脂膜的耐熱性、耐溶劑性等耐久性及顯影後的殘膜率等顯影性。其結果判明,從耐久性及顯影性的觀點考慮,專利文獻1中記載之由感放射線性樹脂組成物形成之樹脂膜還有進一步改善的餘地。 因此,本發明的課題為提供一種能夠在不損害鹼顯影性的情況下,以良好的平衡提高耐久性及顯影性之負型感光性樹脂組成物。 [解決問題之方式]The present inventors produced a resin film formed from a negative photosensitive resin composition, and studied the durability of the resin film such as heat resistance and solvent resistance, and developability such as residual film ratio after development. As a result, it turned out that the resin film formed of the radiation-sensitive resin composition described in Patent Document 1 has room for further improvement from the viewpoints of durability and developability. Therefore, the subject of this invention is to provide the negative photosensitive resin composition which can improve durability and developability with a favorable balance, without impairing alkali developability. [How to solve the problem]
本發明人為了提高由負型感光性樹脂組成物形成之樹脂膜的耐熱性、耐溶劑性等耐久性及顯影後的殘膜率等顯影性,對係共聚物之聚合物所具備之結構單元進行了研究。其結果判明,藉由共聚物具備經含有末端不飽和碳雙鍵之官能基取代之降莰烯型結構單元、經羧基取代之降莰烯型結構單元、來自於馬來酸酐、馬來酸酐衍生物、馬來醯亞胺或馬來醯亞胺衍生物之結構單元,能夠在不損害鹼顯影性之情況下平衡良好地提高耐久性及顯影性。 藉由上述內容,本發明人發現了藉由包含含有特定結構單元之共聚物,能夠在不損害鹼顯影性之情況下提高使用了負型感光性樹脂組成物之樹脂膜的耐久性及顯影性,藉此完成了本發明。In order to improve the durability such as heat resistance and solvent resistance of the resin film formed from the negative photosensitive resin composition, and the developability such as the residual film ratio after development, the present inventors focused on the structural unit of the polymer of the copolymer. Were studied. As a result, it was found that the copolymer has norbornene-type structural units substituted with functional groups containing terminal unsaturated carbon double bonds, norbornene-type structural units substituted with carboxyl groups, derived from maleic anhydride, and maleic anhydride-derived structural units. It is a structural unit of maleimide, maleimide or maleimide derivative, which can improve durability and developability in a well-balanced manner without impairing alkali developability. Based on the above, the present inventors discovered that the durability and developability of a resin film using a negative photosensitive resin composition can be improved without impairing alkali developability by including a copolymer containing a specific structural unit. , thereby completing the present invention.
依本發明,提供一種負型感光性樹脂組成物,其包含: 下述式(1)表示之係共聚物之聚合物; 交聯劑;及 光敏劑。According to the present invention, there is provided a negative photosensitive resin composition comprising: a polymer of a copolymer represented by the following formula (1); a crosslinking agent; and a photosensitizer.
(式(1)中、 l及m表示聚合物中的莫耳含有率, l+m=1, A包含由下述式(A1)表示之結構單元、及 由下述式(A2)表示之結構單元, B包含由下述式(B1)、下述式(B2)、下述式(B3)、下述式(B4)、下述式(B5)或下述式(B6)表示之結構單元中的至少一種以上。) (In the formula (1), l and m represent the molar content in the polymer, l+m=1, A includes a structural unit represented by the following formula (A1), and a structure represented by the following formula (A2) Structural unit, B includes a structure represented by the following formula (B1), the following formula (B2), the following formula (B3), the following formula (B4), the following formula (B5) or the following formula (B6) at least one of the units.)
(式(A1)中,R1 、R2 、R3 及R4 分別獨立地為氫或碳數1~30的有機基,R1 、R2 、R3 及R4 中包含至少一個末端不飽和碳雙鍵。n為0、1或2。) (In formula (A1), R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and R 1 , R 2 , R 3 and R 4 include at least one terminal Saturated carbon double bond. n is 0, 1 or 2.)
(式(A2)中,R5 、R6 及R7 分別獨立地為氫或碳數1~30的有機基,n為0、1或2。) (In formula (A2), R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.)
(式(B1)中,R8 獨立地為碳數1~30的有機基。) (In formula (B1), R 8 is independently an organic group having 1 to 30 carbon atoms.)
(式(B2)中,R9 及R10 分別獨立地為碳數1~30的有機基。) (In formula (B2), R 9 and R 10 are each independently an organic group having 1 to 30 carbon atoms.)
(式(B6)中,R11 獨立地為碳數1~30的有機基。) (In formula (B6), R 11 is independently an organic group having 1 to 30 carbon atoms.)
又,依本發明,提供一種由上述負型感光性樹脂組成物形成之樹脂膜。Moreover, according to this invention, the resin film which consists of the said negative photosensitive resin composition is provided.
另外,依本發明,提供一種具備上述樹脂膜之電子裝置。 [發明之效果]Moreover, according to this invention, the electronic device provided with the said resin film is provided. [Effect of invention]
依本發明,提供一種能夠在不損害鹼顯影性之情況下提高由負型感光性樹脂組成物形成之樹脂膜的耐久性及顯影性的負型感光性樹脂組成物。According to the present invention, there is provided a negative photosensitive resin composition capable of improving the durability and developability of a resin film formed from the negative photosensitive resin composition without impairing the alkali developability.
以下,適當地利用圖式對本實施形態進行說明。另外,在所有圖式中,對相同的構成要素標註相同符號,並省略說明。又,在本實施形態中,A~B係指A以上B以下。Hereinafter, the present embodiment will be described using the drawings as appropriate. In addition, in all drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted. In addition, in this embodiment, A-B means A or more and B or less.
對本實施形態的負型感光性樹脂組成物的概要進行說明。 本實施形態的負型感光性樹脂組成物包含: 下述式(1)表示之係共聚物之聚合物; 交聯劑;及 光敏劑。The outline of the negative photosensitive resin composition of this embodiment is demonstrated. The negative photosensitive resin composition of the present embodiment includes: a polymer of a copolymer represented by the following formula (1); a crosslinking agent; and a photosensitizer.
(式(1)中, l及m表示聚合物中的莫耳含有率, l+m=1, A包含由下述式(A1)表示之結構單元、及 由下述式(A2)表示之結構單元, B包含由下述式(B1)、下述式(B2)、下述式(B3)、下述式(B4)、下述式(B5)或下述式(B6)表示之結構單元中的至少一種以上。) (In the formula (1), l and m represent the molar content in the polymer, l+m=1, A includes a structural unit represented by the following formula (A1), and a structure represented by the following formula (A2) Structural unit, B includes a structure represented by the following formula (B1), the following formula (B2), the following formula (B3), the following formula (B4), the following formula (B5) or the following formula (B6) at least one of the units.)
(式(A1)中,R1 、R2 、R3 及R4 分別獨立地為氫或碳數1~30的有機基,R1 、R2 、R3 及R4 中包含至少一個末端不飽和碳雙鍵。n為0、1或2。) (In formula (A1), R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and R 1 , R 2 , R 3 and R 4 include at least one terminal Saturated carbon double bond. n is 0, 1 or 2.)
(式(A2)中,R5 、R6 及R7 分別獨立地為氫或碳數1~30的有機基,n為0、1或2。) (In formula (A2), R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.)
(式(B1)中,R8 獨立地為碳數1~30的有機基。) (In formula (B1), R 8 is independently an organic group having 1 to 30 carbon atoms.)
(式(B2)中,R9 及R10 分別獨立地為碳數1~30的有機基。) (In formula (B2), R 9 and R 10 are each independently an organic group having 1 to 30 carbon atoms.)
(式(B6)中,R11 獨立地為碳數1~30的有機基。) (In formula (B6), R 11 is independently an organic group having 1 to 30 carbon atoms.)
依本實施形態,共聚物包含經含有末端不飽和碳雙鍵之官能基取代之降莰烯型結構單元、經羧基取代之降莰烯型結構單元、及來自於馬來酸酐、馬來酸酐衍生物、馬來醯亞胺或馬來醯亞胺衍生物之結構單元。According to this embodiment, the copolymer comprises norbornene-type structural units substituted by functional groups containing terminal unsaturated carbon double bonds, norbornene-type structural units substituted by carboxyl groups, and derived from maleic anhydride and maleic anhydride. compound, maleimide or the structural unit of maleimide derivatives.
本實施形態之負型感光性樹脂組成物藉由光敏劑因曝光而產生自由基,並引起自由基連鎖反應而硬化。在本實施形態之負型感光性樹脂組成物中,認為共聚物的降莰烯側鏈的末端不飽和碳雙鍵有助於自由基連鎖反應。藉此,雖然詳細的機理尚不明確,但推測本實施形態之負型感光性樹脂組成物與以往的負型感光性樹脂組成物相比,能夠提高藉由自由基連鎖反應形成之交聯結構的交聯密度,並能夠進一步限制分子鏈的運動性。因此,能夠提高負型感光性樹脂組成物的硬化膜的耐熱性、耐溶劑性等耐久性及顯影後的殘膜率等顯影性。The negative photosensitive resin composition of the present embodiment generates radicals due to exposure by a photosensitizer, and causes a radical chain reaction to be cured. In the negative photosensitive resin composition of the present embodiment, it is considered that the terminal unsaturated carbon double bond of the norbornene side chain of the copolymer contributes to the radical chain reaction. Therefore, although the detailed mechanism is not clear, it is presumed that the negative photosensitive resin composition of the present embodiment can improve the crosslinking structure formed by the radical chain reaction compared with the conventional negative photosensitive resin composition. and can further limit the mobility of molecular chains. Therefore, the heat resistance of the cured film of a negative photosensitive resin composition, durability, such as solvent resistance, and developability, such as the residual film ratio after image development, can be improved.
又,關於本實施形態之負型感光性樹脂組成物,例如如上述般,使一部分曝光並硬化,另一方面,使一部分未曝光且未硬化。然後,藉由鹼溶液去除未硬化之未曝光部分,從而能夠用於所期望的用途。 在本實施形態之共聚物中,經含有末端不飽和碳雙鍵之官能基取代之降莰烯型結構單元,係藉由取代經羧基取代之降莰烯型結構單元的一部分而形成。然後,一部分經羧基取代之降莰烯型結構單元保持原樣殘留在共聚物中。藉此,本實施形態之共聚物包含具備羧基之降莰烯型結構單元。藉此,在去除未曝光部分時,能夠提高鹼溶解性。 而且,藉由共聚物包含來自於馬來酸酐、馬來酸酐衍生物、馬來醯亞胺或馬來醯亞胺衍生物之結構單元,從而能夠適當地控制鹼溶解性。 在以往的負型感光性樹脂組成物中,當提高負型感光性樹脂組成物的硬化膜的耐久性及顯影性時,僅簡單設為容易交聯之結構,則存在導致鹼溶解性降低之不良情況。然而,本實施形態之負型感光性樹脂組成物中,藉由共聚物包含經含有末端不飽和碳雙鍵之官能基取代之降莰烯型結構單元、經羧基取代之降莰烯型結構單元及來自於馬來酸酐、馬來酸酐衍生物、馬來醯亞胺或馬來醯亞胺衍生物之結構單元,能夠在不降低鹼溶解性之情況下提高硬化膜的耐久性及顯影性。 藉由上述內容,本實施形態之負型感光性樹脂組成物係能夠在不損害鹼顯影性之情況下提高由負型感光性樹脂組成物形成之樹脂膜的耐久性及顯影性者。Moreover, about the negative photosensitive resin composition of this embodiment, as mentioned above, for example, a part is exposed and hardened, and a part is unexposed and is not hardened on the other hand. Then, the uncured unexposed portion is removed by an alkaline solution, and it can be used for a desired application. In the copolymer of the present embodiment, the norbornene-type structural unit substituted with a functional group containing a terminal unsaturated carbon double bond is formed by substituting a part of the carboxyl-substituted norbornene-type structural unit. Then, a part of the carboxyl group-substituted norbornene-type structural unit remains in the copolymer as it is. Thereby, the copolymer of this embodiment contains the norbornene type structural unit which has a carboxyl group. Thereby, when removing the unexposed part, the alkali solubility can be improved. Also, by the copolymer containing a structural unit derived from maleic anhydride, a maleic anhydride derivative, maleimide, or a maleimide derivative, the alkali solubility can be appropriately controlled. In the conventional negative-type photosensitive resin composition, when the durability and developability of the cured film of the negative-type photosensitive resin composition are improved, there is a possibility that the alkali solubility is lowered by simply setting the structure to be easily cross-linked. bad condition. However, in the negative-type photosensitive resin composition of the present embodiment, the copolymer includes norbornene-type structural units substituted with functional groups containing terminal unsaturated carbon double bonds, norbornene-type structural units substituted with carboxyl groups And structural units derived from maleic anhydride, maleic anhydride derivatives, maleimide or maleimide derivatives can improve the durability and developability of the cured film without reducing the alkali solubility. From the above, the negative photosensitive resin composition of the present embodiment can improve the durability and developability of the resin film formed from the negative photosensitive resin composition without impairing the alkali developability.
以下,對本實施形態的負型感光性樹脂組成物的各成分進行說明。 本實施形態之負型感光性樹脂組成物包含聚合物、交聯劑及光敏劑。Hereinafter, each component of the negative photosensitive resin composition of this embodiment is demonstrated. The negative photosensitive resin composition of this embodiment contains a polymer, a crosslinking agent, and a photosensitizer.
(聚合物) 首先,對本實施形態之聚合物進行說明。 本實施形態之聚合物係下述式(1)表示之共聚物。另外,下述式(1)並不限定共聚物的排列。作為共聚物的排列,例如能夠選擇無規共聚物、交替共聚物、嵌段共聚物及週期共聚物等。(Polymer) First, the polymer of this embodiment is demonstrated. The polymer of the present embodiment is a copolymer represented by the following formula (1). In addition, the following formula (1) does not limit the arrangement of the copolymer. As the arrangement of the copolymers, for example, random copolymers, alternating copolymers, block copolymers, periodic copolymers, and the like can be selected.
(式(1)中, l及m表示聚合物中的莫耳含有率, l+m=1, A包含由下述式(A1)表示之結構單元、及 由下述式(A2)表示之結構單元, B包含由下述式(B1)、下述式(B2)、下述式(B3)、下述式(B4)、下述式(B5)或下述式(B6)表示之結構單元中的至少一種以上。) (In the formula (1), l and m represent the molar content in the polymer, l+m=1, A includes a structural unit represented by the following formula (A1), and a structure represented by the following formula (A2) Structural unit, B includes a structure represented by the following formula (B1), the following formula (B2), the following formula (B3), the following formula (B4), the following formula (B5) or the following formula (B6) at least one of the units.)
對共聚物中的上述A的結構單元和上述B的結構單元的組成比進行說明。令上述A的結構單元的莫耳含有率(mol%)為l,上述B的結構單元的莫耳含有率(mol%)為m,並且令l+m=1時,l的數值範圍係0.1≤l≤0.9。又,m的數值範圍係0.1≤m≤0.9。藉此,藉由充分包含上述A的結構單元及上述B的結構單元,能夠實現耐熱性的提高、耐溶劑性的提高及顯影後的殘膜率的提高。The composition ratio of the structural unit of the said A and the structural unit of the said B in a copolymer is demonstrated. Let the molar content (mol%) of the structural unit of A above be 1, the molar content (mol%) of the structural unit of B above be m, and let l+m=1, the numerical range of l is 0.1 ≤l≤0.9. In addition, the numerical range of m is 0.1≤m≤0.9. Thereby, the improvement of heat resistance, the improvement of solvent resistance, and the improvement of the residual film rate after image development can be aimed at by fully including the structural unit of the said A and the structural unit of the said B.
在上述式(1)表示之共聚物中,A包含下述式(A1)表示之來自於經含有末端不飽和碳雙鍵之官能基取代之降莰烯型單體的結構單元、及下述式(A2)表示之來自於經羧基取代之降莰烯型單體的結構單元。 藉由共聚物包含由下述式(A1)表示之結構單元,如上述,能夠提高在製成負型感光性樹脂組成物時的耐熱性、耐溶劑性及顯影後的殘膜率。 又,藉由共聚物包含由下述式(A2)表示之結構單元,如上述,能夠調整在製成負型感光性樹脂組成物時的鹼溶解性。In the copolymer represented by the above formula (1), A includes a structural unit represented by the following formula (A1) derived from a norbornene-type monomer substituted with a functional group containing a terminal unsaturated carbon double bond, and the following The formula (A2) represents a structural unit derived from a carboxyl group-substituted norbornene-type monomer. When the copolymer contains the structural unit represented by the following formula (A1), as described above, the heat resistance, solvent resistance, and residual film ratio after image development can be improved when a negative photosensitive resin composition is formed. Moreover, when a copolymer contains the structural unit represented by following formula (A2), as mentioned above, the alkali solubility at the time of making a negative photosensitive resin composition can be adjusted.
(式(A1)中,R1 、R2 、R3 及R4 分別獨立地為氫或碳數1~30的有機基,R1 、R2 、R3 及R4 中包含至少一個末端不飽和碳雙鍵。n為0、1或2。) (In formula (A1), R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and R 1 , R 2 , R 3 and R 4 include at least one terminal Saturated carbon double bond. n is 0, 1 or 2.)
(式(A2)中,R5 、R6 及R7 分別獨立地為氫或碳數1~30的有機基,n為0、1或2。) (In formula (A2), R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.)
在本實施形態中,構成上述式(A1)中的R1 ~R4 及上述式(A2)中的R5 ~R7 之氫或碳數1~30的有機基可在其結構中包含選自O、N、S、P及Si中的1個以上的原子。 進而,在本實施形態中,關於構成R1 、R2 、R3 及R4 之有機基,能夠設為均不具有酸性官能基。藉此,能夠輕易控制聚合物中的酸值。In the present embodiment, the hydrogen or the organic group having 1 to 30 carbon atoms constituting R 1 to R 4 in the above formula (A1) and R 5 to R 7 in the above formula (A2) may include optional One or more atoms selected from O, N, S, P, and Si. Furthermore, in the present embodiment, none of the organic groups constituting R 1 , R 2 , R 3 and R 4 can have an acidic functional group. Thereby, the acid value in the polymer can be easily controlled.
又,在本實施形態中,上述式(A1)中的R1 ~R4 及上述式(A2)中的R5 ~R7 分別獨立地為氫或碳數1~30的有機基,分別獨立地為氫或碳數1~10的有機基較理想,分別獨立地為氫或碳數1~5的有機基更佳,分別獨立地為氫或碳數1~3的有機基為更進一步較佳。Moreover, in this embodiment, R 1 to R 4 in the above formula (A1) and R 5 to R 7 in the above formula (A2) are each independently hydrogen or an organic group having 1 to 30 carbon atoms, each independently Preferably, it is hydrogen or an organic group with 1 to 10 carbon atoms, it is more preferably hydrogen or an organic group with 1 to 5 carbon atoms, and it is even more preferable to be hydrogen or an organic group with 1 to 3 carbon atoms. good.
在本實施形態中,作為構成上述式(A1)中的R1 ~R4 及上述式(A2)中的R5 ~R7 之有機基,例如可列舉:烷基、烯基、炔基、亞烷基、芳基、芳烷基、烷芳基、環烷基及雜環基。 作為烷基,例如可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基及癸基。作為烯基,例如可列舉烯丙基、戊烯基及乙烯基。作為炔基,可列舉乙炔基。作為亞烷基,例如可列舉亞甲基及亞己基。作為芳基,例如可列舉甲苯基、二甲苯基、苯基、萘基及蒽基。作為芳烷基,例如可列舉苄基及苯乙基。作為環烷基,例如可列舉金剛烷基、環戊基、環己基及環辛基。作為雜環基,例如可列舉環氧基及氧雜環丁基。In the present embodiment, examples of the organic groups constituting R 1 to R 4 in the above formula (A1) and R 5 to R 7 in the above formula (A2) include an alkyl group, an alkenyl group, an alkynyl group, Alkylene, aryl, aralkyl, alkaryl, cycloalkyl and heterocyclyl. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, tertiary butyl, pentyl, neopentyl, hexyl, and heptyl. , octyl, nonyl and decyl. As an alkenyl group, an allyl group, a pentenyl group, and a vinyl group are mentioned, for example. As an alkynyl group, an ethynyl group is mentioned. As an alkylene group, a methylene group and a hexylene group are mentioned, for example. As an aryl group, a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group are mentioned, for example. As an aralkyl group, a benzyl group and a phenethyl group are mentioned, for example. As a cycloalkyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are mentioned, for example. As a heterocyclic group, an epoxy group and an oxetanyl group are mentioned, for example.
在本實施形態中,上述式(A1)中,R1 、R2 、R3 及R4 含有至少一個末端不飽和碳雙鍵。藉此,在負型感光性樹脂組成物中,能夠增加在曝光時藉由自由基化而有助於交聯結構之結構單元。除此以外,詳細的機理尚不明確,但藉由降莰烯型結構單元的側鏈有助於交聯結構,能夠更牢固地限制聚合物鏈的運動。藉此,能夠平衡良好地提高負型感光性樹脂組成物的耐熱性、耐溶劑性及顯影後的殘膜率。 另外,在本實施形態中,並不特別限制R1 、R2 、R3 及R4 含有2個以上的末端不飽和碳雙鍵。R1 ~R4 中,含有末端不飽和碳雙鍵者宜R1 ~R4 中的任一個較佳。藉此,含有末端不飽和碳雙鍵之官能基彼此不會成為立體阻礙,就能夠形成較佳的交聯結構之觀點而言較理想。In the present embodiment, in the above formula (A1), R 1 , R 2 , R 3 and R 4 contain at least one terminal unsaturated carbon double bond. Thereby, in a negative photosensitive resin composition, the structural unit which contributes to a crosslinking structure by radicalization at the time of exposure can be increased. Other than that, the detailed mechanism is not clear, but the movement of the polymer chain can be more strongly restricted by the side chain of the norbornene-type structural unit contributing to the cross-linked structure. Thereby, the heat resistance, solvent resistance, and residual film ratio after image development of the negative photosensitive resin composition can be improved in a well-balanced manner. In addition, in the present embodiment, it is not particularly limited that R 1 , R 2 , R 3 and R 4 contain two or more terminal unsaturated carbon double bonds. Among R 1 to R 4 , those containing a terminal unsaturated carbon double bond are preferably any of R 1 to R 4 . Thereby, functional groups containing a terminal unsaturated carbon double bond do not form a steric hindrance to each other, which is preferable from the viewpoint of being able to form a preferable cross-linked structure.
在上述式(A1)、式(A2)中,分別獨立地n為0、1或2,n為0或1,n為0。In the above formula (A1) and formula (A2), n is 0, 1 or 2, n is 0 or 1, and n is 0, respectively.
R1 、R2 、R3 及R4 含有末端不飽和碳雙鍵,故包含由下述式(E1)表示之結構較理想。式(E1)表示之結構中,包含由下述式(E2)表示之結構為更佳。藉此,能夠形成較佳的交聯結構。因此,能夠平衡良好地提高負型感光性樹脂組成物的耐熱性、耐溶劑性及顯影後的殘膜率。Since R 1 , R 2 , R 3 and R 4 contain terminal unsaturated carbon double bonds, it is preferable to include a structure represented by the following formula (E1). Among the structures represented by the formula (E1), it is more preferable to include a structure represented by the following formula (E2). Thereby, a preferable crosslinked structure can be formed. Therefore, the heat resistance, solvent resistance, and residual film ratio after image development of the negative photosensitive resin composition can be improved in a well-balanced manner.
(式(E1)中,Re 獨立地為氫或碳數1~10的有機基。) (In formula (E1), Re is independently hydrogen or an organic group having 1 to 10 carbon atoms.)
(式(E2)中,Re 獨立地為氫或碳數1~10的有機基。) (In formula (E2), Re is independently hydrogen or an organic group having 1 to 10 carbon atoms.)
在上述式(E1)、(E2)中,Re 獨立地為氫或碳數1~10的有機基,氫或碳數1~7的有機基較理想,氫或碳數1~5的有機基更佳,氫或碳數1~3的有機基為更進一步較佳,氫或碳數1的有機基為尤佳。In the above formulae (E1) and (E2), R e is independently hydrogen or an organic group having 1 to 10 carbon atoms, preferably hydrogen or an organic group having 1 to 7 carbon atoms, and hydrogen or an organic group having 1 to 5 carbon atoms. The group is more preferred, hydrogen or an organic group having 1 to 3 carbon atoms is even more preferred, and hydrogen or an organic group having 1 carbon atoms is particularly preferred.
作為含有末端不飽和碳雙鍵之R1 、R2 、R3 及R4 的具體例,可列舉乙烯基、亞乙烯基、丙烯酸基、甲基丙烯酸基、丙烯酸酯基、甲基丙烯酸酯基等。該等中,含有末端不飽和碳雙鍵之R1 、R2 、R3 及R4 係選自由丙烯酸基、甲基丙烯酸基、丙烯酸酯基及甲基丙烯酸酯基組成的群中的一種以上較理想,係丙烯酸酯基或甲基丙烯酸酯基更佳。Specific examples of R 1 , R 2 , R 3 and R 4 having terminal unsaturated carbon double bonds include vinyl groups, vinylene groups, acrylic groups, methacrylic groups, acrylate groups, and methacrylate groups. Wait. Among these, R 1 , R 2 , R 3 and R 4 containing terminal unsaturated carbon double bonds are at least one selected from the group consisting of acrylic group, methacrylic group, acrylate group and methacrylate group Preferably, it is an acrylate group or a methacrylate group.
共聚物中的上述式(A1)表示之結構單元的含量的下限值相對於上述式(A2)表示之結構單元1mol,例如係0.1mol以上較理想,0.2mol以上為更佳。藉此,能夠形成較佳的交聯結構。 又,共聚物中的上述式(A1)表示之結構單元的含量的上限值相對於上述式(A2)表示之結構單元1mol,例如係3.0mol以下較理想,2.0mol以下更佳,1.0mol以下為更進一步較佳,0.7mol以下為尤佳。藉此,能夠較佳地顯現出鹼溶解性。 另外,在本實施形態中,相對於聚合物中的上述式(A1)表示之結構單元1mol,上述式(A1)表示之結構單元的含量例如能夠藉由使用核磁共振器(例如,JEOL Ltd.製)進行之1H-NMR測量來進行評價。The lower limit of the content of the structural unit represented by the above formula (A1) in the copolymer is preferably 0.1 mol or more, more preferably 0.2 mol or more, relative to 1 mol of the structural unit represented by the above formula (A2). Thereby, a preferable crosslinked structure can be formed. In addition, the upper limit of the content of the structural unit represented by the above formula (A1) in the copolymer is preferably 3.0 mol or less, more preferably 2.0 mol or less, and 1.0 mol relative to 1 mol of the structural unit represented by the above-mentioned formula (A2). The following is more preferable, and 0.7 mol or less is particularly preferable. Thereby, alkali solubility can be preferably exhibited. In addition, in the present embodiment, the content of the structural unit represented by the above formula (A1) with respect to 1 mol of the structural unit represented by the above formula (A1) in the polymer can be determined, for example, by using a nuclear magnetic resonance apparatus (for example, JEOL Ltd. 1H-NMR measurement performed by the system) was used for evaluation.
又,在上述式(1)表示之共聚物中,B包含由下述式(B1)、下述式(B2)、下述式(B3)、下述式(B4)、下述式(B5)或下述式(B6)表示之結構單元中的至少一種以上。 該等中,包含下述式(B5)或下述式(B6)表示之結構單元較理想。藉此,能夠提高鹼溶解性,並能夠提高顯影性。 進而,在下述式(B5)或下述式(B6)中,包含下述式(B6)更佳。藉此,能夠調整在製成負型感光性樹脂組成物時的鹼溶解性,進而能夠提高耐熱性。In addition, in the copolymer represented by the above formula (1), B includes the following formula (B1), the following formula (B2), the following formula (B3), the following formula (B4), the following formula (B5) ) or at least one of the structural units represented by the following formula (B6). Among these, it is preferable to include a structural unit represented by the following formula (B5) or the following formula (B6). Thereby, alkali solubility can be improved, and developability can be improved. Furthermore, it is more preferable to include the following formula (B6) in the following formula (B5) or the following formula (B6). Thereby, the alkali solubility at the time of making a negative photosensitive resin composition can be adjusted, and heat resistance can be improved further.
(式(B1)中,R8 獨立地為碳數1~30的有機基。) (In formula (B1), R 8 is independently an organic group having 1 to 30 carbon atoms.)
(式(B2)中,R9 及R10 分別獨立地為碳數1~30的有機基。) (In formula (B2), R 9 and R 10 are each independently an organic group having 1 to 30 carbon atoms.)
(式(B6)中,R11 獨立地為碳數1~30的有機基。) (In formula (B6), R 11 is independently an organic group having 1 to 30 carbon atoms.)
在本實施形態中,B除了包含上述式(B6)表示之結構單元以外,還包含上述式(B5)表示之結構單元較理想。藉由同時包含上述式(B6)及上述式(B5)表示之結構單元,在製成負型感光性樹脂組成物時,能夠提高鹼溶解性,進而提高靈敏度。藉此,在製成負型感光性樹脂組成物時,除了能夠提高耐熱性、耐溶劑性及顯影後的殘膜率以外,還能夠兼顧維持優異的靈敏度。In this embodiment, it is preferable that B contains the structural unit represented by the said formula (B5) in addition to the structural unit represented by the said formula (B6). By including the structural units represented by the above formula (B6) and the above formula (B5) at the same time, when a negative photosensitive resin composition is prepared, the alkali solubility can be improved, and the sensitivity can be further improved. Thereby, when a negative photosensitive resin composition is used, in addition to improving heat resistance, solvent resistance, and the residual film ratio after image development, it is possible to maintain excellent sensitivity at the same time.
在本實施形態中,構成上述式(B1)、式(B2)及式(B6)中的R8 ~R11 之碳數1~30的有機基可以在其結構中包含選自O、N、S、P及Si中之1個以上的原子。 進而,在本實施形態中,關於構成R8 ~R11 之有機基,能夠設為均不具有酸性官能基。藉此,能夠容易地控制聚合物中的酸值。In the present embodiment, the organic group having 1 to 30 carbon atoms constituting R 8 to R 11 in the above-mentioned formula (B1), formula (B2) and formula (B6) may include in its structure a group selected from O, N, One or more atoms of S, P and Si. Furthermore, in the present embodiment, none of the organic groups constituting R 8 to R 11 can have an acidic functional group. Thereby, the acid value in the polymer can be easily controlled.
又,在本實施形態中,上述式(B1)、式(B2)及式(B6)中的R8 ~R11 分別獨立地為碳數1~30的有機基,分別獨立地為碳數1~10的有機基較理想,分別獨立地為碳數1~5的有機基更佳,分別獨立地為碳數1~3的有機基為更進一步較佳。Moreover, in the present embodiment, R 8 to R 11 in the above-mentioned formula (B1), formula (B2) and formula (B6) are each independently an organic group having 1 to 30 carbon atoms, and each independently is a carbon number of 1 The organic group of ~10 is preferable, the organic group of each independently having 1 to 5 carbon atoms is more preferable, and the organic group of each independently having 1 to 3 carbon atoms is even more preferable.
在本實施形態中,作為構成上述式(B1)、式(B2)及式(B6)中的R8 ~R11 之有機基,能夠使用與構成上述式(A1)中的R1 ~R4 及上述式(A2)中的R5 ~R7 之有機基相同的有機基。In the present embodiment, as the organic groups constituting R 8 to R 11 in the above formula (B1), formula (B2) and formula (B6), R 1 to R 4 in the above formula (A1) can be used and the same organic groups as the organic groups of R 5 to R 7 in the above formula (A2).
本實施形態之聚合物的Mw(重量平均分子量)的上限值例如為30000以下,設為20000以下較理想,設為14000以下更佳,設為10000以下為更進一步較佳。藉此,藉由提高分子鏈的運動性能夠製作更適當的交聯結構。 又,聚合物Mw的下限值例如為1500以上,設為2000以上較理想,設為3000以上為更佳。藉此,對負型感光性樹脂組成物進行曝光時,能夠快速形成交聯結構。因此,能夠提高負型感光性樹脂組成物的靈敏度。The upper limit of Mw (weight average molecular weight) of the polymer of the present embodiment is, for example, 30,000 or less, preferably 20,000 or less, more preferably 14,000 or less, and even more preferably 10,000 or less. Thereby, a more appropriate cross-linked structure can be produced by improving the mobility of the molecular chain. Moreover, the lower limit of the polymer Mw is, for example, 1500 or more, preferably 2000 or more, and more preferably 3000 or more. Thereby, when exposing a negative photosensitive resin composition, a crosslinked structure can be formed rapidly. Therefore, the sensitivity of the negative photosensitive resin composition can be improved.
又,本實施形態之聚合物的分散度、亦即Mw(重量平均分子量)/Mn(數量平均分子量)的上限值例如為2.5以下,設為2.2以下較理想,設為2.0以下更佳。藉此,能夠減小聚合物的分子量分佈的寬度,並能夠在整個負型感光性樹脂組成物中形成相同的交聯結構。因此,能夠在整個負型感光性樹脂組成物的硬化物中,使物性均勻。 又,Mw/Mn的下限值例如可以設為1.0以上,能夠設為1.5以上。另外,Mw/Mn越接近單分散越好。 另外,Mw/Mn係表示分子量分佈的寬度之分散度。藉由將聚合物的Mw/Mn設為上述範圍,能夠使由含有聚合物之樹脂組成物形成之樹脂膜的形狀良好。另外,同時當如上述般減少聚合物的低分子量成分時,該種效果顯現得尤為明顯。Further, the upper limit of the dispersity of the polymer of the present embodiment, that is, Mw (weight average molecular weight)/Mn (number average molecular weight) is, for example, 2.5 or less, preferably 2.2 or less, and more preferably 2.0 or less. Thereby, the width|variety of the molecular weight distribution of a polymer can be made small, and the same crosslinked structure can be formed in the whole negative photosensitive resin composition. Therefore, the physical properties can be made uniform throughout the cured product of the negative photosensitive resin composition. Moreover, the lower limit value of Mw/Mn can be set to 1.0 or more, for example, and can be set to 1.5 or more. In addition, the closer Mw/Mn is to monodispersity, the better. In addition, Mw/Mn represents the degree of dispersion of the width of the molecular weight distribution. By setting the Mw/Mn of the polymer to be in the above range, the shape of the resin film formed from the polymer-containing resin composition can be improved. In addition, at the same time, when the low-molecular-weight components of the polymer are reduced as described above, this effect is particularly evident.
另外,重量平均分子量(Mw)、數量平均分子量(Mn)及分子量分佈(Mw/Mn),使用例如依據藉由GPC測量而獲得之標準聚苯乙烯(PS)的校準曲線求出之聚苯乙烯換算值。測量條件例如為如下。 東曹公司製的凝膠滲透層析法裝置HLC-8320GPC 柱:東曹公司製的TSK-GEL Supermultipore HZ-M 檢測器:液相層析圖用RI檢測器 測量溫度:40℃ 溶劑:THF 試樣濃度:2.0mg/毫升In addition, as the weight average molecular weight (Mw), the number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn), polystyrene obtained by, for example, a calibration curve of standard polystyrene (PS) obtained by GPC measurement is used. Converted value. The measurement conditions are, for example, as follows. Gel permeation chromatography apparatus HLC-8320GPC manufactured by Tosoh Corporation Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation Detector: RI detector for liquid chromatography Measurement temperature: 40°C Solvent: THF Test Sample concentration: 2.0mg/ml
本實施形態中的聚合物的鹼溶解速度例如為500埃/秒以上20,000埃/秒以下。聚合物的鹼溶解速度藉由以下方式來算出:例如使聚合物溶解於丙二醇一甲醚乙酸酯,調整為固體成分20重量%之聚合物溶液後,以旋轉方式塗佈於矽晶圓上,在110℃將該聚合物溶液軟烤100秒鐘而獲得聚合物膜,在23℃使該聚合物膜浸漬於2.38%的氫氧化四甲基銨水溶液中,並測量直到視覺上前述聚合物膜消失為止的時間。 藉由將聚合物的鹼溶解速度設為500埃/秒以上,能夠使基於鹼顯影液之顯影步驟中的處理量(throughput)變得良好。又,藉由將聚合物的鹼溶解速度設為20,000埃/秒以下,能夠提高基於鹼顯影液之顯影步驟後的殘膜率。因此,能夠抑制基於微影步驟的膜的減少。The alkali dissolution rate of the polymer in the present embodiment is, for example, 500 angstroms/sec or more and 20,000 angstroms/sec or less. The alkali dissolution rate of the polymer is calculated by, for example, dissolving the polymer in propylene glycol monomethyl ether acetate, adjusting it to a polymer solution with a solid content of 20% by weight, and then applying it to a silicon wafer by spin coating , soft-bake the polymer solution at 110°C for 100 seconds to obtain a polymer film, immerse the polymer film in a 2.38% aqueous tetramethylammonium hydroxide solution at 23°C, and measure until the aforementioned polymer is visually The time until the film disappears. By setting the alkali dissolution rate of the polymer to be 500 angstroms/sec or more, the throughput in the development step by an alkali developer can be improved. Moreover, by making the alkali dissolution rate of a polymer into 20,000 angstroms/sec or less, the residual film rate after the developing process by an alkali developing solution can be improved. Therefore, the reduction of the film by the lithography step can be suppressed.
(聚合物的製造方法) 本實施形態之聚合物例如如下製造。 至少包含:使單體A和單體B聚合,並聚合共聚物1之聚合步驟(處理S1);接著,藉由具有末端不飽和碳雙鍵之化合物取代來自於共聚物1的單體A之羧基,從而獲得共聚物2之取代步驟(處理S2);及從共聚物2去除低分子量成分而獲得聚合物之低分子量去除步驟(處理S3)。 當單體B包含馬來酸酐時,亦可在聚合步驟(處理S1)之後且低分子量去除步驟(處理S3)之前,包含:將一部分來自於馬來酸酐的重複單元開環之開環步驟(處理S'1);接著,去除殘留金屬成分之清洗步驟(處理S'2)。 以下,對各步驟的詳細內容進行說明。(Manufacturing method of a polymer) The polymer of this embodiment is manufactured as follows, for example. At least comprising: polymerizing the monomer A and the monomer B, and polymerizing the polymerization step of the copolymer 1 (treatment S1); then, replacing the monomer A from the copolymer 1 with a compound having a terminal unsaturated carbon double bond. carboxyl groups to obtain a substitution step of copolymer 2 (treatment S2 ); and a low molecular weight removal step of removing low molecular weight components from copolymer 2 to obtain a polymer (treatment S3 ). When the monomer B contains maleic anhydride, after the polymerization step (treatment S1) and before the low molecular weight removal step (treatment S3), it may also include: a ring-opening step ( Treatment S'1); then, a cleaning step for removing residual metal components (treatment S'2). Hereinafter, the details of each step will be described.
(聚合步驟(處理S1)) 首先,準備經羧基取代之降莰烯型單體、及馬來酸酐、馬來醯亞胺或馬來醯亞胺衍生物。 在上述式(1)表示之共聚物中,上述經羧基取代之降莰烯型單體(以下,設為單體A。)成為由A表示之結構單元的來源。又,選自由馬來酸酐、馬來醯亞胺及馬來醯亞胺衍生物組成的群中的一種或兩種以上的單體(以下,設為單體B。)成為由B表示之結構單元的來源。(Polymerization Step (Treatment S1 )) First, a carboxyl group-substituted norbornene-type monomer, and maleic anhydride, maleimide, or a maleimide derivative are prepared. In the copolymer represented by the above formula (1), the carboxyl group-substituted norbornene-type monomer (hereinafter, referred to as monomer A) serves as a source of the structural unit represented by A. In addition, one or two or more monomers (hereinafter referred to as monomers B) selected from the group consisting of maleic anhydride, maleimide, and maleimide derivatives have a structure represented by B. The source of the unit.
單體A以下式(2)表示。在下式(2)中,R5 ~R7 能夠設為與上述式(A2)的R5 ~R7 相同。Monomer A is represented by the following formula (2). In the following formula (2), R 5 to R 7 can be the same as R 5 to R 7 in the above formula (A2).
(式(2)中,R5 、R6 及R7 分別獨立地為氫或碳數1~30的有機基,n為0、1或2。) (In formula (2), R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.)
作為上述式(2)表示之經羧基取代之降莰烯型單體,具體而言,可列舉5-降莰烯-2-羧酸、5-降莰烯-2,3-二羧酸及四環十二烯羧酸(tetracyclodecene carboxylic acid)等。 作為經羧基取代之降莰烯型單體,能夠使用該等中的一種或兩種以上。其中,從提高耐熱性的觀點考慮,使用5-降莰烯-2-羧酸較理想。Specific examples of the carboxyl-substituted norbornene-type monomer represented by the above formula (2) include 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and Tetracyclodecene carboxylic acid, etc. As the carboxyl group-substituted norbornene-type monomer, one or two or more of these can be used. Among them, it is preferable to use 5-norbornene-2-carboxylic acid from the viewpoint of improving heat resistance.
單體B係選自由馬來酸酐、馬來醯亞胺及馬來醯亞胺衍生物組成的群中的一種或兩種以上的單體,係選自由馬來醯亞胺及馬來醯亞胺衍生物組成的群中的一種或兩種以上的單體較理想。藉由使用馬來醯亞胺衍生物,能夠提高耐熱性、硬化後殘膜率及耐溶劑性。又,藉由併用馬來醯亞胺及馬來醯亞胺衍生物,能夠提高負型感光性樹脂組成物的鹼溶解速度,進而提高靈敏度。 作為上述馬來醯亞胺衍生物,示於下述式(3)。Monomer B is one or more monomers selected from the group consisting of maleic anhydride, maleimide and maleimide derivatives, and is selected from maleimide and maleimide One or two or more monomers from the group consisting of amine derivatives are preferred. By using the maleimide derivative, it is possible to improve heat resistance, residual film rate after curing, and solvent resistance. Moreover, by using maleimide and a maleimide derivative in combination, the alkali dissolution rate of the negative photosensitive resin composition can be increased, and the sensitivity can be further improved. The maleimide derivative is shown in the following formula (3).
(式(3)中,R11 獨立地為碳數1~30的有機基。) (In formula (3), R 11 is independently an organic group having 1 to 30 carbon atoms.)
作為上述式(3)表示之馬來醯亞胺衍生物,例如可列舉N-甲基馬來醯亞胺、N-乙基馬來醯亞胺等N-直鏈狀烷基馬來醯亞胺;N-異丙基馬來醯亞胺等N-分支烷基馬來醯亞胺;N-環己基馬來醯亞胺等N-環烷基馬來醯亞胺;N-苯基馬來醯亞胺、N-萘基馬來醯亞胺等N-芳基馬來醯亞胺等。該等當中,使用直鏈狀N-烷基馬來醯亞胺、分支烷基馬來醯亞胺或N-環烷基馬來醯亞胺較理想,包含N-環烷基馬來醯亞胺更佳。作為N-環烷基馬來醯亞胺,使用N-環己基馬來醯亞胺較理想。藉此,能夠提高耐熱性、硬化後殘膜率及耐溶劑性。Examples of maleimide derivatives represented by the above formula (3) include N-straight-chain alkylmaleimide such as N-methylmaleimide and N-ethylmaleimide. Amines; N-branched alkylmaleimides such as N-isopropylmaleimide; N-cycloalkylmaleimides such as N-cyclohexylmaleimide; N-phenylmaleimide N-arylmaleimide such as lyimide, N-naphthylmaleimide, etc. Among these, straight-chain N-alkylmaleimides, branched alkylmaleimides or N-cycloalkylmaleimides are preferably used, including N-cycloalkylmaleimides Amines are better. As N-cycloalkylmaleimide, N-cyclohexylmaleimide is preferably used. Thereby, the heat resistance, the residual film rate after curing, and the solvent resistance can be improved.
接著。將單體A和單體B加成聚合而合成共聚物1。 作為加成聚合的方法沒有特別限定,但在本實施形態中,藉由自由基聚合來合成共聚物1。 藉由加成聚合,能夠合成具有來自於單體A之結構單元和來自於單體B之結構單元之共聚物1。 在此,將來自於單體A之結構單元示於下述式(A2)。 又,藉由作為單體B而使用馬來酸酐、馬來醯亞胺、馬來醯亞胺衍生物,能夠獲得具有分別來自於下述式(B3)、下述式(B5)、下述式(B6)之結構單元之共聚物1。then. The copolymer 1 was synthesized by addition-polymerizing the monomer A and the monomer B. The method of addition polymerization is not particularly limited, but in this embodiment, the copolymer 1 is synthesized by radical polymerization. The copolymer 1 having the structural unit derived from the monomer A and the structural unit derived from the monomer B can be synthesized by addition polymerization. Here, the structural unit derived from the monomer A is shown in the following formula (A2). Furthermore, by using maleic anhydride, maleimide, and a maleimide derivative as the monomer B, it is possible to obtain compounds having the following formulae (B3), the following formula (B5), the following Copolymer 1 of the structural unit of formula (B6).
(式(A2)中,R5 、R6 及R7 分別獨立地為氫或碳數1~30的有機基,n為0、1或2。) (In formula (A2), R 5 , R 6 and R 7 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and n is 0, 1 or 2.)
(式(B6)中,R11 獨立地為碳數1~30的有機基。) (In formula (B6), R 11 is independently an organic group having 1 to 30 carbon atoms.)
單體A與單體B的莫耳比係0.5:1~1:0.5較理想。其中,從控制分子結構的觀點考慮,莫耳比係1:1較理想。 將單體A、單體B、聚合起始劑溶解於溶劑中,然後,藉由加熱規定時間來進行加成聚合。加熱溫度例如為50~80℃,加熱時間為10~20小時。The molar ratio of the monomer A and the monomer B is preferably 0.5:1 to 1:0.5. Among them, from the viewpoint of controlling the molecular structure, a molar ratio of 1:1 is preferable. The monomer A, the monomer B, and the polymerization initiator are dissolved in a solvent, and then addition polymerization is performed by heating for a predetermined time. The heating temperature is, for example, 50 to 80° C., and the heating time is 10 to 20 hours.
作為聚合起始劑,能夠使用偶氮化合物及有機過氧化物中的一種或兩種以上。 作為偶氮化合物,例如可列舉偶氮雙異丁腈(AIBN)、2,2’-偶氮雙(2-甲基丙酸)二甲酯、1,1’-偶氮雙(環己甲腈)(ABCN),該等當中,能夠使用任一種以上。 又,作為有機過氧化物,例如能夠列舉過氧化氫、過氧化二第三丁基(DTBP)、過氧化苯甲醯(benzoyl peroxide,BPO)及過氧化甲基乙酮(MEKP),該等當中,能夠使用任一種以上。As the polymerization initiator, one or two or more of azo compounds and organic peroxides can be used. Examples of the azo compound include azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 1,1'-azobis(cyclohexylmethyl) Nitrile) (ABCN), among these, any one or more can be used. In addition, examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (BPO), and methyl ethyl ketone peroxide (MEKP). Among them, any one or more can be used.
聚合起始劑的量(莫耳數),宜為成為上述A的結構單元的來源之經羧基取代之降莰烯型單體與成為上述B的結構單元的來源之單體的合計莫耳數的1%~10%較理想。藉由在前述範圍內適當設定聚合起始劑的量,且適當設定反應溫度、反應時間,能夠將所獲得之聚合物的重量平均分子量(Mw)調整為5000~30000。The amount (molar number) of the polymerization initiator is preferably the total number of moles of the carboxyl-substituted norbornene-type monomer that is the source of the structural unit of A and the monomer that is the source of the structural unit of B above 1% to 10% is ideal. The weight-average molecular weight (Mw) of the polymer obtained can be adjusted to 5,000 to 30,000 by appropriately setting the amount of the polymerization initiator within the aforementioned range, and by appropriately setting the reaction temperature and reaction time.
作為溶劑,例如能夠使用二***、四氫呋喃、甲苯等中的一種或兩種以上。As the solvent, for example, one or two or more of diethyl ether, tetrahydrofuran, toluene, and the like can be used.
藉由該聚合步驟,能夠聚合作為單體A和單體B的共聚物之共聚物1。共聚物1的排列沒有特別限定,可以係無規共聚物、交替共聚物、嵌段共聚物及週期共聚物中的任一種。 在共聚物1例如使用上述式(2)所示之單體作為單體A且使用上述式(3)所示之單體作為單體B時,形成具有由下述式(4)表示之結構單元之共聚物。By this polymerization step, the copolymer 1, which is a copolymer of the monomer A and the monomer B, can be polymerized. The arrangement of the copolymer 1 is not particularly limited, and may be any of a random copolymer, an alternating copolymer, a block copolymer, and a periodic copolymer. When the copolymer 1 uses, for example, the monomer represented by the above formula (2) as the monomer A and the monomer represented by the above formula (3) as the monomer B, it has a structure represented by the following formula (4) copolymers of units.
(在式(4)中,R5 ~R7 與上述式(A2)相同。又,R11 與上述式(3)相同。) (In the formula (4), R 5 to R 7 are the same as the above formula (A2). In addition, R 11 is the same as the above formula (3).)
在共聚物1中,來自於單體A之R5 ~R7 的官能基在各重複單元中可不同,亦可相同。該等中相同較理想。藉此,能夠提高負型感光性樹脂組成物的圖案化的精度。In the copolymer 1, the functional groups of R 5 to R 7 derived from the monomer A may be different or the same in each repeating unit. Of these, the same is preferable. Thereby, the precision of patterning of a negative photosensitive resin composition can be improved.
(取代步驟(S2)) 接著,在所獲得之共聚物1中,藉由具有末端不飽和碳雙鍵之化合物取代一部分上述式(A2)表示之結構單元的羧基,製成共聚物2。(Substitution step (S2)) Next, in the obtained copolymer 1, a part of the carboxyl groups of the structural unit represented by the above formula (A2) is substituted by a compound having a terminal unsaturated carbon double bond to prepare a copolymer 2.
對取代共聚物1並合成共聚物2之方法並沒有特別限定,例如能夠以以下方法來進行。 藉由將上述共聚物1和具有末端不飽和碳雙鍵之化合物溶解於溶劑中,並加熱規定時間而進行取代反應並合成共聚物2。在此,加熱溫度例如為50~100℃,加熱時間為2~20小時。 藉此,能夠獲得在A的結構單元中具備來自於單體A之重複單元、單體A經具有末端不飽和碳雙鍵之化合物取代之重複單元及來自於單體B的結構單元。 將單體A經具有末端不飽和碳雙鍵之化合物取代之結構單元示於下述式(A1)。The method for synthesizing the copolymer 2 in place of the copolymer 1 is not particularly limited, and for example, it can be carried out by the following method. The copolymer 2 is synthesized by dissolving the above-mentioned copolymer 1 and the compound having a terminal unsaturated carbon double bond in a solvent and heating for a predetermined time to perform a substitution reaction. Here, the heating temperature is, for example, 50 to 100° C., and the heating time is 2 to 20 hours. Thereby, a repeating unit derived from the monomer A, a repeating unit in which the monomer A is substituted with a compound having a terminal unsaturated carbon double bond, and a structural unit derived from the monomer B can be obtained in the structural unit of A. The structural unit in which the monomer A is substituted with a compound having a terminal unsaturated carbon double bond is shown in the following formula (A1).
(式(A1)中,R1 、R2 、R3 及R4 分別獨立地為氫或碳數1~30的有機基,R1 、R2 、R3 及R4 中包含至少一個末端不飽和碳雙鍵。n為0、1或2。) (In formula (A1), R 1 , R 2 , R 3 and R 4 are each independently hydrogen or an organic group having 1 to 30 carbon atoms, and R 1 , R 2 , R 3 and R 4 include at least one terminal Saturated carbon double bond. n is 0, 1 or 2.)
作為上述具有末端不飽和碳雙鍵之化合物,使用丙烯酸化合物較理想。 作為丙烯酸化合物,例如可列舉甲基丙烯酸環氧丙酯(glycidyl methacrylate)、丙烯酸環氧丙酯、丙烯酸4-羥丁酯環氧丙醚、甲基丙烯酸羥乙酯等。該等當中,使用甲基丙烯酸環氧丙酯較理想。As the compound having the above-mentioned terminal unsaturated carbon double bond, an acrylic compound is preferably used. Examples of the acrylic compound include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, and hydroxyethyl methacrylate. Among these, it is preferable to use glycidyl methacrylate.
作為溶劑,例如能夠使用二***、四氫呋喃、甲苯等中的一種或兩種以上。As the solvent, for example, one or two or more of diethyl ether, tetrahydrofuran, toluene, and the like can be used.
在共聚物2中,例如相對於由A表示之所有結構單元,將5mol%以上的結構單元取代為上述式(A1)表示之結構單元較理想,取代10mol%以上為更佳,取代15mol%以上更佳,取代20mol%以上為更進一步較佳。藉由這樣設定取代率,能夠適當地交聯來自於降莰烯單元之末端不飽和碳雙鍵。藉此,能夠提高含有共聚物2之負型感光性樹脂組成物的耐熱性、殘膜率及耐溶劑性。In the copolymer 2, for example, 5 mol% or more of the structural units represented by the above-mentioned formula (A1) are preferably substituted with respect to all the structural units represented by A, more preferably 10 mol% or more, and 15 mol% or more. More preferably, it is even more preferable to substitute 20 mol% or more. By setting the substitution ratio in this way, the terminal unsaturated carbon double bond derived from the norbornene unit can be appropriately cross-linked. Thereby, the heat resistance, residual film ratio, and solvent resistance of the negative photosensitive resin composition containing the copolymer 2 can be improved.
在此,關於取代了來自於經羧基取代之降莰烯型單體之重複單元中一部分的重複單元,能夠藉由1H-NMR測量的光譜數據來鑑別。Here, the repeating unit substituted for a part of the repeating unit derived from the carboxyl group-substituted norbornene-type monomer can be identified by the spectral data measured by 1 H-NMR.
又,藉由丙烯酸化合物取代了羧基的取代率能夠如下測量。 對共聚物2的聚合物溶液進行1H-NMR測量。關於藉由1H-NMR測量而得到之光譜數據,計算來自於羧基之每單位質子的信號積分值X、來自於藉由所添加之丙烯酸化合物而形成之末端不飽和碳雙鍵之每單位質子的信號積分值Y。能夠利用上述信號積分值,並藉由以下式計算取代率。 取代率(%)=Y/(X+Y)×100In addition, the substitution rate of the carboxyl group by the acrylic compound can be measured as follows. 1H-NMR measurement was performed on the polymer solution of Copolymer 2. Regarding the spectral data obtained by the 1H-NMR measurement, the signal integral value X per unit proton derived from the carboxyl group, the per unit proton derived from the terminal unsaturated carbon double bond formed by the added acrylic compound were calculated Signal integral value Y. The substitution rate can be calculated by the following equation using the above-mentioned signal integral value. Substitution rate (%)=Y/(X+Y)×100
(低分子量去除步驟(S3)) 接著,將含有共聚物2及殘留單體和寡聚物等低分子量成分之前述有機層進行濃縮之後,再次溶解於THF等有機溶劑中。然後,在該溶液中添加己烷及甲醇,以使含有共聚物2之聚合物凝固沉澱。在此,作為低分子量成分,包含殘留單體、寡聚物、以及聚合起始劑等。接著,進行過濾並對所獲得之凝固物進行乾燥。藉此,能夠獲得以去除了低分子量成分之共聚物2為主成份(主產物)之聚合物。 在本實施形態中,在該低分子量成分去除步驟(處理S3)中,反覆進行萃取操作直到共聚物2中的分子量1000以下的低核體含有率成為1%以下為止。藉此,能夠將第一聚合物中的低分子量成分的量減少至足夠的程度來抑制硬化時膜的圖案變形。(Low Molecular Weight Removal Step ( S3 )) Next, the organic layer containing the copolymer 2 and low molecular weight components such as residual monomers and oligomers is concentrated, and then dissolved again in an organic solvent such as THF. Then, hexane and methanol were added to the solution to coagulate and precipitate the polymer containing the copolymer 2. Here, residual monomers, oligomers, polymerization initiators, and the like are included as low molecular weight components. Next, filtration was performed and the obtained coagulation was dried. In this way, a polymer containing the copolymer 2 from which low molecular weight components have been removed as a main component (main product) can be obtained. In the present embodiment, in this low molecular weight component removal step (treatment S3 ), the extraction operation is repeatedly performed until the content rate of low nuclear bodies having a molecular weight of 1000 or less in the copolymer 2 becomes 1% or less. Thereby, the quantity of the low molecular weight component in a 1st polymer can be reduced to a sufficient degree, and the pattern deformation|transformation of a film at the time of hardening can be suppressed.
另外。當單體B包含馬來酸酐時,可在上述聚合步驟(S1)之後且上述低分子量去除步驟(S3)之前進行開環步驟(S'1)及清洗步驟(S'2)。在以下進行說明。in addition. When the monomer B contains maleic anhydride, the ring-opening step (S'1) and the washing step (S'2) may be performed after the above-mentioned polymerization step (S1) and before the above-mentioned low-molecular-weight removal step (S3). It will be described below.
(開環步驟(S'1)) 一邊將所獲得之共聚物1或共聚物2的來自於馬來酸酐之重複單元中之一部分的重複單元設為閉環之狀態,一邊使其餘的重複單元開環。 藉此,能夠調整共聚物1中的羧基的量。亦即,能夠控制所製作之聚合物的酸值。 在本實施形態中,使共聚物1或共聚物2的來自於馬來酸酐之重複單元中之例如50%以上的重複單元不開環,並使前述其餘的重複單元的環狀結構(酐環)開環。亦即,共聚物1的開環率例如為小於50%。其中,使共聚物1的來自於馬來酸酐之環狀結構的重複單元的全部個數中之60%以上90%以下的重複單元不開環較理想。(Ring-opening step (S'1)) The remaining repeating units are opened while part of the repeating units derived from maleic anhydride in the obtained copolymer 1 or copolymer 2 are closed. ring. Thereby, the amount of carboxyl groups in the copolymer 1 can be adjusted. That is, the acid value of the produced polymer can be controlled. In this embodiment, for example, 50% or more of the repeating units derived from maleic anhydride in the copolymer 1 or the copolymer 2 are not ring-opened, and the cyclic structure (anhydride ring) of the remaining repeating units is not opened. ) open loop. That is, the ring opening rate of the copolymer 1 is, for example, less than 50%. Among them, it is preferable that 60% or more and 90% or less of the total number of repeating units derived from the cyclic structure of maleic anhydride in the copolymer 1 are not ring-opened.
在此,來自於馬來酸酐之重複單元的開環率能夠以下述方式測量。 測量開環前的共聚物1或共聚物2的酸酐結構中之(C=O)的IR吸收強度(A1),利用開環後的酸酐結構中之(C=O)的IR吸收強度(A2),並藉由以下式計算開環率。 開環率(%)=((A1-A2)/A1)×100 另外,使用乙腈作為內部標準物質。Here, the ring opening ratio of the repeating unit derived from maleic anhydride can be measured in the following manner. Measure the IR absorption intensity (A1) of (C=O) in the acid anhydride structure of copolymer 1 or copolymer 2 before ring opening, and use the IR absorption intensity (A2) of the (C=O) in the acid anhydride structure after ring opening ), and calculate the open loop rate by the following formula. Ring opening rate (%)=((A1-A2)/A1)×100 In addition, acetonitrile was used as an internal standard substance.
具體而言,將 (A)作為鹼的金屬烷氧化物 (B)醇及作為鹼的鹼金屬的氫氧化物 中的任一者添加至前述聚合步驟中聚合有前述共聚物1之反應液中,並且進一步添加甲基乙酮(MEK)等有機溶劑,在40~50℃攪拌1~5小時,而獲得反應液L1。在反應液L1中,共聚物1的來自於馬來酸酐之重複單元的一部分酐環開環,並且藉由開環而形成之一部分末端被酯化。另外,其餘的末端未被酯化,而成為金屬鹽結構。Specifically, any one of (A) an alkali metal alkoxide (B) alcohol and an alkali metal hydroxide as an alkali is added to the reaction liquid in which the copolymer 1 is polymerized in the polymerization step. , and an organic solvent such as methyl ethyl ketone (MEK) was further added, and the mixture was stirred at 40 to 50° C. for 1 to 5 hours to obtain a reaction solution L1. In the reaction liquid L1, a part of the anhydride ring of the maleic anhydride-derived repeating unit of the copolymer 1 is ring-opened, and a part of the terminal formed by the ring-opening is esterified. In addition, the remaining terminals are not esterified, but have a metal salt structure.
在本實施形態中,將金屬烷氧化物或鹼金屬的氫氧化物的莫耳數設為聚合步驟中所使用之馬來酸酐的莫耳數的50%以下較理想。其中,將金屬烷氧化物或鹼金屬的氫氧化物的莫耳數設為聚合步驟中所使用之馬來酸酐的莫耳數的40%以下10%以上較理想,設為30%以下更佳。藉由設為如此,能夠減少金屬烷氧化物或鹼金屬的氫氧化物的量,並能夠降低最終獲得之聚合物中的鹼金屬濃度。 藉由降低聚合物中的鹼金屬濃度,能夠抑制在形成使用了該聚合物之器件時金屬離子的遷移。In the present embodiment, the molar number of the metal alkoxide or the alkali metal hydroxide is preferably 50% or less of the molar number of the maleic anhydride used in the polymerization step. Among them, the molar number of the metal alkoxide or alkali metal hydroxide is preferably 40% or less of the molar number of maleic anhydride used in the polymerization step and 10% or more, more preferably 30% or less. . By setting it in this way, the amount of a metal alkoxide or an alkali metal hydroxide can be reduced, and the alkali metal concentration in the polymer finally obtained can be reduced. By reducing the alkali metal concentration in the polymer, the migration of metal ions during the formation of devices using the polymer can be suppressed.
作為前述金屬烷氧化物,以M(OR8 )表示者(M為一價金屬,R8 為碳數1~18的有機基。)較理想。作為金屬M,可列舉鹼金屬,其中,從操作性之觀點考慮,鈉較理想。作為R8 ,例如可列舉與上述式(B1)中的R8 相同者。 另外,作為金屬烷氧化物,亦可使用兩種以上的不同者。但是,從製造穩定性之觀點考慮,使用一種金屬烷氧化物較理想。The metal alkoxide is preferably represented by M(OR 8 ) (M is a monovalent metal, and R 8 is an organic group having 1 to 18 carbon atoms.) Examples of the metal M include alkali metals, and among them, sodium is preferable from the viewpoint of handleability. Examples of R 8 include the same ones as R 8 in the above formula (B1). Moreover, as a metal alkoxide, it is also possible to use two or more different ones. However, from the viewpoint of production stability, it is preferable to use one kind of metal alkoxide.
另一方面,如前述,亦可在(B)醇及作為鹼之鹼金屬的氫氧化物的存在下使共聚物1或共聚物2的來自於馬來酸酐之結構體開環。 作為鹼金屬的氫氧化物,從操作性之觀點考慮,氫氧化鈉較理想。 作為醇,一元醇(R8 OH)較理想。作為有機基之R8 能夠使用前述者。另外,R8 的碳數係30以下較理想。On the other hand, as described above, the maleic anhydride-derived structure of the copolymer 1 or the copolymer 2 may be ring-opened in the presence of the (B) alcohol and the alkali metal hydroxide as the base. As the alkali metal hydroxide, sodium hydroxide is preferable from the viewpoint of workability. As the alcohol, a monohydric alcohol (R 8 OH) is preferable. The aforementioned ones can be used as R 8 of the organic group. In addition, the carbon number coefficient of R 8 is preferably 30 or less.
在該開環步驟(處理S'1)中開環之來自於馬來酸酐之重複單元成為以下式(6)所表示之結構,並成為具有羧基之鹽部分之結構。The repeating unit derived from maleic anhydride which is ring-opened in this ring-opening step (treatment S'1) becomes a structure represented by the following formula (6), and becomes a structure having a salt moiety of a carboxyl group.
另外,利用(A)作為鹼的金屬烷氧化物或、(B)醇及作為鹼的鹼金屬的氫氧化物使共聚物開環時,雖然僅為少許量,但有時會形成以下式(8)、下式(B2)表示之結構體。另外,在下式(B2)中,R9 、R10 亦可與上述R8 相同。In addition, when the copolymer is ring-opened with (A) the metal alkoxide as the base or (B) the alcohol and the hydroxide of the alkali metal as the base, although only a small amount is used, the following formula ( 8), the structure represented by the following formula (B2). In addition, in the following formula (B2), R 9 and R 10 may be the same as the above-mentioned R 8 .
接著,藉由向反應液L1中添加鹽酸或甲酸等酸性水溶液,對共聚物1或共聚物2進行酸處理,而將金屬離子(Na+)取代為質子(H+)。 以上式(6)、(8)表示之結構單元藉由質子取代而成為分別以以下(B1)、(B4)表示之結構單元。Next, by adding an acidic aqueous solution such as hydrochloric acid or formic acid to the reaction liquid L1, the copolymer 1 or the copolymer 2 is acid-treated to replace the metal ion (Na+) with a proton (H+). The structural units represented by the above formulae (6) and (8) become structural units represented by the following (B1) and (B4), respectively, by proton substitution.
在該開環步驟(處理S'1)中,使共聚物1或共聚物2的來自於馬來酸酐之重複單元中之50%以上的重複單元不開環較理想。在共聚物2中,如前述,金屬(例如Na)鍵結於由馬來酸酐環開環而形成之一末端,但藉由使50%以上的重複單元不開環,能夠減少作為產物之聚合物中所含有之金屬量。藉此,能夠降低本實施形態中最終獲得之聚合物中的鹼金屬的量,能夠在使用了該聚合物之負型感光性樹脂組成物中發揮所期望之特性。In this ring-opening step (treatment S'1), it is preferable that 50% or more of the repeating units derived from maleic anhydride in the copolymer 1 or the copolymer 2 are not ring-opened. In the copolymer 2, as described above, a metal (eg, Na) is bonded to one terminal formed by ring-opening of the maleic anhydride ring, but by keeping more than 50% of the repeating units from ring-opening, the polymerization as a product can be reduced. The amount of metal contained in the material. Thereby, the amount of alkali metal in the polymer finally obtained in this embodiment can be reduced, and the desired characteristic can be exhibited in the negative photosensitive resin composition using this polymer.
(清洗步驟(處理S'2)) 利用水與有機溶劑(例如甲基乙酮)的混合物對進行了上述開環步驟(處理S'1)時藉由上述步驟所獲得之含有開環後的共聚物1或共聚物2之溶液進行清洗,而去除殘留金屬成分。開環後的共聚物1或共聚物2、殘留單體及寡聚物移動到有機層。然後,去除水層(第一清洗)。 然後,再次向有機層中添加水與有機溶劑(例如甲基乙酮)的混合物進行清洗(第二清洗)。 在本實施形態中,將如上所述之清洗步驟(處理S'2)反覆進行例如5次以上、更佳為10次。又,藉由調節清洗步驟中所使用之水與有機溶劑的添加量而藉由1次的清洗步驟去除所殘留之鈉的85%以上較理想,去除90%以上為更佳。藉此,能夠充分地降低開環後的共聚物1或共聚物2中之鹼金屬之濃度。 另外,宜反覆進行清洗步驟(處理S3)以使開環後的共聚物1或共聚物2中的鹼金屬濃度成為10ppm以下,較佳為5ppm以下。(Washing Step (Treatment S'2)) The ring-opening step (Treatment S'1) obtained by the above-described step is carried out with a mixture of water and an organic solvent (eg, methyl ethyl ketone) containing the ring-opened The solution of copolymer 1 or copolymer 2 is washed to remove residual metal components. The ring-opened copolymer 1 or copolymer 2, residual monomers and oligomers move to the organic layer. Then, the water layer is removed (first wash). Then, a mixture of water and an organic solvent (eg, methyl ethyl ketone) is added to the organic layer again for washing (second washing). In the present embodiment, the above-described cleaning step (treatment S'2) is repeated, for example, 5 times or more, more preferably 10 times. In addition, it is preferable to remove 85% or more of the remaining sodium by one cleaning step by adjusting the addition amount of water and an organic solvent used in the cleaning step, and more preferably 90% or more. Thereby, the concentration of the alkali metal in the copolymer 1 or the copolymer 2 after ring opening can be sufficiently reduced. In addition, the washing step (treatment S3 ) is preferably repeated so that the alkali metal concentration in the copolymer 1 or the copolymer 2 after ring-opening becomes 10 ppm or less, preferably 5 ppm or less.
在本實施形態中,負型感光性樹脂組成物能夠包含上述聚合物、光敏劑、交聯劑。還能夠包含溶劑、密接改善劑、界面活性劑等添加物。In this embodiment, a negative photosensitive resin composition can contain the said polymer, a photosensitizer, and a crosslinking agent. Additives, such as a solvent, an adhesion improving agent, and a surfactant, can also be contained.
本實施形態中的聚合物的含量的上限值,相對於負型感光性樹脂組成物的總固體成分100質量份為80質量份以下,75質量份以下較理想,70質量份以下更佳。 又,聚合物的含量的下限值相對於負型感光性樹脂組成物的總固體成分100質量份為5質量份以上,10質量份以上較理想,20質量份以下更佳。 聚合物的含量藉由在上述上限下限的範圍內,能夠藉由對負型感光性樹脂組成物進行曝光來形成適當的交聯結構。The upper limit of the content of the polymer in the present embodiment is 80 parts by mass or less, preferably 75 parts by mass or less, and more preferably 70 parts by mass or less, relative to 100 parts by mass of the total solid content of the negative photosensitive resin composition. Moreover, the lower limit of content of a polymer is 5 mass parts or more with respect to 100 mass parts of total solids of a negative photosensitive resin composition, Preferably it is 10 mass parts or more, More preferably, it is 20 mass parts or less. An appropriate crosslinked structure can be formed by exposing the negative photosensitive resin composition to the content of the polymer within the range of the above-mentioned upper limit and lower limit.
(光敏劑) 在本實施形態中,光敏劑能夠使用光自由基聚合起始劑。 作為光自由基聚合起始劑,具體而言,可列舉烷基苯酮型起始劑、肟酯型起始劑、醯基氧化膦型起始劑等。作為光自由基聚合起始劑,能夠使用上述具體例中的一種或將兩種以上組合使用。該等當中,使用肟酯型光自由基聚合起始劑較理想。藉此,能夠以低曝光量使光敏劑自由基化,並能夠提高靈敏度。(Photosensitizer) In this embodiment, a photo-radical polymerization initiator can be used as a photosensitizer. As a photoradical polymerization initiator, an alkylphenone type initiator, an oxime ester type initiator, an acylphosphine oxide type initiator, etc. are mentioned specifically,. As a photoradical polymerization initiator, one of the above-mentioned specific examples can be used, or two or more of them can be used in combination. Among these, it is preferable to use an oxime ester type photo-radical polymerization initiator. Thereby, the photosensitizer can be radicalized with a low exposure amount, and the sensitivity can be improved.
作為具體的光自由基聚合起始劑,例如可列舉1-羥基環己基苯酮、2,2-二甲氧基-1,2-二苯乙-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉丙-1-酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙-1-酮、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、1,2-辛二酮、1-[4-(苯硫基)-2-(鄰苯甲醯基肟)]乙酮、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(鄰乙醯基肟)等。該等當中,亦可使用一種或兩種以上。Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenone, 2,2-dimethoxy-1,2-diphenethan-1-one, 2-methyl-1- [4-(Methylthio)phenyl]-2-morpholin-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyl Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 1, 2-Octanedione, 1-[4-(phenylthio)-2-(o-benzyl oxime)]ethanone, 1-[9-ethyl-6-(2-methylbenzyl oxime) )-9H-carbazol-3-yl]-1-(o-acetyloxime) and so on. Among these, one type or two or more types may be used.
本實施形態中的光敏劑的含量的上限值相對於聚合物100質量份,可以為1質量份以上,1.5質量份以上較理想,2質量份以上更佳。藉此,在負型感光性樹脂組成物中,能夠提高由曝光引起的反應速度。因此,能夠提高靈敏度。 又,光敏劑的含量的下限值設為20質量份以下較理想,15質量份以下為更佳,10質量份以下更佳。藉此,在負型感光性樹脂組成物中,能夠顯現對聚合物的適當的反應性。The upper limit of the content of the photosensitizer in the present embodiment may be 1 part by mass or more, preferably 1.5 parts by mass or more, and more preferably 2 parts by mass or more, relative to 100 parts by mass of the polymer. Thereby, in a negative photosensitive resin composition, the reaction rate by exposure can be improved. Therefore, the sensitivity can be improved. Moreover, the lower limit of the content of the photosensitizer is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. Thereby, in the negative photosensitive resin composition, appropriate reactivity to the polymer can be expressed.
(交聯劑) 在本實施形態中,作為交聯劑能夠使用公知的交聯劑。作為交聯劑,例如使用包含(甲基)丙烯酸基之丙烯酸系交聯劑較理想。丙烯酸系交聯劑例如為多官能丙烯酸化合物。在此,多官能丙烯酸化合物係指具有2個以上的(甲基)丙烯酸基之化合物。 另外,在本實施形態中,(甲基)丙烯酸基係指丙烯酸基或甲基丙烯酸基、亦即甲基丙烯酸基。另外。丙烯酸基包含丙烯酸酯基。又,甲基丙烯酸基包含甲基丙烯酸酯基、亦即甲基丙烯酸酯基。 在此,作為交聯劑及共聚物的末端不飽和碳雙鍵的組合,例如交聯劑為丙烯酸系交聯劑,且具備共聚物的末端不飽和碳雙鍵之官能基包含以上述通式(E1)或通式(E2)表示之結構較理想。藉此,能夠使交聯劑及共聚物的自由基連鎖反應的反應性保持為相同程度。因此,能夠形成較佳的交聯結構。(Crosslinking agent) In the present embodiment, a known crosslinking agent can be used as the crosslinking agent. As a crosslinking agent, it is preferable to use, for example, an acrylic crosslinking agent containing a (meth)acrylic group. The acrylic crosslinking agent is, for example, a polyfunctional acrylic compound. Here, the polyfunctional acrylic compound refers to a compound having two or more (meth)acrylic groups. In addition, in this embodiment, a (meth)acrylic group means an acrylic group or a methacrylic group, that is, a methacrylic group. in addition. Acrylic groups contain acrylate groups. In addition, the methacrylate group includes a methacrylate group, that is, a methacrylate group. Here, as the combination of the crosslinking agent and the terminal unsaturated carbon double bond of the copolymer, for example, the crosslinking agent is an acrylic crosslinking agent, and the functional group having the terminal unsaturated carbon double bond of the copolymer contains the above-mentioned general formula The structure represented by (E1) or general formula (E2) is ideal. Thereby, the reactivity of the radical chain reaction of the crosslinking agent and the copolymer can be kept at the same level. Therefore, a preferable cross-linked structure can be formed.
作為具體的多官能丙烯酸化合物,可列舉三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯等三官能(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二(三羥甲基)丙烷四(甲基)丙烯酸酯等四官能(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等六官能(甲基)丙烯酸酯。可以使用該等當中的一種或兩種以上。 另外,在本實施形態中,(甲基)丙烯酸酯基係指丙烯酸酯基或甲基丙烯酸酯基。Specific polyfunctional acrylic compounds include trimethylolpropane tri(meth)acrylate, trifunctional (meth)acrylates such as neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate, etc. Tetrafunctional (meth)acrylates such as meth)acrylates, di(trimethylol)propane tetra(meth)acrylates, and hexafunctional (meth)acrylates such as dipeotaerythritol hexa(meth)acrylates Acrylate. One or more of these can be used. In addition, in this embodiment, a (meth)acrylate group means an acrylate group or a methacrylate group.
本實施形態中的、交聯劑的含量的下限值相對於聚合物100質量份,可以為20質量份以上,25質量份以上較理想,設為30質量份以上更佳。藉此,除了來自於降莰烯型結構單元的末端不飽和碳雙鍵之交聯結構以外,還能夠形成交聯結構。因此,能夠實現耐熱性的提高、耐溶劑性的提高及顯影後的殘膜率的提高。 又,交聯劑的含量的上限值相對於聚合物100質量份,可以為80質量份以下,75質量份以下較理想,70質量份以下更佳。藉此,能夠防止交聯劑過度地貢獻於交聯結構,並能夠適當地抑制降莰烯型結構單元的運動性。因此,能夠實現耐熱性的提高耐溶劑性的提高、及顯影後的殘膜率的提高。In the present embodiment, the lower limit of the content of the crosslinking agent may be 20 parts by mass or more, preferably 25 parts by mass or more, and more preferably 30 parts by mass or more, relative to 100 parts by mass of the polymer. Thereby, in addition to the crosslinked structure derived from the terminal unsaturated carbon double bond of the norbornene-type structural unit, a crosslinked structure can be formed. Therefore, the improvement of heat resistance, the improvement of solvent resistance, and the improvement of the residual film rate after image development can be aimed at. In addition, the upper limit of the content of the crosslinking agent may be 80 parts by mass or less, preferably 75 parts by mass or less, and more preferably 70 parts by mass or less, relative to 100 parts by mass of the polymer. Thereby, the crosslinking agent can be prevented from contributing excessively to the crosslinked structure, and the mobility of the norbornene-type structural unit can be appropriately suppressed. Therefore, the improvement of heat resistance, the improvement of solvent resistance, and the improvement of the residual film rate after image development can be aimed at.
(溶劑) 本實施形態中記載之負型感光性樹脂組成物能夠藉由將上述各成分溶解於溶劑中,作成清漆而使用。 作為該種溶劑的例子,可列舉N-甲基-2-吡咯啶酮、γ-丁內酯、N,N-二甲基乙醯胺、二甲亞碸、二乙二醇二甲醚、二乙二醇二***、二乙二醇二丁醚、丙二醇一甲醚、二丙二醇一甲醚、丙二醇一甲醚乙酸酯、乳酸甲酯、乳酸乙酯、乳酸丁酯、甲基-1,3-丁二醇乙酸酯、1,3-丁二醇-3-一甲醚、丙酮酸甲酯、丙酮酸乙酯及甲基-3-甲氧基丙酸酯等。 另外,從顯著地抑制樹脂膜的龜裂產生之觀點考慮,在該等化合物中,使用選自由γ-丁內酯、二甲亞碸、二乙二醇二甲醚、二乙二醇二***、二乙二醇二丁醚、丙二醇一甲醚、二丙二醇一甲醚、丙二醇一甲醚乙酸酯組成的群之化合物較理想的態樣。(Solvent) The negative photosensitive resin composition described in this embodiment can be used as a varnish by dissolving each of the above-mentioned components in a solvent. Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1 , 3-Butanediol acetate, 1,3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxypropionate, etc. In addition, from the viewpoint of remarkably suppressing the occurrence of cracks in the resin film, among these compounds, a compound selected from the group consisting of γ-butyrolactone, dimethylsulfoxide, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether is used. , Diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
(其他添加劑) 在本實施形態中,負型感光性樹脂組成物視需要可包含密接改善劑、界面活性劑、抗氧化劑、填料、敏化劑、矽烷偶聯劑及末端密封劑等添加劑。(Other Additives) In the present embodiment, the negative photosensitive resin composition may contain additives such as an adhesion improver, a surfactant, an antioxidant, a filler, a sensitizer, a silane coupling agent, and a terminal sealant as necessary.
本實施形態之樹脂膜由負型感光性樹脂組成物的硬化物形成。The resin film of this embodiment is formed from the hardened|cured material of a negative photosensitive resin composition.
本實施形態的樹脂膜係由上述負型感光性樹脂組成物形成者,能夠由該等的乾燥膜或硬化膜構成。 本實施形態的負型感光性樹脂組成物用於形成阻劑和永久膜等樹脂膜。該種用途從耐熱性的觀點考慮較理想。 又,上述阻劑由樹脂膜構成,該樹脂膜係藉由例如用旋轉塗佈、輥塗、流塗、浸漬塗佈、噴塗、刮塗等方法塗佈負型感光性樹脂組成物並去除溶劑而獲得。 上述永久膜由硬化膜構成,該硬化膜係藉由對上述樹脂膜進行曝光及顯影,圖案形成為所期望的形狀之後,以熱處理等使其硬化而獲得。永久膜例如能夠用於保護膜、層間膜或屏障材料(dam material)等。The resin film of this embodiment is formed from the above-mentioned negative photosensitive resin composition, and can be formed of these dry films or cured films. The negative photosensitive resin composition of the present embodiment is used to form resin films such as resists and permanent films. Such use is preferable from the viewpoint of heat resistance. In addition, the above-mentioned resist is composed of a resin film which is coated with a negative photosensitive resin composition by, for example, spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, and the like, and removes the solvent. and obtained. The said permanent film consists of a cured film obtained by exposing and developing the said resin film, after forming a pattern into a desired shape, and making it harden by heat processing etc.. The permanent film can be used for, for example, a protective film, an interlayer film, a dam material, or the like.
本實施形態之電子裝置使用上述樹脂膜。The electronic device of the present embodiment uses the above-mentioned resin film.
本實施形態的電子裝置100能夠具備上述樹脂膜。 圖1所示之電子裝置100例如為半導體晶圓。此時,例如將電子裝置100經由凸塊52搭載於配線基板上,藉此獲得半導體封裝體。電子裝置100具備設置有電晶體等半導體元件之半導體基板、及設置於半導體基板上之多層配線層(未圖示)。在多層配線層中的最上層設置有層間絕緣膜30及設置於層間絕緣膜30上之最上層配線34。最上層配線34例如由Al構成。又,在層間絕緣膜30上及最上層配線34上設置有鈍化膜32。在鈍化膜32的一部分設置有露出最上層配線34之開口。The
在鈍化膜32上設置有再配線層40。再配線層40具有設置於鈍化膜32上之絕緣層42、設置於絕緣層42上之再配線46、及設置於絕緣層42上及再配線46上之絕緣層44。在絕緣層42形成有與最上層配線34連接之開口。再配線46形成於絕緣層42上及設置於絕緣層42之開口內,與最上層配線34連接。在絕緣層44設置有與再配線46連接之開口。 在本實施形態中,能夠例如藉由樹脂膜構成鈍化膜32、絕緣層42及絕緣層44中的一個以上,該樹脂膜藉由使上述感光性樹脂組成物硬化而形成。此時,例如藉由對塗佈膜曝光紫外線,進行顯影而形成圖案,然後對此進行加熱硬化,藉此形成鈍化膜32、絕緣層42或絕緣層44,該塗佈膜由負型感光性樹脂材料形成。The
在設置於絕緣層44之開口內,例如隔著UBM(Under Bump Metallurgy(凸塊下金屬))層50而形成凸塊52。電子裝置100例如經由凸塊52與配線基板等連接。
另外,本發明並不限定於前述實施形態,在能夠達成本發明的目的之範圍內的變形、改良等包括在本發明中。 [實施例]In addition, this invention is not limited to the said embodiment, The deformation|transformation, improvement, etc. within the range which can achieve the objective of this invention are included in this invention. [Example]
接著,對本發明的實施例進行說明。首先,針對實施例中使用之各材料,如下進行準備。Next, the Example of this invention is demonstrated. First, preparations were made as follows for each material used in the examples.
(合成例1) 以50/50的投入莫耳比使用5-降莰烯-2-羧酸和N-環己基馬來醯亞胺來製作共聚物,並藉由在該共聚物中加入甲基丙烯酸環氧丙酯來合成係共聚物之聚合物而作為合成例1。以下進行詳細說明。 在具備攪拌機、冷卻管之適當尺寸的反應容器中,稱量5-降莰烯-2-羧酸(NC,Honshu Chemical Industry Co.,Ltd.製,87.7g,0.630mol)及2,2’-偶氮雙(2-甲基丙酸)二甲酯(V-601,Wako Pure Chemical Industries, Ltd.製,14.5g,63mmol)並溶解於甲基乙酮(MEK,58.0g)中,從而製作了溶解液。對該溶解液通入氮氣10分鐘而去除氧氣,然後,一邊攪拌一邊在70℃反應了6小時。在反應6小時的期間,費時6小時向反應容器內連續添加了N-環己基馬來醯亞胺(CMI,NIPPON SHOKUBAI CO., LTD.製,112.9g,0.630mol)和MEK127.5g的混合液。結束CMI的混合液的添加之後,在70℃進一步反應了3小時。在反應液中添加MEK266.7g並稀釋後,滴加到大量的甲醇/水混合液(重量比8/2)中並析出固體。在50℃將濾出之固體在真空乾燥機中乾燥16小時,獲得了作為5-降莰烯-2-羧酸與N-環己基馬來醯亞胺的共聚物之聚合物。產量為128.1g,Mw為4,700,Mw/Mn為1.63。 在具備攪拌機、冷卻管之適當尺寸的反應容器中,稱量作為上述5-降莰烯-2-羧酸與N-環己基馬來醯亞胺的共聚物之聚合物(60.0g),並溶解於PGMEA(140.0g)中。進一步添加甲基丙烯酸環氧丙酯(GMA,Tokyo Chemical Industry Co., Ltd.製,20.7g,0.146mol)、三乙胺(1.8g),在80℃加熱了5小時。向反應液中添加甲酸並進行酸處理之後,滴加到大量的甲醇/水混合液(重量比8/2)中並析出了合成例1的聚合物。在40℃將濾出之固體在真空乾燥機中乾燥40小時,獲得了合成例1的聚合物。產量為50.5g,Mw為5,500,Mw/Mn為1.65。(Synthesis Example 1) A copolymer was prepared by using 5-norbornene-2-carboxylic acid and N-cyclohexylmaleimide in an input molar ratio of 50/50, and by adding methyl alcohol to the copolymer. Synthesis Example 1 was obtained by synthesizing a polymer of a copolymer based on glycidyl acrylate. A detailed description will be given below. In a reaction vessel of appropriate size equipped with a stirrer and a cooling pipe, weigh 5-norbornene-2-carboxylic acid (NC, manufactured by Honshu Chemical Industry Co., Ltd., 87.7 g, 0.630 mol) and 2,2' -Azobis(2-methylpropionic acid) dimethyl ester (V-601, manufactured by Wako Pure Chemical Industries, Ltd., 14.5 g, 63 mmol) and dissolved in methyl ethyl ketone (MEK, 58.0 g), thereby A solution was prepared. The dissolved liquid was purged with nitrogen gas for 10 minutes to remove oxygen, and then reacted at 70° C. for 6 hours while stirring. During the 6-hour reaction, a mixture of N-cyclohexylmaleimide (CMI, manufactured by NIPPON SHOKUBAI CO., LTD., 112.9 g, 0.630 mol) and MEK 127.5 g was continuously added to the reaction vessel over 6 hours. liquid. After the addition of the mixed solution of CMI was completed, the reaction was further carried out at 70° C. for 3 hours. After adding 266.7 g of MEK to the reaction liquid and diluting, it was added dropwise to a large amount of methanol/water mixed liquid (weight ratio 8/2) to precipitate a solid. The filtered solid was dried in a vacuum dryer at 50°C for 16 hours to obtain a polymer as a copolymer of 5-norbornene-2-carboxylic acid and N-cyclohexylmaleimide. The yield was 128.1 g, the Mw was 4,700, and the Mw/Mn was 1.63. In an appropriately sized reaction vessel equipped with a stirrer and a cooling pipe, the polymer (60.0 g) of the copolymer of the above-mentioned 5-norbornene-2-carboxylic acid and N-cyclohexylmaleimide was weighed, and Dissolved in PGMEA (140.0 g). Further, glycidyl methacrylate (GMA, manufactured by Tokyo Chemical Industry Co., Ltd., 20.7 g, 0.146 mol) and triethylamine (1.8 g) were added, and the mixture was heated at 80° C. for 5 hours. After adding formic acid to the reaction liquid and performing acid treatment, it was added dropwise to a large amount of methanol/water mixed liquid (weight ratio 8/2), and the polymer of Synthesis Example 1 was precipitated. The filtered solid was dried in a vacuum dryer at 40°C for 40 hours to obtain a polymer of Synthesis Example 1. The yield was 50.5 g, the Mw was 5,500, and the Mw/Mn was 1.65.
將所獲得之合成例1的聚合物溶解於重DMSO中,藉由JEOL Ltd.製的核磁共振器進行了1H-NMR測量。依據藉由1H-NMR測量獲得之光譜,在δ5.68和δ6.07中確認到來自於附加GMA的甲基丙烯醯基之信號,並且在δ12.13中確認到來自於聚合物中的羧基之信號。 另外,依據各自的信號的積分比,確認到羧基與甲基丙烯醯基的mol比為1:0.3。 藉此,確認到來自於5-降莰烯-2-羧酸的一部分結構單元中的羧基被甲基丙烯酸環氧丙酯取代。因此,確認到在合成例1中獲得具有以下式(9)表示之各結構單元之共聚物。The obtained polymer of Synthesis Example 1 was dissolved in heavy DMSO, and 1H-NMR measurement was carried out with a nuclear magnetic resonance apparatus manufactured by JEOL Ltd. According to the spectrum obtained by 1H-NMR measurement, the signal derived from the methacryloyl group to which GMA was added was confirmed in δ 5.68 and δ 6.07, and the signal derived from the carboxyl group in the polymer was confirmed in δ 12.13 the signal. In addition, it was confirmed that the mol ratio of the carboxyl group and the methacryloyl group was 1:0.3 from the integral ratio of the respective signals. Thereby, it was confirmed that the carboxyl groups in some structural units derived from 5-norbornene-2-carboxylic acid were substituted with glycidyl methacrylate. Therefore, it was confirmed that a copolymer having each structural unit represented by the following formula (9) was obtained in Synthesis Example 1.
(合成例2) 以50/15/35的投入莫耳比使用5-降莰烯-2-羧酸、馬來醯亞胺及N-環己基馬來醯亞胺來製備共聚物,並藉由在該共聚物中加入甲基丙烯酸環氧丙酯來合成係共聚物之聚合物而作為合成例2。以下進行詳細說明。 在具備攪拌機、冷卻管之適當尺寸的反應容器中,稱量5-降莰烯-2-羧酸(NC,Honshu Chemical Industry Co.,Ltd.製,70.8g,0.512mol)、N-環己基馬來醯亞胺(CMI,NIPPON SHOKUBAI CO., LTD.製,14.23g,0.079mol)及2,2’-偶氮雙(2-甲基丙酸)二甲酯(V-601,Wako Pure Chemical Industries, Ltd.製,11.8g,51mmol)並溶解於甲基乙酮(MEK,47.2g)中,從而製作了溶解液。對該溶解液通入氮氣10分鐘而去除氧氣,然後,一邊攪拌一邊在70℃反應了6小時。在該反應6小時的期間,費時6小時向反應容器內連續添加了馬來醯亞胺(14.9g,0.154mol)、CMI(50.1g,0.279mol)和MEK91.0g的混合液。結束溶液的添加之後,在70℃進一步反應了3小時。在反應液中添加MEK200g並稀釋後,滴加到大量的甲醇/水混合液(重量比5/5)中並析出了固體。在50℃將濾出之固體在真空乾燥機中乾燥64小時,獲得了作為5-降莰烯-2-羧酸、馬來醯亞胺和N-環己基馬來醯亞胺的共聚物之聚合物。產量為124.3g,Mw為4,500,Mw/Mn為1.75。 在具備攪拌機、冷卻管之適當尺寸的反應容器中,稱量作為上述5-降莰烯-2-羧酸、馬來醯亞胺和N-環己基馬來醯亞胺的共聚物之聚合物(50.0g),並溶解於PGMEA(100.0g)中。進一步添加甲基丙烯酸環氧丙酯(GMA,Tokyo Chemical Industry Co., Ltd.製,24.3g,0.171mol)、三乙胺(1.5g),在90℃加熱了4小時。向反應液中添加甲酸並進行酸處理之後,滴加到大量的甲醇/水混合液(重量比5/5)中並析出了合成例2的聚合物。在40℃將濾出之固體在真空乾燥機中乾燥40小時,獲得了合成例2的聚合物。產量為31.2g,Mw為4,900,Mw/Mn為1.72。(Synthesis Example 2) A copolymer was prepared by using 5-norbornene-2-carboxylic acid, maleimide and N-cyclohexylmaleimide in a molar ratio of 50/15/35, and by The polymer of the copolymer was synthesized by adding glycidyl methacrylate to this copolymer, and it was set as Synthesis Example 2. A detailed description will be given below. In an appropriately sized reaction vessel equipped with a stirrer and a cooling pipe, weigh 5-norbornene-2-carboxylic acid (NC, manufactured by Honshu Chemical Industry Co., Ltd., 70.8 g, 0.512 mol), N-cyclohexyl Maleimide (CMI, manufactured by NIPPON SHOKUBAI CO., LTD., 14.23 g, 0.079 mol) and 2,2'-azobis(2-methylpropionic acid) dimethyl ester (V-601, Wako Pure Chemical Industries, Ltd. product, 11.8 g, 51 mmol) and dissolved in methyl ethyl ketone (MEK, 47.2 g) to prepare a solution. The dissolved liquid was purged with nitrogen gas for 10 minutes to remove oxygen, and then reacted at 70° C. for 6 hours while stirring. During the 6-hour reaction, a mixed solution of maleimide (14.9 g, 0.154 mol), CMI (50.1 g, 0.279 mol) and MEK 91.0 g was continuously added to the reaction vessel over 6 hours. After the addition of the solution was completed, it was further reacted at 70°C for 3 hours. After adding 200 g of MEK to the reaction solution and diluting it, it was added dropwise to a large amount of methanol/water mixed solution (weight ratio 5/5) to precipitate a solid. The filtered solid was dried in a vacuum dryer at 50°C for 64 hours to obtain a copolymer of 5-norbornene-2-carboxylic acid, maleimide and N-cyclohexylmaleimide polymer. The yield was 124.3 g, the Mw was 4,500, and the Mw/Mn was 1.75. In an appropriately sized reaction vessel equipped with a stirrer and a cooling pipe, weigh the polymer as a copolymer of the above-mentioned 5-norbornene-2-carboxylic acid, maleimide and N-cyclohexylmaleimide (50.0 g) and dissolved in PGMEA (100.0 g). Further, glycidyl methacrylate (GMA, manufactured by Tokyo Chemical Industry Co., Ltd., 24.3 g, 0.171 mol) and triethylamine (1.5 g) were added, and the mixture was heated at 90° C. for 4 hours. After adding formic acid to the reaction liquid and performing acid treatment, it was added dropwise to a large amount of methanol/water mixed liquid (weight ratio 5/5), and the polymer of Synthesis Example 2 was precipitated. The filtered solid was dried in a vacuum dryer at 40°C for 40 hours to obtain a polymer of Synthesis Example 2. The yield was 31.2 g, the Mw was 4,900, and the Mw/Mn was 1.72.
將所獲得之合成例2的聚合物溶解於重DMSO中,藉由JEOL Ltd.製的核磁共振器進行了1H-NMR測量。與合成例1同樣地確認到來自於羧基之峰和來自於甲基丙烯醯基的結構之峰。藉此,確認到來自於5-降莰烯-2-羧酸的一部分結構單元中的羧基被甲基丙烯酸環氧丙酯取代。因此,確認到在合成例2中獲得具有以下式(10)表示之各結構單元之共聚物。The obtained polymer of Synthesis Example 2 was dissolved in heavy DMSO, and 1H-NMR measurement was carried out with a nuclear magnetic resonance apparatus manufactured by JEOL Ltd. In the same manner as in Synthesis Example 1, a peak derived from a carboxyl group and a peak derived from a structure derived from a methacryloyl group were confirmed. Thereby, it was confirmed that the carboxyl groups in some structural units derived from 5-norbornene-2-carboxylic acid were substituted with glycidyl methacrylate. Therefore, it was confirmed that a copolymer having each structural unit represented by the following formula (10) was obtained in Synthesis Example 2.
(合成例3) 以50/50的投入莫耳比使用2-降莰烯和馬來酸酐來製作共聚物,並藉由乙酸鈉使該共聚物的來自馬來酸酐之結構單元開環,並添加甲基丙烯酸環氧丙酯來合成係共聚物之聚合物而作為合成例3。以下進行詳細說明。 在具備攪拌機、冷卻管之適當尺寸的反應容器中,稱量馬來酸酐(NIPPON SHOKUBAI CO., LTD.製,122.4g,1.25mol)、2-降莰烯(75wt%甲苯溶液,Maruzen Petrochemical Co., Ltd.製,156.8g,1.25mol)及2,2’-偶氮雙(2-甲基丙酸)二甲酯(V-601、Wako Pure Chemical Industries, Ltd.製,11.5g,50mmol)並溶解於甲基乙酮(MEK,150.8g)及甲苯(38.5g)中,從而製作了溶解液。對該溶解液通入氮氣10分鐘而去除氧氣,然後,一邊攪拌一邊加熱至60℃。16小時後添加MEK(320g)稀釋並冷卻。將該反應混合物滴加到大量的甲醇中並析出固體,利用吸濾器過濾之後,進一步用甲醇清洗並濾出固體。將所獲得之固體在70℃進行真空乾燥,獲得了2-降莰烯和馬來酸酐的共聚物。產量為208.1g,重量平均分子量(Mw)為11,100,分散度(Mw/Mn)為2.25。 在具備攪拌機、冷卻管之適當尺寸的反應容器中,稱量上述2-降莰烯和馬來酸酐的共聚物(10.0g)並溶解於MEK(30.0g)中。進一步添加甲基丙烯酸-2-羥乙酯(HEMA,NIPPON SHOKUBAI CO., LTD.製,8.5g,65mmol)、乙酸鈉(1.0g),在70℃加熱了8小時。對該反應液添加甲基丙烯酸環氧丙酯(GMA,1.5g,10mmol),進而在70℃攪拌了16小時。向反應液中加入甲酸進行酸處理之後,滴加到大量的純水中並析出了聚合物。在40℃將濾出之固體在真空乾燥機中乾燥16小時,獲得了合成例3的聚合物。產量為11.5g,Mw為14,100,Mw/Mn為2.30。 在合成例3中獲得了具有以下式(13)表示之各結構單元之共聚物。(Synthesis Example 3) A copolymer was prepared using 2-norbornene and maleic anhydride at a molar ratio of 50/50, and the structural unit derived from maleic anhydride was ring-opened by sodium acetate, and Glycidyl methacrylate was added to synthesize a polymer of the copolymer, which was used as Synthesis Example 3. A detailed description will be given below. In an appropriately sized reaction vessel equipped with a stirrer and a cooling pipe, maleic anhydride (manufactured by NIPPON SHOKUBAI CO., LTD., 122.4 g, 1.25 mol), 2-norbornene (75 wt% toluene solution, Maruzen Petrochemical Co., Ltd.) were weighed. ., Ltd., 156.8 g, 1.25 mol) and 2,2'-azobis(2-methylpropionic acid) dimethyl ester (V-601, manufactured by Wako Pure Chemical Industries, Ltd., 11.5 g, 50 mmol) ) and dissolved in methyl ethyl ketone (MEK, 150.8 g) and toluene (38.5 g) to prepare a solution. The dissolved liquid was purged with nitrogen gas for 10 minutes to remove oxygen, and then heated to 60° C. with stirring. After 16 hours MEK (320 g) was added to dilute and cool. The reaction mixture was added dropwise to a large amount of methanol to precipitate a solid, which was filtered with a suction filter, and then washed with methanol, and the solid was collected by filtration. The obtained solid was vacuum-dried at 70°C to obtain a copolymer of 2-norbornene and maleic anhydride. The yield was 208.1 g, the weight average molecular weight (Mw) was 11,100, and the degree of dispersion (Mw/Mn) was 2.25. In an appropriately sized reaction vessel equipped with a stirrer and a cooling pipe, the above-mentioned copolymer of 2-norbornene and maleic anhydride (10.0 g) was weighed and dissolved in MEK (30.0 g). Further, 2-hydroxyethyl methacrylate (manufactured by HEMA, NIPPON SHOKUBAI CO., LTD., 8.5 g, 65 mmol) and sodium acetate (1.0 g) were added, and the mixture was heated at 70° C. for 8 hours. To this reaction liquid, glycidyl methacrylate (GMA, 1.5 g, 10 mmol) was added, and the mixture was further stirred at 70° C. for 16 hours. After adding formic acid to the reaction liquid for acid treatment, it was added dropwise to a large amount of pure water to precipitate a polymer. The filtered solid was dried in a vacuum dryer at 40°C for 16 hours to obtain a polymer of Synthesis Example 3. The yield was 11.5 g, the Mw was 14,100, and the Mw/Mn was 2.30. In Synthesis Example 3, a copolymer having each structural unit represented by the following formula (13) was obtained.
(酸值) 針對各合成例,如下算出所獲得之聚合物的酸值。 稱量已合成之聚合物約0.2g,並溶解於THF/甲醇=1/1(v/v)的溶液50mL中。使用濃度0.1M的甲醇鈉/甲醇溶液對所獲得之溶液進行了電位滴定。進行電位滴定時,藉由直至電極中產生之電位的反曲點為止的試劑添加量對聚合物的酸值進行了評價。(Acid value) For each synthesis example, the acid value of the obtained polymer was calculated as follows. About 0.2 g of the synthesized polymer was weighed and dissolved in 50 mL of a solution of THF/methanol=1/1 (v/v). The obtained solution was potentiometrically titrated with a 0.1 M sodium methoxide/methanol solution. In potentiometric titration, the acid value of the polymer was evaluated by the amount of the reagent added up to the inflection point of the potential generated in the electrode.
(鹼溶解速度) 針對各合成例,如下測量了所獲得之聚合物的鹼溶解速度。 將聚合物溶解於PGMEA中,製備了固體成分濃度25%的溶液。將該聚合物溶液以旋轉方式塗佈於矽晶圓上,並在100℃對其進行120秒鐘的軟烤,形成了厚度H為約2.0μm的聚合物膜。將形成有該聚合物膜之矽晶圓浸漬於2.38%、23℃的氫氧化四甲基銨水溶液中,測量了直至視覺上聚合物膜消失為止的時間T。依據H及T,由以下式算出鹼溶解速度。 (鹼溶解速度)[埃/秒]=(膜厚H)/(直至聚合物膜消失為止的時間T)(Alkali dissolution rate) For each synthesis example, the alkali dissolution rate of the obtained polymer was measured as follows. The polymer was dissolved in PGMEA to prepare a solution with a solid content concentration of 25%. The polymer solution was spin-coated on a silicon wafer and soft-baked at 100° C. for 120 seconds to form a polymer film having a thickness H of about 2.0 μm. The silicon wafer on which the polymer film was formed was immersed in a 2.38%, 23° C. tetramethylammonium hydroxide aqueous solution, and the time T until the polymer film disappeared visually was measured. Based on H and T, the alkali dissolution rate was calculated by the following formula. (Alkali dissolution rate) [Angstrom/sec]=(film thickness H)/(time T until polymer film disappears)
針對各合成例的聚合物,將酸值和鹼溶解速度的評價結果示於以下表1。Table 1 below shows the results of evaluation of the acid value and the alkali dissolution rate for the polymers of each synthesis example.
[表1]
(光敏劑) 光敏劑1:使用了下式(11)表示之光自由基聚合起始劑(BASF公司製Irgacure OXE02)。(Photosensitizer) Photosensitizer 1: A photo-radical polymerization initiator (Irgacure OXE02 manufactured by BASF Corporation) represented by the following formula (11) was used.
(交聯劑) 交聯劑1:使用了下式(12)表示之丙烯酸系交聯劑(Daicel-Cytec Company, Ltd.製DPHA)。(Crosslinking agent) Crosslinking agent 1: An acrylic crosslinking agent represented by the following formula (12) (DPHA manufactured by Daicel-Cytec Company, Ltd.) was used.
(密接改善劑) 密接改善劑1:3-環氧丙氧基丙基三甲氧基矽烷(Shin-Etsu Chemical Co., Ltd.製 KBM-403)(Adhesion Improver) Adhesion Improver 1: 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
(界面活性劑) 界面活性劑1:Megaface F-556(DIC Corporation製)(Surfactant) Surfactant 1: Megaface F-556 (manufactured by DIC Corporation)
接著,對本發明的實施例中製作之負型感光性樹脂組成物進行說明。Next, the negative photosensitive resin composition produced in the Example of this invention is demonstrated.
(實施例1、實施例2及比較例1的負型感光性樹脂組成物的製備) 針對各實施例、各比較例,以表2所示之摻合量,將合成例1~3中製作之聚合物的20%PGMEA溶液、光敏劑、交聯劑、密接改善劑及界面活性劑溶解於適量的PGMEA中並進行了攪拌。攪拌後,用0.2μm過濾器進行過濾,製備了負型樹脂組成物。 另外,當製備各實施例及各比較例的負型感光性樹脂組成物時,將PGMEA調整為樹脂成分的含量(酚醛樹脂與聚合物的總和)成為30%。(Preparation of Negative Photosensitive Resin Compositions of Example 1, Example 2, and Comparative Example 1) For each Example and each Comparative Example, the compounding amounts shown in Table 2 were prepared in Synthesis Examples 1 to 3 The 20% PGMEA solution of the polymer, photosensitizer, crosslinking agent, adhesion improving agent and surfactant were dissolved in an appropriate amount of PGMEA and stirred. After stirring, it filtered through a 0.2 μm filter to prepare a negative resin composition. In addition, when preparing the negative photosensitive resin composition of each Example and each comparative example, PGMEA was adjusted so that content of a resin component (the sum total of a phenol resin and a polymer) might become 30%.
(重量減少5%之溫度) 針對各實施例、各比較例,使用所獲得之負型感光性樹脂組成物以如下方式評價了硬化後的升溫過程中的重量減少5%之溫度。 首先,對6英吋晶圓塗佈負型感光性樹脂組成物之後,在80℃、90秒的條件下實施熱處理,藉此進行了脫溶劑。接著,在烘箱中對負型感光性樹脂組成物進行熱處理,並使感光性樹脂組成物硬化。該熱處理係藉由如下方式而進行:在30℃,利用氮氣以30分鐘對載置有上述晶圓之烘箱內進行置換,以升溫速度5℃/min升溫至硬化溫度(200℃)之後,以硬化溫度(200℃)保持30分鐘。在上述熱處理之後,以降溫速度5℃/min使烘箱內的溫度降溫至70℃以下,取出上述晶圓。接著,使用氫氟酸從上述晶圓剝離感光性樹脂組成物的硬化膜,在60℃、10小時的條件下進行了乾燥。這樣,針對各實施例及各比較例分別獲得了藉由硬化溫度200℃而硬化之硬化膜。 接著,測量了上述樣品的重量減少5%之溫度(℃)。測量係針對稱量10mg硬化膜而獲得之試樣,使用熱重量/差示熱測量裝置(TG/DTA),在開始溫度30℃、測量溫度範圍30~500℃、升溫速度5℃/min的條件下進行。將稱量之試樣的重量減少5%之時點的溫度作為重量減少5%之溫度。(Temperature at which weight is reduced by 5%) The temperature at which the weight is reduced by 5% in the heating process after curing was evaluated as follows using the obtained negative photosensitive resin composition for each Example and each comparative example. First, after applying the negative photosensitive resin composition to a 6-inch wafer, the solvent was removed by heat treatment at 80° C. for 90 seconds. Next, the negative photosensitive resin composition is heat-treated in an oven to harden the photosensitive resin composition. This heat treatment was performed by replacing the inside of the oven on which the wafers were placed with nitrogen gas at 30°C for 30 minutes, heating up to the curing temperature (200°C) at a heating rate of 5°C/min, The hardening temperature (200°C) was maintained for 30 minutes. After the above-mentioned heat treatment, the temperature in the oven was lowered to 70° C. or lower at a cooling rate of 5° C./min, and the above-mentioned wafer was taken out. Next, the cured film of the photosensitive resin composition was peeled off from the said wafer using hydrofluoric acid, and it dried on the conditions of 60 degreeC and 10 hours. In this way, a cured film cured at a curing temperature of 200° C. was obtained for each example and each comparative example. Next, the temperature (°C) at which the weight of the above-mentioned sample was reduced by 5% was measured. The measurement is performed on a sample obtained by weighing 10 mg of the cured film, using a thermogravimetric/differential calorimetry device (TG/DTA), at an initial temperature of 30°C, a measurement temperature range of 30 to 500°C, and a heating rate of 5°C/min. conditions. The temperature at the point where the weight of the weighed sample was reduced by 5% was taken as the temperature at which the weight was reduced by 5%.
(硬化後殘膜率) 針對各實施例、各比較例,使用所獲得之負型感光性樹脂組成物以如下方式進行了硬化後的殘膜率的評價。 將所獲得之負型感光性樹脂組成物旋轉塗佈於經HMDS(Hexamethyldisilazane(六甲基二矽氮烷))處理之4英吋矽晶圓上,在110℃利用加熱板烘烤100秒鐘之後,獲得了約3.0μm厚度的薄膜A。藉由Canon Inc.製的g+h+i射線光罩對準曝光機(PLA-501F),使用10μm的線與間距的寬度為1:1的光罩,以圖案尺寸成為10μm的線與間距的寬度為1:1之最佳曝光量(50mJ/cm2 )對該薄膜A進行曝光,利用2.38質量%四甲基氫氧化銨水溶液在23℃進行90秒鐘的顯影,藉此獲得了線與間距寬度為1:1的附線&間距圖案之薄膜B。 依據利用上述方法而獲得之薄膜A、薄膜B的膜厚,由以下式算出了殘膜率。 硬化後殘膜率(%)={(薄膜B的膜厚(μm))/(薄膜A的膜厚(μm))}×100(Remaining film rate after hardening) About each Example and each comparative example, the evaluation of the residual film rate after hardening was performed as follows using the obtained negative photosensitive resin composition. The obtained negative photosensitive resin composition was spin-coated on a 4-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked at 110°C for 100 seconds on a hot plate After that, a thin film A with a thickness of about 3.0 μm was obtained. A g+h+i ray mask alignment exposure machine (PLA-501F) manufactured by Canon Inc. was used, using a mask with a 10 μm line-to-space width of 1:1, and a pattern size of 10 μm line-to-space The film A was exposed to an optimum exposure amount (50 mJ/cm 2 ) with a width of 1:1, and developed with a 2.38 mass % aqueous tetramethylammonium hydroxide solution at 23° C. for 90 seconds, thereby obtaining a line Film B with a 1:1 line & space pattern with space width. From the film thickness of the thin film A and the thin film B obtained by the above-mentioned method, the residual film ratio was calculated by the following formula. Residual film ratio after curing (%)={(film thickness of film B (μm))/(film thickness of film A (μm))}×100
(耐溶劑性) 針對各實施例、各比較例,使用所獲得之負型感光性樹脂組成物,以如下方式進行了耐溶劑性的評價。 將所獲得之負型感光性樹脂組成物旋轉塗佈於縱100mm、橫100mm尺寸的Corning Incorporated製的1737玻璃基板上,在110℃利用加熱板烘烤100秒鐘之後,獲得了約3.0μm厚的附薄膜之玻璃基板。 在室溫(25℃)下將上述附薄膜之玻璃基板浸漬於N-甲基吡咯啶酮(KANTO CHEMICAL CO.,INC.)中10分鐘,然後用純水清洗。算出由以下運算式定義之膜厚變化率。 膜厚變化率(%)=[{(溶劑浸漬後的膜厚)-(溶劑浸漬前的膜厚)}/(溶劑浸漬前的膜厚)]×100(Solvent resistance) The solvent resistance evaluation was performed as follows using the obtained negative photosensitive resin composition about each Example and each comparative example. The obtained negative photosensitive resin composition was spin-coated on a 1737 glass substrate made by Corning Incorporated with a size of 100 mm in length and 100 mm in width, and after baking at 110° C. for 100 seconds on a hot plate, a thickness of about 3.0 μm was obtained. The glass substrate with film. The glass substrate with the thin film was immersed in N-methylpyrrolidone (KANTO CHEMICAL CO., INC.) for 10 minutes at room temperature (25° C.), and then washed with pure water. The film thickness change rate defined by the following formula was calculated. Film thickness change rate (%)=[{(film thickness after solvent immersion)-(film thickness before solvent immersion)}/(film thickness before solvent immersion)]×100
(靈敏度) 針對各實施例、各比較例,使用所獲得之負型感光性樹脂組成物,以如下方式進行了靈敏度的評價。 將所獲得之負型感光性樹脂組成物旋轉塗佈於經HMDS(Hexamethyldisilazane(六甲基二矽氮烷))處理之4英吋矽晶圓上,在90℃利用加熱板烘烤120秒鐘後,獲得了約3.0μm厚的薄膜。藉由Canon Inc.製的g+h+i射線光罩對準曝光機(PLA-501F),使用10μm的線與間距的寬度為1:1的光罩對該薄膜及進行了曝光。接著,在110℃利用加熱板烘烤120秒鐘後,利用2.38質量%四甲基氫氧化銨水溶液在23℃進行60秒鐘的顯影,藉此形成阻劑圖案,將阻劑圖案為10μm的線寬:間距寬=1:1時的曝光量(mJ/cm2 )作為靈敏度。(Sensitivity) For each Example and each comparative example, the sensitivity evaluation was performed as follows using the obtained negative photosensitive resin composition. The obtained negative photosensitive resin composition was spin-coated on a 4-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked at 90°C for 120 seconds with a hot plate After that, a thin film with a thickness of about 3.0 μm was obtained. The film and the film were exposed by a g+h+i ray mask alignment exposure machine (PLA-501F) manufactured by Canon Inc. using a mask with a line-to-space width of 10 μm and a width of 1:1. Next, after baking on a hot plate at 110° C. for 120 seconds, a resist pattern was formed by developing a 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23° C. for 60 seconds, and the resist pattern was 10 μm in size. Line width: The exposure amount (mJ/cm 2 ) when the pitch width = 1:1 was used as the sensitivity.
[表2]
如表1所示,確認到合成例1、合成例2係保持了適當的酸值及鹼溶解速度之共聚物。 又,如表2所示,能夠確認到實施例1的負型感光性樹脂組成物與比較例1的負型感光性樹脂組成物相比,耐熱性、硬化後殘膜率及耐溶劑性得到提高。進而,能夠確認到實施例2的負型感光性樹脂組成物與比較例1的負型感光性樹脂組成物相比,耐熱性、硬化後殘膜率及耐溶劑性得到提高,進而保持靈敏度。As shown in Table 1, it was confirmed that Synthesis Example 1 and Synthesis Example 2 are copolymers in which appropriate acid value and alkali dissolution rate are maintained. In addition, as shown in Table 2, it was confirmed that the negative photosensitive resin composition of Example 1 had better heat resistance, residual film ratio after curing, and solvent resistance than the negative photosensitive resin composition of Comparative Example 1. improve. Furthermore, compared with the negative photosensitive resin composition of Comparative Example 1, the negative photosensitive resin composition of Example 2 was confirmed to have improved heat resistance, residual film rate after curing, and solvent resistance, and further maintained sensitivity.
本申請主張基於2017年1月10日申請之日本專利申請特願2017-002022號的優先權,並將其揭示之全部內容援用於此。The present application claims priority based on Japanese Patent Application No. 2017-002022 for which it applied on January 10, 2017, and the entire contents of the disclosure are incorporated herein by reference.
30‧‧‧層間絕緣膜32‧‧‧鈍化膜34‧‧‧最上層配線40‧‧‧再配線層42‧‧‧絕緣層44‧‧‧絕緣層46‧‧‧再配線50‧‧‧凸塊下金屬層52‧‧‧凸塊100‧‧‧電子裝置30‧‧‧Interlayer insulating
上述目的和其他目的、特徵及優點,藉由以下說明之較佳實施形態及附隨於此之以下圖式變得更加明確。The above-mentioned objects and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the following drawings that accompany them.
圖1係表示本實施形態之電子裝置的一例之剖面圖。FIG. 1 is a cross-sectional view showing an example of an electronic device according to the present embodiment.
30‧‧‧層間絕緣膜 30‧‧‧Interlayer insulating film
32‧‧‧鈍化膜 32‧‧‧Passivation film
34‧‧‧最上層配線 34‧‧‧Top layer wiring
40‧‧‧再配線層 40‧‧‧Redistribution layer
42‧‧‧絕緣層 42‧‧‧Insulation
44‧‧‧絕緣層 44‧‧‧Insulation
46‧‧‧再配線 46‧‧‧Rewiring
50‧‧‧凸塊下金屬層 50‧‧‧Under bump metal layer
52‧‧‧凸塊 52‧‧‧Bumps
100‧‧‧電子裝置 100‧‧‧Electronic Devices
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