JPH10125671A - Organic insulating film material and its preparation - Google Patents
Organic insulating film material and its preparationInfo
- Publication number
- JPH10125671A JPH10125671A JP27346796A JP27346796A JPH10125671A JP H10125671 A JPH10125671 A JP H10125671A JP 27346796 A JP27346796 A JP 27346796A JP 27346796 A JP27346796 A JP 27346796A JP H10125671 A JPH10125671 A JP H10125671A
- Authority
- JP
- Japan
- Prior art keywords
- insulating film
- organic insulating
- film material
- reactor
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- 229920000620 organic polymer Polymers 0.000 claims abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 6
- -1 magnesium sulfate anhydride Chemical class 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 150000002170 ethers Chemical class 0.000 claims 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- ZOQOPXVJANRGJZ-UHFFFAOYSA-N 2-(trifluoromethyl)phenol Chemical compound OC1=CC=CC=C1C(F)(F)F ZOQOPXVJANRGJZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 abstract 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 abstract 1
- 235000019341 magnesium sulphate Nutrition 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000019000 fluorine Nutrition 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Formation Of Insulating Films (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyethers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は有機絶縁膜材料お
よびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic insulating film material and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】今日、半導体装置に用いる絶縁膜として
は、ＣＶＤ法で形成したシリコン酸化膜を一般的に用い
ているが、今後、パターンサイズが微細化し、特にサブ
クォーターミクロン程度になると、配線による信号遅延
や電力消費量の増大が顕著となることが予想される。こ
こで、信号遅延は通常ＲＣ（Ｒは配線抵抗、Ｃは配線間
容量）で表され、また電力消費量は配線間容量Ｃの大き
さに対応して変化する。そして、配線間容量Ｃは絶縁膜
の比誘電率により決定される。2. Description of the Related Art At present, a silicon oxide film formed by a CVD method is generally used as an insulating film used in a semiconductor device. It is expected that the signal delay and the increase in power consumption due to will be remarkable. Here, the signal delay is usually represented by RC (R is the wiring resistance, C is the capacitance between wirings), and the power consumption changes according to the magnitude of the capacitance C between the wirings. The inter-wiring capacitance C is determined by the relative permittivity of the insulating film.
【０００３】したがって、信号遅延や、電力消費量を抑
制するためには、絶縁膜の比誘電率を低下させる必要が
ある。比誘電率を低下させるためには、絶縁膜として、
有機物からなる絶縁膜（有機絶縁膜）を用いることが有
効であるということは以前より知られていることであ
る。例えば文献：「Journal of Electronic Materials,
Vol.19,No.12,1990,p1357-1366」 には、ベンゾシクロブ
テンを用いて形成した有機絶縁膜（以下、従来の有機絶
縁膜と称する。）について検討している。この従来の有
機絶縁膜の比誘電率は２．７であり、ＣＶＤ法で形成し
たシリコン酸化膜の比誘電率は４．３程度であることと
比較して大きく低下している。Therefore, it is necessary to lower the relative dielectric constant of the insulating film in order to suppress signal delay and power consumption. In order to lower the relative dielectric constant, as an insulating film,
It has been known that it is effective to use an insulating film made of an organic material (organic insulating film). For example, reference: "Journal of Electronic Materials,
Vol.19, No.12, 1990, p1357-1366, discusses an organic insulating film formed using benzocyclobutene (hereinafter referred to as a conventional organic insulating film). The relative dielectric constant of this conventional organic insulating film is 2.7, which is much lower than the relative dielectric constant of a silicon oxide film formed by the CVD method, which is about 4.3.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、パター
ンサイズがサブクォーターミクロン程度になることを想
定した場合には、この従来の有機絶縁膜の比誘電率は未
だ大きい。However, when it is assumed that the pattern size is on the order of sub-quarter microns, the relative permittivity of this conventional organic insulating film is still large.
【０００５】したがって、比誘電率が十分小さい有機絶
縁膜を形成することができる有機絶縁膜材料およびその
製造方法の出現が望まれていた。Therefore, the appearance of an organic insulating film material capable of forming an organic insulating film having a sufficiently small relative dielectric constant and a method of manufacturing the same have been desired.
【０００６】[0006]
【課題を解決するための手段】このため、この発明で
は、まず、以下に示す〜の公知事実を考慮して、有
機絶縁膜材料として用いることのできる樹脂の設計を行
った。Therefore, in the present invention, first, a resin which can be used as an organic insulating film material was designed in consideration of the following known facts (1) to (4).
【０００７】：樹脂中にフッ素を導入すると、その樹
脂を用いて形成した膜の比誘電率を下げることができ
る。[0007] When fluorine is introduced into a resin, the relative dielectric constant of a film formed using the resin can be reduced.
【０００８】：樹脂中に共有結合や、カルボニル基、
ニトロ基等の置換基を導入すると、その樹脂を用いて形
成した膜の比誘電率が上がる。A covalent bond, a carbonyl group,
When a substituent such as a nitro group is introduced, the relative dielectric constant of a film formed using the resin increases.
【０００９】：樹脂中に芳香環を導入すると、その樹
脂を用いて形成した膜の比誘電率を上げてしまうが、膜
の耐熱性を上げるためには、樹脂中に芳香環を導入する
ことが必須である。When an aromatic ring is introduced into a resin, the relative dielectric constant of a film formed using the resin is increased. However, in order to increase the heat resistance of the film, it is necessary to introduce an aromatic ring into the resin. Is required.
【００１０】以上の〜の公知事実に基づいて設計さ
れたこの発明の有機絶縁膜材料は、フッ化物の置換基を
もつ多数の芳香環同士を、酸素を介して結合して構成さ
れる有機ポリマーから成ることを特徴とする。The organic insulating film material of the present invention designed on the basis of the above-mentioned known facts is an organic polymer constituted by bonding a large number of aromatic rings having a substituent of fluoride via oxygen. Characterized by comprising:
【００１１】この有機絶縁膜材料には、置換基として、
フッ化物が導入されているので、この材料を用いて形成
した膜の比誘電率を下げることができる。This organic insulating film material has, as a substituent,
Since the fluoride is introduced, the relative dielectric constant of a film formed using this material can be reduced.
【００１２】また、この材料を形成する有機ポリマーを
フッ素を含んでいるポリアリールエーテル誘導体とす
る。Further, the organic polymer forming this material is a polyarylether derivative containing fluorine.
【００１３】芳香環として最小単位であるベンゼン環が
繰り返されてなる材料であるため、この材料を用いて形
成した膜の芳香環の影響による比誘電率の上昇は最小限
に抑えることができる。Since the aromatic ring is a material in which a benzene ring as a minimum unit is repeated, an increase in the relative dielectric constant due to the influence of the aromatic ring of a film formed using this material can be minimized.
【００１４】また、上記のフッ素を含んでいるポリアリ
ールエーテル誘導体を下記の（１）式で表される構造単
位の繰り返しからなることを特徴とする。Further, the above-mentioned fluorine-containing polyarylether derivative is characterized by being composed of repeating structural units represented by the following formula (1).
【００１５】[0015]
【化２】 Embedded image
【００１６】このような有機絶縁膜材料によれば、１つ
の繰り返し単位中に３つのフッ素と１つのベンゼン環が
導入されてある。このため、この材料を用いて形成した
有機絶縁膜の比誘電率を低くすることができる。According to such an organic insulating film material, three fluorines and one benzene ring are introduced into one repeating unit. Therefore, the relative dielectric constant of the organic insulating film formed using this material can be reduced.
【００１７】なお、この有機絶縁膜材料中には、比誘電
率を上げる要因となる共有結合や、カルボニル基、ニト
ロ基等の置換基は導入していない。In the organic insulating film material, no covalent bond or a substituent such as a carbonyl group or a nitro group, which is a factor for increasing the relative dielectric constant, is introduced.
【００１８】また、この発明の有機絶縁膜材料の製造方
法によれば、下記の（２）式で表されるフッ素を含んで
いるフェノール化合物をモノマーとし、前記モノマーと
塩基性触媒とを含む反応溶液を反応器に入れ、酸素存在
下で、前記モノマーを脱水縮合反応によって重合させる
ことを特徴とする。Further, according to the method for producing an organic insulating film material of the present invention, a phenol compound containing fluorine represented by the following formula (2) is used as a monomer, and the reaction comprising the monomer and a basic catalyst is used. The solution is put into a reactor, and the monomer is polymerized by a dehydration condensation reaction in the presence of oxygen.
【００１９】[0019]
【化３】 Embedded image
【００２０】このような有機絶縁膜材料の製造方法によ
れば、モノマー（式（２））同士の間で脱水縮合反応が
おこり、主鎖が実質的に上記（１）式で表される単位を
繰り返して成るポリマーが生成する。According to such a method for producing an organic insulating film material, a dehydration-condensation reaction occurs between monomers (formula (2)), and the main chain is substantially a unit represented by the above formula (1). Is repeated to produce a polymer.
【００２１】また、この有機絶縁膜材料の製造方法にお
いて、酸素存在を、反応溶液中に酸素をオーバーフロー
させることにより達成することを特徴とする。Further, in the method for producing an organic insulating film material, the presence of oxygen is achieved by overflowing oxygen into the reaction solution.
【００２２】また、この酸素存在を、密閉した反応容器
内を酸素雰囲気にすることにより達成してもよい。The presence of oxygen may be achieved by setting the inside of the sealed reaction vessel to an oxygen atmosphere.
【００２３】また、この有機絶縁膜材料の製造方法にお
いて、反応溶液中に、さらに脱水剤を加えておく。In the method for producing an organic insulating film material, a dehydrating agent is further added to the reaction solution.
【００２４】反応させる前に脱水剤を入れておくと、重
合反応中に反応系内より脱水を行うことができるため、
この反応を促進することができる。このため、生成物の
高分子量化を図ることができる。よって、この製造方法
によって得られた材料を用いて有機絶縁膜を形成すれば
耐熱性の向上が期待できる。If a dehydrating agent is added before the reaction, dehydration can be performed from the reaction system during the polymerization reaction.
This reaction can be accelerated. Therefore, it is possible to increase the molecular weight of the product. Therefore, if an organic insulating film is formed using a material obtained by this manufacturing method, improvement in heat resistance can be expected.
【００２５】また、この製造方法において、反応器内を
密閉して、反応溶液を加熱しながら反応を行わせる。Further, in this production method, the reaction is carried out while heating the reaction solution by sealing the inside of the reactor.
【００２６】反応溶液を加熱することで、反応が促進さ
れ、より生成物の高分子量化を図ることができる。また
反応器内を密閉しているので、反応溶液中の低沸点物質
の損失を防ぐことができるため十分な加熱処理を行うこ
とができる。By heating the reaction solution, the reaction is promoted and the product can be made higher in molecular weight. In addition, since the inside of the reactor is sealed, loss of low-boiling substances in the reaction solution can be prevented, so that sufficient heat treatment can be performed.
【００２７】なお、ここでいう反応溶液とは、反応させ
るモノマー、触媒、溶媒等の反応器に入れる物質を含ん
でいる。Here, the reaction solution includes substances to be put into the reactor, such as a monomer to be reacted, a catalyst and a solvent.
【００２８】また、得られる有機絶縁膜材料は、反応終
了後、溶媒を除去したり、洗浄、乾燥などの一連の後処
理を経たものを指している。Further, the obtained organic insulating film material indicates a material which has been subjected to a series of post-treatments such as removal of a solvent, washing and drying after completion of the reaction.
【００２９】[0029]
【実施例】以下、この発明の各実施例についてそれぞれ
説明する。なお、以下の説明中で挙げる使用材料および
その量、その他の数値的条件、並びに処理方法は、好適
な発明の範囲内の一例に過ぎず、したがってこの発明で
はなんらこれに限定されるものではない。Embodiments of the present invention will be described below. It should be noted that the materials used and the amounts thereof, other numerical conditions, and treatment methods mentioned in the following description are merely examples within the scope of the preferred invention, and therefore, the invention is not limited thereto. .
【００３０】＜第１の実施例＞この実施例の有機絶縁膜
材料は以下の方法で製造した。<First Embodiment> The organic insulating film material of this embodiment was manufactured by the following method.
【００３１】まず、攪拌機、酸素導入管、排気管、温度
計を装着した反応器に、塩基性触媒としてピリジン８
０．０ｍｌ（１．０ｍｏｌ）と、塩化銅（Ｉ）０．９９
０ｇ（１０ｍｍｏｌ）と、溶媒としてニトロベンゼン２
l(2リットル)を加えて攪拌した。次にこの溶液内に酸素を導
入し、オーバーフローさせた。次に、モノマーとしてｏ
−トリフルオロメチルフェノール６４．８ｇ（０．４ｍ
ｏｌ）を４０ｍｌのニトロベンゼンに溶解させた後、上
記の溶液内に加えて、室温で５０時間攪拌した。その後
反応液からニトロベンゼンを留去して、残った溶液をト
ルエンで希釈した後塩酸を加え、ピリジンを除去した。
このとき、反応器内の溶液は酸性の水層と有機層とに別
れている。この水層が中性になるまで水による洗浄を繰
り返した。次に有機層を無水硫酸マグネシウムにより脱
水して、溶媒を留去した後、真空乾燥により有機絶縁膜
材料である有機ポリマー２３．０ｇ（収率３６％）を得
た。First, pyridine 8 as a basic catalyst was placed in a reactor equipped with a stirrer, an oxygen introduction pipe, an exhaust pipe, and a thermometer.
0.0 ml (1.0 mol) and copper chloride (I) 0.99
0 g (10 mmol) and nitrobenzene 2 as a solvent.
l (2 liters) was added and stirred. Next, oxygen was introduced into the solution to cause overflow. Next, o as a monomer
-64.8 g of trifluoromethylphenol (0.4 m
ol) was dissolved in 40 ml of nitrobenzene, added to the above solution, and stirred at room temperature for 50 hours. Thereafter, nitrobenzene was distilled off from the reaction solution, the remaining solution was diluted with toluene, and hydrochloric acid was added to remove pyridine.
At this time, the solution in the reactor is separated into an acidic aqueous layer and an organic layer. Washing with water was repeated until the aqueous layer became neutral. Next, the organic layer was dehydrated with anhydrous magnesium sulfate, the solvent was distilled off, and then vacuum drying was performed to obtain 23.0 g (yield: 36%) of an organic polymer as an organic insulating film material.
【００３２】このポリマーに対して、単分散ポリスチレ
ンを標準に用いたＧＰＣ（ゲル浸透クロマトグラフィ
ー）分析を行ったところ、重量平均分子量は３２６０で
あった。The polymer was subjected to GPC (gel permeation chromatography) analysis using monodispersed polystyrene as a standard. As a result, the weight average molecular weight was 3,260.
【００３３】また、このポリマーのＩＲスペクトルを測
定した結果、１１００ｃｍ-1と、１３２０ｃｍ-1付近に
目的の物質であることを示すピークが見られた。１１０
０ｃｍ-1付近のピークはエーテル結合に由来するもの
で、１３２０ｃｍ-1付近のピークはトリフルオロメチル
基に由来するものと考えられ、ポリマー中にエーテル結
合とトリフルオロメチル基が存在することを確認するこ
とができた。よって、このポリマーは実質的に下記の
（１）式で表される繰り返し単位から成るものであると
考えられる。[0033] As a result of IR spectrum of this polymer, and 1100 cm -1, a peak indicating the purpose of the substance in the vicinity of 1320 cm -1 were observed. 110
Peak around 0 cm -1 is derived from the ether bond, the peak around 1320 cm -1 is considered to be derived from a trifluoromethyl group, confirm the presence of an ether bond and a trifluoromethyl group in the polymer We were able to. Therefore, it is considered that this polymer substantially consists of a repeating unit represented by the following formula (1).
【００３４】[0034]
【化４】 Embedded image
【００３５】次に、得られたポリマー１６ｇ（０．１ｍ
ｏｌ）を溶剤であるトルエン６４ｇに溶解し、孔径０．
２μｍのメンブレンフィルターでろ過し、ポリマー濃度
２５ｗｔ％の塗布液を調整した。この塗布液をシリコン
基板上に１．０μｍの膜厚に回転塗布して、ホットプレ
ート上で１００℃、２分間プリベークを行った。その
後、３００℃で１時間、Ｎ2 雰囲気中でベークを行い、
有機絶縁膜を得た。Next, 16 g of the obtained polymer (0.1 m
ol) was dissolved in 64 g of toluene as a solvent, and the pore size was adjusted to 0.
The solution was filtered through a 2 μm membrane filter to prepare a coating solution having a polymer concentration of 25 wt%. This coating solution was spin-coated on a silicon substrate to a thickness of 1.0 μm, and prebaked on a hot plate at 100 ° C. for 2 minutes. After that, baking is performed at 300 ° C. for 1 hour in an N 2 atmosphere,
An organic insulating film was obtained.
【００３６】この有機絶縁膜上にさらにアルミニウム電
極をスパッタ法により形成した試料を用いて、有機絶縁
膜の容量を測定し、この有機絶縁膜の比誘電率を求めた
ところ、比誘電率は２．５であった。Using a sample in which an aluminum electrode was further formed on the organic insulating film by sputtering, the capacity of the organic insulating film was measured, and the relative dielectric constant of the organic insulating film was determined. Was 5.5.
【００３７】以上のＩＲ測定結果、および比誘電率測定
結果から、この有機絶縁膜材料は上記の（１）式で示さ
れる繰り返し単位から成り、この材料を用いて形成した
有機絶縁膜は従来の有機絶縁膜と比べて、比誘電率を低
くすることができる。これは、トリフルオロメチル基が
置換基として導入されていることによる。また、モノマ
ーを、芳香環をもつ化合物としては最小単位であるフェ
ノール化合物としたことによって比誘電率を高くなるの
を最小限に抑えることができた。From the above IR measurement results and relative dielectric constant measurement results, this organic insulating film material is composed of the repeating unit represented by the above formula (1), and the organic insulating film formed using this material is a conventional one. The relative dielectric constant can be lower than that of the organic insulating film. This is because a trifluoromethyl group is introduced as a substituent. Further, by using a phenol compound, which is the minimum unit as a compound having an aromatic ring, as a monomer, it was possible to minimize an increase in relative dielectric constant.
【００３８】＜第２の実施例＞第２の実施例として、第
１の実施例と同じポリマーを製造するにあたり、第１の
実施例の製造工程に加えて、反応器内にあらかじめ、脱
水剤として無水硫酸マグネシウムを添加しておいた。そ
の後の製造工程は第１の実施例で説明したとおりである
ため、ここでは省略する。<Second Embodiment> As a second embodiment, in producing the same polymer as in the first embodiment, in addition to the production steps of the first embodiment, a dehydrating agent was previously installed in the reactor. As anhydrous magnesium sulfate. Subsequent manufacturing steps are the same as those described in the first embodiment, and a description thereof will be omitted.
【００３９】その結果、有機絶縁膜材料であるポリマー
１２．３ｇ（収率３８％）が得られた。第１の実施例と
同様に、ＧＰＣ分析により、平均分子量を測定したとこ
ろ、重量平均分子量は５８４０で、このポリマーを用い
て有機絶縁膜を形成して第１の実施例と同様な方法で比
誘電率を測定したところ、第１の実施例と変わらず、
２．５という値が得られた。As a result, 12.3 g (yield: 38%) of a polymer as an organic insulating film material was obtained. When the average molecular weight was measured by GPC analysis in the same manner as in the first embodiment, the weight average molecular weight was 5840. An organic insulating film was formed using this polymer, and the ratio was determined in the same manner as in the first embodiment. When the dielectric constant was measured, it was the same as in the first embodiment.
A value of 2.5 was obtained.
【００４０】以上のように、第２の実施例によれば、反
応前に脱水剤を加えて、反応系内より脱水することで、
このポリマーを形成する反応である脱水縮合反応が促進
され、高分子量化を図ることができる。高分子量化によ
り、この材料を用いて形成される有機絶縁膜の耐熱性の
向上が期待される。As described above, according to the second embodiment, the dehydrating agent is added before the reaction and dehydration is performed from the reaction system.
The dehydration / condensation reaction, which is a reaction for forming this polymer, is promoted, and a high molecular weight can be achieved. The increase in the molecular weight is expected to improve the heat resistance of the organic insulating film formed using this material.
【００４１】＜第３の実施例＞第３の実施例として、第
１の実施例における酸素の導入を、オーバーフローさせ
るのではなく、密閉した反応器内を酸素雰囲気とするこ
ととした。また、５０時間反応液を攪拌させて重合反応
させる工程に、この例では１００℃に加熱する処理を加
えた。その後の製造工程は第１の実施例と同様であるた
め、説明を省略する。<Third Embodiment> As a third embodiment, the introduction of oxygen in the first embodiment was not made to overflow, but an oxygen atmosphere was set in the sealed reactor. In addition, in this example, a process of heating to 100 ° C. was added to the step of stirring the reaction solution for 50 hours to cause a polymerization reaction. Subsequent manufacturing steps are the same as in the first embodiment, and a description thereof will be omitted.
【００４２】この結果、有機絶縁膜材料であるポリマー
９．３ｇ（収率２９％）が得られた。第１の実施例と同
様に、ＧＰＣ分析により平均分子量を測定したところ、
重量平均分子量は１０１００であり、このポリマーを用
いて有機絶縁膜を形成して第１の実施例と同様な方法で
比誘電率を測定したところ、２．５であった。As a result, 9.3 g (yield: 29%) of a polymer as an organic insulating film material was obtained. When the average molecular weight was measured by GPC analysis in the same manner as in the first example,
The weight average molecular weight was 10,100. An organic insulating film was formed using this polymer, and the relative dielectric constant was measured by the same method as in the first example. As a result, it was 2.5.
【００４３】以上のように、第３の実施例によれば、加
熱することにより、重合反応を促進することができ、よ
り高分子量化を図ることができる。また、反応器内は密
閉されているので、加熱処理による触媒のピリジンのよ
うな低沸点物質を損失する心配もない。高分子量化によ
り、この材料を用いて形成される有機絶縁膜の耐熱性の
向上が期待できる。As described above, according to the third embodiment, by heating, the polymerization reaction can be promoted, and the molecular weight can be further increased. Further, since the inside of the reactor is sealed, there is no fear of losing a low-boiling substance such as pyridine of the catalyst due to the heat treatment. By increasing the molecular weight, an improvement in the heat resistance of an organic insulating film formed using this material can be expected.
【００４４】なお、以上説明した実施例において、塗布
液を用いて有機絶縁膜を形成するための成膜方法として
は、回転塗布法、浸漬法、吹き付け法、プレス法などを
用いることが可能である。In the embodiments described above, a spin coating method, a dipping method, a spraying method, a pressing method, etc. can be used as a film forming method for forming an organic insulating film using a coating solution. is there.
【００４５】また、この有機絶縁膜を設ける基板として
は、Ｃｕ、Ａｌ、Ｗなどの配線金属や、酸化膜などが設
けてある基板などを用いることができる。As a substrate on which the organic insulating film is provided, a wiring metal such as Cu, Al, W, etc., or a substrate provided with an oxide film or the like can be used.
【００４６】また、有機絶縁膜材料中の置換基であるフ
ッ化物は、フッ素やフルオロアルキル基などが適用可能
である。As the fluoride as a substituent in the organic insulating film material, a fluorine or fluoroalkyl group can be used.
【００４７】また、有機絶縁膜の成膜後、さらにこの有
機絶縁膜にアニール処理を行ってもよい。After the formation of the organic insulating film, the organic insulating film may be further subjected to an annealing treatment.
【００４８】また、塗布液中に、さらに架橋剤を添加し
てもよい。Further, a crosslinking agent may be further added to the coating solution.
【００４９】また、この有機絶縁膜を形成する有機絶縁
膜材料の平均分子量の好適な範囲については、ある程度
の耐熱性を付与させるために１０００以上が良いが、高
すぎると溶剤に溶けにくくなるため、１００万程度まで
が好ましい。The preferable range of the average molecular weight of the organic insulating film material forming the organic insulating film is 1000 or more in order to impart a certain degree of heat resistance. However, if it is too high, it is difficult to dissolve in a solvent. , Up to about 1,000,000.
【００５０】[0050]
【発明の効果】上述した説明から明らかなように、この
発明の有機絶縁膜材料によれば、従来の有機絶縁膜と比
べて、比誘電率が低い有機絶縁膜を形成することができ
る。As is clear from the above description, according to the organic insulating film material of the present invention, it is possible to form an organic insulating film having a lower dielectric constant than a conventional organic insulating film.
【００５１】また、この有機絶縁膜材料を製造するにあ
たり、モノマーの重合反応前に脱水剤を添加しておくこ
とで、脱水縮合反応が促進され、有機絶縁膜材料の高分
子量化を図ることができる。In addition, in producing this organic insulating film material, by adding a dehydrating agent before the polymerization reaction of the monomer, the dehydration condensation reaction is promoted and the organic insulating film material can be made to have a high molecular weight. it can.
【００５２】また、反応器内を密閉して、さらに器内を
酸素雰囲気にして反応させる際に加熱処理を行うこと
で、反応が促進され、有機絶縁膜材料の高分子量化を図
ることができる。Further, by performing a heat treatment when the reactor is sealed and the reactor is further subjected to an oxygen atmosphere for the reaction, the reaction is promoted and the organic insulating film material can be made higher in molecular weight. .
【００５３】有機絶縁膜材料の高分子量化により、この
材料を用いて形成した有機絶縁膜にはより高い耐熱性が
期待できる。By increasing the molecular weight of the organic insulating film material, higher heat resistance can be expected for the organic insulating film formed using this material.
Claims (8)
士を、酸素を介して結合して構成される有機ポリマーか
ら成ることを特徴とする有機絶縁膜材料。1. An organic insulating film material comprising an organic polymer constituted by connecting a large number of aromatic rings having a substituent of a fluoride via oxygen.
て、 前記有機ポリマーを、フッ素を含んでいるポリアリール
エーテル誘導体とすることを特徴とする有機絶縁膜材
料。2. The organic insulating film material according to claim 1, wherein the organic polymer is a polyaryl ether derivative containing fluorine.
て、 前記ポリアリールエーテル誘導体を、下記の（１）式で
表される構造単位の繰り返しからなることを特徴とする
有機絶縁膜材料。 【化１】 3. The organic insulating film material according to claim 2, wherein the polyaryl ether derivative is composed of repeating structural units represented by the following formula (1). Embedded image
士を、酸素を介して結合して構成される有機ポリマーか
らなる有機絶縁膜材料を製造するにあたり、 フッ素を含んでいるフェノール化合物をモノマーとし、
前記モノマーと塩基性触媒とを含む反応溶液を反応器に
入れ、 酸素存在下で、前記モノマーを脱水縮合反応によって重
合させて前記有機絶縁膜材料を得ることを特徴とする有
機絶縁膜材料の製造方法。4. A method for producing an organic insulating film material comprising an organic polymer constituted by bonding a large number of aromatic rings having a substituent of a fluoride via oxygen, a phenol compound containing fluorine is used. Monomer
A reaction solution containing the monomer and a basic catalyst is placed in a reactor, and the monomer is polymerized by a dehydration condensation reaction in the presence of oxygen to obtain the organic insulating film material. Method.
方法において、 前記酸素存在を、反応溶液中に酸素をオーバーフローさ
せることにより達成することを特徴とする有機絶縁膜材
料の製造方法。5. The method for manufacturing an organic insulating film material according to claim 4, wherein the presence of oxygen is achieved by overflowing oxygen into a reaction solution.
方法において、 前記酸素存在を、密閉した前記反応器内を酸素雰囲気に
することにより達成することを特徴とする有機絶縁膜材
料の製造方法。6. The method for producing an organic insulating film material according to claim 4, wherein the presence of oxygen is achieved by setting the inside of the sealed reactor to an oxygen atmosphere. Production method.
方法において、 前記反応溶液中に、さらに脱水剤を加えておくことを特
徴とする有機絶縁膜材料の製造方法。7. The method for producing an organic insulating film material according to claim 4, wherein a dehydrating agent is further added to the reaction solution.
方法において、 前記反応器内を密閉して、前記反応溶液を加熱しながら
反応を行わせることを特徴とする有機絶縁膜材料の製造
方法。8. The method for producing an organic insulating film material according to claim 4, wherein the reaction is carried out while heating the reaction solution by sealing the inside of the reactor. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27346796A JPH10125671A (en) | 1996-10-16 | 1996-10-16 | Organic insulating film material and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27346796A JPH10125671A (en) | 1996-10-16 | 1996-10-16 | Organic insulating film material and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10125671A true JPH10125671A (en) | 1998-05-15 |
Family
ID=17528335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27346796A Withdrawn JPH10125671A (en) | 1996-10-16 | 1996-10-16 | Organic insulating film material and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10125671A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004002627A (en) * | 2002-03-25 | 2004-01-08 | Jsr Corp | Method for producing aromatic polymer, composition for film formation, method for film formation and organic film |
-
1996
- 1996-10-16 JP JP27346796A patent/JPH10125671A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004002627A (en) * | 2002-03-25 | 2004-01-08 | Jsr Corp | Method for producing aromatic polymer, composition for film formation, method for film formation and organic film |
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