JPS6066437A - Forming method of heat-resistant resin film - Google Patents
Forming method of heat-resistant resin filmInfo
- Publication number
- JPS6066437A JPS6066437A JP17410583A JP17410583A JPS6066437A JP S6066437 A JPS6066437 A JP S6066437A JP 17410583 A JP17410583 A JP 17410583A JP 17410583 A JP17410583 A JP 17410583A JP S6066437 A JPS6066437 A JP S6066437A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- resin film
- solution
- silicon
- resistant resin
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 12
- 229920006015 heat resistant resin Polymers 0.000 title claims description 11
- 229920001721 polyimide Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000009719 polyimide resin Substances 0.000 claims abstract description 12
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000004642 Polyimide Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 4
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- JXJTWJYTKGINRZ-UHFFFAOYSA-J silicon(4+);tetraacetate Chemical compound [Si+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JXJTWJYTKGINRZ-UHFFFAOYSA-J 0.000 claims description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 abstract description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000002210 silicon-based material Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Formation Of Insulating Films (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【発明の詳細な説明】
（技術分野）
本発明は半導体集積回路１−用いる耐熱性樹脂膜の形成
方法に関し、特に約５００℃程度の比較的高温に耐える
高耐熱性の樹脂膜の形成方法に関するものである。Detailed Description of the Invention (Technical Field) The present invention relates to a method for forming a heat-resistant resin film used in a semiconductor integrated circuit 1, and particularly relates to a method for forming a highly heat-resistant resin film that can withstand relatively high temperatures of about 500°C. It is something.
（従来技術）
従来かかる高耐熱性樹脂膜としてはポリイミド樹脂、耐
熱性ホトレノスト、ラダーシリコン、あるいは有機シリ
コン材料等が用いられエレクトロンデバイスへの応用技
術の開発が非常にめざましい。(Prior Art) Conventionally, polyimide resin, heat-resistant photorenost, ladder silicon, or organic silicon materials have been used as such highly heat-resistant resin films, and the development of application technology to electron devices has been extremely remarkable.
例えば、ＬＳＩの高集積化を実現するための多層配線技
術として、樹脂絶縁多層配線技術が開発され、それらの
絶縁材料としては高純度ポリイミド系樹脂が一般に使用
されている。For example, resin insulated multilayer wiring technology has been developed as a multilayer wiring technology to achieve high integration of LSIs, and high purity polyimide resin is generally used as the insulating material.
そしてかかるポリイミド系樹脂の他に、前記耐熱性ホト
レジストや、ラダーシリコンらるい線有機シリコン材料
が同様にＬＳＩの高集積化を目的として応用検討が進め
られて居シ、そして特に前記ポリイミド樹脂と有機シリ
コン拐料に関する開発研究の進展が目ざましい。In addition to such polyimide resins, the heat-resistant photoresists and ladder silicon linear organic silicon materials are also being considered for application with the aim of increasing the integration of LSIs. Research and development on silicone additives has made remarkable progress.
しかし上述のポリイミド樹脂は、４５０℃程度の熱処理
で重量減少が生じ上述の多層配線工程に必要とされる熱
処理温度５００℃以上ではその耐熱性が十分とは言え難
い。However, the above-mentioned polyimide resin loses weight when heat treated at about 450°C, and its heat resistance cannot be said to be sufficient at heat treatment temperatures of 500°C or higher required for the above-mentioned multilayer wiring process.
一方有機シリコン樹脂は耐熱性が極めて高く、例えば１
０００℃程度の熱処理にも十分側える特性を有するが、
比較的厚い膜厚、具体的にＶ１１〜２μｍ厚の膜を形成
することが著しく困難である。On the other hand, organic silicone resins have extremely high heat resistance, for example 1
It has characteristics that can withstand heat treatment at around 000℃,
It is extremely difficult to form a relatively thick film, specifically a film with a thickness of V11 to 2 μm.
一般に有機シリコン樹脂は熱処理によシ収縮してクラッ
クを生じ易く概ね１００ＯＡ程度迄は十分に実用に耐え
るが上述のＬＳＩに必要な膜厚１〜２μｍでは該クラッ
クにより殆んど実用に供しえない。In general, organic silicone resins tend to shrink and crack due to heat treatment, and are sufficiently durable for practical use up to approximately 100 OA, but cannot be used practically at the film thickness of 1 to 2 μm, which is required for the above-mentioned LSI, due to cracks. .
即ち、十分な膜厚の点ではポリイミド樹脂が望ましいが
耐熱性に問題があり、該耐熱性については有機シリコン
材料の使用が望ましいとしても上記クラックを生ずる重
大な問題が免かれないことになる。That is, polyimide resin is preferable in terms of sufficient film thickness, but it has a problem with heat resistance.Even if it is preferable to use an organic silicon material in terms of heat resistance, the above-mentioned serious problem of causing cracks cannot be avoided.
（発明の目的）
ここに本発明者等は、かかる問題に鑑み、耐熱性にすぐ
れしかも十分な膜厚を有する優れた特性を有する樹脂膜
の形成に関し横側を重ねこの発明全完成したのである。(Purpose of the Invention) In view of this problem, the inventors of the present invention have completed this invention by stacking sideways on the formation of a resin film having excellent heat resistance and sufficient film thickness. .
即ち本発明は、ピロメリティックジアンヒドライドと、
３．３’、４．４’−ペンゾフェニルテトラカルボキシ
リイツクアシドジアンヒドライドと、４．４′−ジアミ
ノジフェニルエーテルと、４．４′−ノアミノジフェニ
ルエーテル−３−カルボンアミドとの反応体を含む溶液
からなるポリイミド樹脂前駆体溶液と、シリコン化合物
溶液との混合液をシリコン基板上に塗布し、加熱処理す
る仁とを特徴とする耐熱樹脂膜の形成方法である。That is, the present invention provides pyromellitic dianhydride;
A reactant of 3.3',4.4'-penzophenyltetracarboxylic acid dianhydride, 4.4'-diaminodiphenyl ether, and 4.4'-noaminodiphenyl ether-3-carbonamide. This method of forming a heat-resistant resin film is characterized in that a mixed solution of a polyimide resin precursor solution containing a solution containing a silicon compound solution and a silicon compound solution is applied onto a silicon substrate and then heat-treated.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
まず一般的にポリイミド樹脂及び有機シリコン材料を使
用した場合について簡単に説明する。ポリイミド樹脂を
用いた膜形底にはポリイミド前駆体であるポリアミック
酸溶液をシリコン基板上にスピナー等により塗布する。First, a case where a polyimide resin and an organic silicon material are generally used will be briefly explained. For the film-shaped bottom using polyimide resin, a polyamic acid solution, which is a polyimide precursor, is applied onto a silicon substrate using a spinner or the like.
ここでポリアミック酸の構造は次式で示される。Here, the structure of polyamic acid is shown by the following formula.
その後、２００℃程度の温度で加熱処理すると溶剤が蒸
発し、該ポリアミック酸が脱水閉環してこのようにして
得られるＩリイミド樹脂膜は、空気中（酸素雰囲気中）
で熱処理すると、約４２０℃〜４７０℃の温度下で徐々
にＭ１藍の減少が認められ膜厚が狗くなる（例えば儀公
昭５１−４４８７１等参照）。Thereafter, when heat-treated at a temperature of about 200°C, the solvent evaporates, and the polyamic acid undergoes dehydration and ring closure.
When heat-treated at a temperature of about 420° C. to 470° C., a gradual decrease in M1 indigo is observed and the film thickness becomes thicker (see, for example, Gikosho 51-44871).
次に有機シリコン化合物はシリカフィルムとして広く知
られており、例えば酢酸硅素をエチルアルコールに溶解
したものを主成分とする（有機シリコン材料の組成につ
いては例えは特公昭５２−２０８２５．５２−１６４８
８号公報等参照ン。Next, organic silicon compounds are widely known as silica films, and their main component is, for example, silicon acetate dissolved in ethyl alcohol (for the composition of organic silicon materials, see Japanese Patent Publication No. 52-20825.52-1648).
See Publication No. 8, etc.
有機シリコン材料の場合は、上述の酢酸硅素溶液を同様
にスピン塗布法によりシリコン基板上に塗布し、突気中
（酸素雰囲気中〕で４０１） ℃程度に加熱することに
よジ、ｓｉｏ□膜に転する。得られたＳｉｎ、膜は例え
ば１０００℃程度の熱処理にも耐え、弗酸によるエツチ
ング加工も１１゛能であることから不純物拡散のマスク
としても使用でき、その性質は通常の５ＩＯｚ膜と変ら
ないが前述の如くクラック金主じ易い。In the case of organic silicon materials, the silicon acetate solution described above is similarly applied onto a silicon substrate by the spin coating method, and heated to about 401°C in a sudden atmosphere (in an oxygen atmosphere) to form a di-sio□ film. Change to. The obtained Sin film can withstand heat treatment at temperatures of, for example, 1000°C, and can also be etched with hydrofluoric acid to 11 degrees, so it can be used as a mask for impurity diffusion, and its properties are the same as those of ordinary 5IOz films. As mentioned above, it is easy to become a crack owner.
これに対して本発明は上述の如く、特に限定されたビロ
メリティックノアンヒドライドと、３゜３’ 、 ４
、４’−ペンゾフェニルテトラヵルゴキシリイツクアシ
ドノアノヒドライドと、 ４ 、４’−ジアミノジフェ
ニルエーテルと、４ 、４’−ジアミノジフェニルエー
テル−３−カルボンアミドとの反応体を含む溶液からな
るｓ９ リイミド樹脂前駆体溶液と、Ｍ機シリコン溶液
とを混合しシリコン基板上に塗布し加熱したことにより
、後記詳述する如く得られる塗膜中に５ｉ−０−８ｉ成
分とポリイミド成分の周成分を含有した樹脂膜が形成さ
れることになυ上記耐熱性ｆ：、著しく向上式せがっ茜
い耐クラツク性が得られたのである。On the other hand, the present invention, as mentioned above, uses particularly limited bilomeritic anhydrides and 3°3', 4
, 4'-benzophenyltetracalgoxylic acidinoanohydride, 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether-3-carbonamide. By mixing the resin precursor solution and the M-machine silicone solution, applying the mixture onto a silicon substrate, and heating it, the resulting coating film contains surrounding components of the 5i-0-8i component and the polyimide component, as will be detailed later. As a result of the formation of a resin film, significantly improved heat resistance f: and significantly improved crack resistance were obtained.
次に本発明において有機シリコン化合物とは、例えは次
式
％式％
（式中ＲＦｉ１価の炭化水素基、ｎは０を含む１〜４の
整数）
で表わされる硅素化合物及び添加剤（ガラス質形成剤、
’；’ｗａバインダー等）をアルコール主凧分、エステ
ル、ケトン等の有機溶剤に溶解したものであシ、上記硅
素化合物が２０重量％以下のものである。Next, in the present invention, the organosilicon compound is, for example, a silicon compound and an additive (vitreous forming agent,
';'wa binder, etc.) dissolved in an organic solvent such as alcohol, ester, or ketone, and the silicon compound is 20% by weight or less.
次に本発明において、シリコン基板上に塗布した上述塗
布膜の加熱は８０〜５ｏｏ℃の範囲にて行うのが適幽で
ある。Next, in the present invention, it is appropriate to heat the above-mentioned coating film applied on the silicon substrate at a temperature in the range of 80 to 50°C.
（実施例）
以下本発明を具体的な実施例に基づいて詳細に説明する
。(Examples) The present invention will be described in detail below based on specific examples.
実施例１゜
ポリイミド前駆体として、ピロメリティックジアンヒト
２イドと、３．３’、４．４’−ペンゾフェニルテトラ
カルボキシリイックアシドジアンヒドライｌ’ト、４．
４’−ジアミノジフェニルエーテルと、 ４ 、４’−
ジアミノジフェニルニーテルル３−カルボンアミドとを
Ｎ−メチル−２ピロリドン溶液に溶解した反応体（轡脂
濃度分１４．２％）の溶液２０ＣＣと、上述の有機シリ
コン化合物溶液（例えば酢酸硅素、５ｉｎ２濃度分３％
）ＩＯＣＣとを準備しこれらを混合した。得られた混合
物をスピナーによフシリコン基板上にスピン塗布した後
膣シリコン基板ｔ−１００℃で１時間加熱した１、その
結果１〜２μｍの膜厚全有し、後記の如（Ｓｔ−０−８
ｉ構造及びポリイミド構造を有する樹脂被膜がシリコン
基板上に形成されていた。この被膜の耐熱特性を調べた
ところ第１図の如く耐熱特性ＴＧＡ 。Example 1 Polyimide precursors include pyromellitic dianhydride and 3.3',4.4'-benzophenyltetracarboxyliic acid dianhydride;4.
4'-diaminodiphenyl ether, 4,4'-
20 cc of a solution of a reactant (fat concentration: 14.2%) in which diaminodiphenylniterurium-3-carbonamide was dissolved in an N-methyl-2-pyrrolidone solution, and the above-mentioned organosilicon compound solution (e.g., silicon acetate, 5 in2 concentration). minute 3%
) IOCC were prepared and mixed. The resulting mixture was spin-coated onto a silicon substrate using a spinner, and then heated at t-100°C for 1 hour on the silicon substrate, resulting in a total film thickness of 1 to 2 μm, as described below (St-0- 8
A resin film having an i-structure and a polyimide structure was formed on a silicon substrate. When we investigated the heat resistance properties of this film, we found that the heat resistance properties were TGA as shown in Figure 1.
ＤＴＡにより測定された実線で示した特性曲線１２が得
られた。尚ことでＴＧＡ特性とは５００℃（ａｉｒ中）
での樹脂の重さを時間に対して計測したものである。A characteristic curve 12, shown as a solid line, measured by DTA was obtained. Furthermore, TGA characteristics are 500℃ (in air)
The weight of the resin is measured against time.
同様に前記ポリイミド樹脂単体（以後ＰＩと略記するン
の耐熱特性は同曲Ｍ３，４で示される。Similarly, the heat resistance properties of the polyimide resin alone (hereinafter abbreviated as PI) are shown in M3 and M4.
両者を比較すると先ず特性的ｗＭ１と３において本発明
の減量率は上記ＰＩ３よシも長時間側にシフトしている
ことが明らかに認められる。Comparing the two, it is clearly recognized that in characteristic wM1 and wM3, the weight loss rate of the present invention is also shifted to the long-term side compared to the above-mentioned PI3.
次に１）ＴＡ％性は樹脂の温度に対する吸熱反応あるい
れ発熱反応を示すものであるが、同様に特性的１Ｍ２と
４゛とを比較すると本発明の樹脂の特性はＰＩよシも長
時間側にシフトしていることが判り、即ち発熱反応が樹
脂の分解反応を示しておシ分温度に対する耐性が大きい
ことを示し高耐熱性を有することが示されている。Next, 1) TA% indicates an endothermic reaction or an exothermic reaction with respect to the temperature of the resin. Similarly, when comparing the characteristics 1M2 and 4゛, the characteristics of the resin of the present invention are similar to those of PI. It was found that the exothermic reaction was a decomposition reaction of the resin, and the resistance to the decomposition temperature was high, indicating that the resin had high heat resistance.
次に顕微鏡等による塗膜表面の観察結果では本発明樹脂
膜はＰＩ樹脂膜と比較してクラック等が生じやすくなる
という欠点は特に見出されなかった。Next, as a result of observing the surface of the coating film using a microscope or the like, no particular drawback was found in the resin film of the present invention such that cracks were more likely to occur compared to the PI resin film.
なおこれらの樹脂膜に関してＦＴＩＲ（フーリエ変換赤
外吸収スペクトル分析）による分析の吸収差スペクトル
を調べた結果を竿２図に示す（樹脂膜ｇ３５０℃ＩＨキ
ュアした後ＦＴＩＲ分析したもの）。波数１７９０に５
ｉ−０−８ｔによる吸収が見られると同時にイミド結合
による吸収が出ており本発明樹脂膜は５ｔ−０−８ｉ成
分とポリイミド成分との合成されたものであることを示
すと同時にイミド虫取反応がＰＩよυも早いことを示し
ている。The absorption difference spectra of these resin films analyzed by FTIR (Fourier transform infrared absorption spectroscopy) are shown in Figure 2 (resin films were subjected to FTIR analysis after IH curing at 350° C.). wave number 1790 to 5
At the same time absorption by i-0-8t is observed, absorption by imide bonds is also observed, indicating that the resin film of the present invention is a composite of the 5t-0-8i component and the polyimide component, and at the same time, imide insect repellent reaction. This shows that PI is also faster than υ.
実施例２゜
ポリイミド前駆体溶液２０ＣＣと有機シリコン化合物溶
液２０Ｃ１１，と全混合したものを用いた外は上記実施
例１と同様に行ない上述の耐熱性を調べたＪｔ中自泗加
１１ ち掴 ４１ 互基（吻九枇を云 ２．か−実施例
３゜
実施例１における酢酸硅素の代シに水酸化硅素を用いた
外は実施例１と全く同様に行ったところ上記各側と同等
あるいはそれ以上の特性を有する膜が得られることが確
認された。Example 2 The heat resistance was investigated in the same manner as in Example 1 except that a complete mixture of polyimide precursor solution 20CC and organic silicon compound solution 20C11 was used. 2. - Example 3 The procedure was carried out in exactly the same manner as in Example 1 except that silicon hydroxide was used instead of silicon acetate in Example 1. It was confirmed that a film with superior properties could be obtained.
（発明の効果）
本発明は以上説明した如くシリコン基板上に優れた耐熱
性、耐被覆性を有する膜を形成しイｕるので特に超高集
積回路の各種絶縁膜に利用して優れた効果を発揮し、工
業的利用価値は極めて高い。(Effects of the Invention) As explained above, the present invention forms a film having excellent heat resistance and coating resistance on a silicon substrate, so it can be particularly applied to various insulating films of ultra-high integrated circuits. It exhibits extremely high industrial utility value.
第１図は本発明耐熱樹脂膜の耐熱！侍性図、第２図は同
ＦＴＩＲ分析特性図である。
手続補正書（自発）
特許庁長官 若杉和夫殿
１ 事件の表示
特願昭５８−１７４１０５号
２ 発明の名称
耐熱樹脂膜の形成方法
３ 補正をする者
事件との関係 特許出願人
（０２９１沖電気工業株式会社
４代理人
５、７Ｉ１１正の対象
発明の詳細な説明の鼎
６、７１１１正の内容
別 紙 の 通 リ
（１ン 明細書１０頁１］行ｒｌ ７９０Ｊをｒ１０７
０Ｊと訂正する。
２） 同１０頁１２行 「同時に」の次に 「波数１７
９０に」を加入する。Figure 1 shows the heat resistance of the heat-resistant resin film of the present invention! Figure 2 of the Samurai Figure is an FTIR analysis characteristic diagram of the same. Procedural amendment (spontaneous) Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Indication of the case Patent Application No. 174105/1983 2 Name of the invention Method for forming a heat-resistant resin film 3 Person making the amendment Relationship to the case Patent applicant (0291 Oki Electric Industry Co., Ltd. Co., Ltd. 4 Agent 5, 7I11 Detailed Explanation of the Subject Invention 6, 7111 Main Contents Separate Paper (1) Specification Page 10 Page 1] Line RL 790J to R107
Correct it to 0J. 2) On page 10, line 12, after “at the same time”, “wave number 17”
Add ``90''.
Claims (4)
、４．４’−ベンゾフェニルテトラカル〆キシリイツク
アシドジアンヒドライドと、４，４′−ソアミノジフェ
ニルエーテルと、４．４′−ジアミノジフェニルエーテ
ル−３−カルヴンアミドとの反応体を含む溶液からなる
ポリイミド樹脂前駆体溶液と、シリコン化合物溶液との
混合液をシリコン基板上に塗布し、加熱処理することを
特徴とする耐熱樹脂膜の形成方法。(1) Pyromelitic dianhydride and 3°3'
, a polyimide comprising a solution containing a reactant of 4,4'-benzophenyltetracarpoxyacide dianhydride, 4,4'-soamino diphenyl ether, and 4,4'-diaminodiphenyl ether-3-carvnamide. A method for forming a heat-resistant resin film, which comprises applying a mixture of a resin precursor solution and a silicon compound solution onto a silicon substrate and heat-treating the mixture.
アルコールに溶解したものを特徴とする特許請求の範囲
第１項記載の耐熱樹脂膜の形成方法。(2) The method for forming a heat-resistant resin film according to claim 1, wherein the organic silicon compound solution is a solution of silicon acetate dissolved in ethyl alcohol.
合物溶液との混合物をシリコン基板上に塗布し、加熱す
ることにより該樹脂膜中にＳｔ −０−８ｉ構造を形成
し含有させる特許請求の範囲第１項記載の耐熱樹脂膜の
形成方法。(3) A mixture of the polyimide resin precursor solution and an organic silicon compound solution is applied onto a silicon substrate and heated to form and contain an St-0-8i structure in the resin film. A method for forming a heat-resistant resin film according to item 1.
ルアルコールに溶解したものを主成分とするものである
特許請求の範囲第１項記載の耐熱樹脂膜の形成方法。(4) The method for forming a heat-resistant resin film according to claim 1, wherein the organic silicon compound solution contains silicon hydroxide dissolved in ethyl alcohol as a main component.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17410583A JPS6066437A (en) | 1983-09-22 | 1983-09-22 | Forming method of heat-resistant resin film |
| US06/581,365 US4528216A (en) | 1983-02-24 | 1984-02-17 | Process for forming heat-resistant resin films of polyimide and organosilicic reactants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17410583A JPS6066437A (en) | 1983-09-22 | 1983-09-22 | Forming method of heat-resistant resin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6066437A true JPS6066437A (en) | 1985-04-16 |
| JPH0120531B2 JPH0120531B2 (en) | 1989-04-17 |
Family
ID=15972730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17410583A Granted JPS6066437A (en) | 1983-02-24 | 1983-09-22 | Forming method of heat-resistant resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6066437A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62283153A (en) * | 1986-06-02 | 1987-12-09 | Toray Ind Inc | Polyimide coating agent composition |
| JPS62291119A (en) * | 1986-06-11 | 1987-12-17 | Toray Ind Inc | Manufacture of semiconductor element |
| JPS6315424A (en) * | 1986-07-08 | 1988-01-22 | Toray Ind Inc | Passivation method of semiconductor element |
| EP1146074A3 (en) * | 2000-04-05 | 2002-05-02 | Hitachi, Ltd. | Heat resistant resin composition and process for producing the same |
-
1983
- 1983-09-22 JP JP17410583A patent/JPS6066437A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62283153A (en) * | 1986-06-02 | 1987-12-09 | Toray Ind Inc | Polyimide coating agent composition |
| JPS62291119A (en) * | 1986-06-11 | 1987-12-17 | Toray Ind Inc | Manufacture of semiconductor element |
| JPS6315424A (en) * | 1986-07-08 | 1988-01-22 | Toray Ind Inc | Passivation method of semiconductor element |
| EP1146074A3 (en) * | 2000-04-05 | 2002-05-02 | Hitachi, Ltd. | Heat resistant resin composition and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0120531B2 (en) | 1989-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5114757A (en) | Enhancement of polyimide adhesion on reactive metals | |
| CA2069521A1 (en) | Process for coating a substrate with a silica precursor | |
| JPH04224824A (en) | Polyimide having low tce | |
| JP3998979B2 (en) | Method for forming low dielectric constant silica-based film and semiconductor substrate with low dielectric constant film | |
| JPH0145493B2 (en) | ||
| JPS6066437A (en) | Forming method of heat-resistant resin film | |
| JPH0292535A (en) | Composite molding of metal and polyimide | |
| US4528216A (en) | Process for forming heat-resistant resin films of polyimide and organosilicic reactants | |
| JPS584816B2 (en) | Semiconductor elements and their manufacturing methods | |
| JPH05279856A (en) | Vapor growth method | |
| JPH0214242A (en) | Polyamic acid composition and production thereof | |
| JPS6066438A (en) | Forming method of heat-resistant resin film | |
| JP3897908B2 (en) | Method for forming low dielectric constant insulating film, interlayer insulating film, and semiconductor device | |
| JPS61273806A (en) | Insulation covered wire | |
| JPS6064441A (en) | Formation of heat-resistant resin film | |
| JPS63193935A (en) | Polyimide polymer molded article | |
| JPS59155137A (en) | Formation of heat-proof resin film | |
| JPS62261149A (en) | Manufacture of semiconductor device | |
| Matsuoka et al. | Ester‐type photosensitive polyimide precursor with low thermal expansion coefficient | |
| JP2979558B2 (en) | Method of forming multilayer wiring interlayer insulating film of semiconductor device | |
| JPS6222830A (en) | Silicon-containing polyimide resin and its production | |
| JPS59107524A (en) | Method for formation of interlayer insulating film for semiconductor element | |
| JPH0685090A (en) | Maleimide resin composition | |
| JP2000265057A (en) | Heat-resistant resin precursor composition, production of heat-resistant resin, and heat-resistant resin | |
| JPS62133736A (en) | Flattened multilayer interconnection forming method |