JPH10313002A - Formation of sio2 coatings - Google Patents

Formation of sio2 coatings

Info

Publication number
JPH10313002A
JPH10313002A JP9120685A JP12068597A JPH10313002A JP H10313002 A JPH10313002 A JP H10313002A JP 9120685 A JP9120685 A JP 9120685A JP 12068597 A JP12068597 A JP 12068597A JP H10313002 A JPH10313002 A JP H10313002A
Authority
JP
Japan
Prior art keywords
coating
film
solution
sio
trialkoxysilane
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
Application number
JP9120685A
Other languages
Japanese (ja)
Other versions
JP3635443B2 (en
Inventor
Isao Sato
功 佐藤
Yoshio Hagiwara
嘉男 萩原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Ohka Kogyo Co Ltd
Original Assignee
Tokyo Ohka Kogyo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokyo Ohka Kogyo Co Ltd filed Critical Tokyo Ohka Kogyo Co Ltd
Priority to JP12068597A priority Critical patent/JP3635443B2/en
Priority to KR1019980016692A priority patent/KR100303895B1/en
Publication of JPH10313002A publication Critical patent/JPH10313002A/en
Application granted granted Critical
Publication of JP3635443B2 publication Critical patent/JP3635443B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently forming SiO2 coatings having a high crack limitation by such an application method that source and drain layers will not be excessively diffused. SOLUTION: A wiring layer made of material having a melting point of 500 deg.C or more is provided on a substrate, an application solution containing product of an acid hydrolysis reaction of trialkoxysilane is applied thereon and dried, and then resultant coatings are burned at a temperature of 550 to 800 deg.C until Si-H couplings cannot be recognized in the coatings to thereby form SiO2 coatings.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、半導体素子や液晶
素子などの製造に用いられる平坦化膜や層間絶縁膜など
として有用なクラック限界の高いＳｉＯ2被膜を、塗布
法によりソース層及びドレイン層の過度の拡散が起こら
ないように、かつ効率よく形成させる方法に関するもの
である。The present invention relates to the high SiO 2 coating of useful crack limiting the like planarizing film or an interlayer insulating film used in the manufacture of semiconductor devices or liquid crystal devices, the source and drain layers by coating The present invention relates to a method for efficiently forming a layer without excessive diffusion.

【０００２】[0002]

【従来の技術】従来、半導体素子や液晶素子の製造にお
いて使用される平坦化膜や層間絶縁膜には、通常シリカ
系被膜が用いられている。そして、このような用途に供
するシリカ系被膜を形成させる方法としては、例えば化
学的気相成長法（ＣＶＤ法）や塗布法が知られている。
このＣＶＤ法によるシリカ系被膜は、特殊な装置を用い
て、基板表面にシリカ又は必要に応じてリンやホウ素を
含有させたシリカを蒸着、成長させることにより形成さ
れ、絶縁膜や平坦化膜などとして利用されているが、特
に平坦化膜として利用される場合には、コンフォーマル
性は良好であるが、平坦化性に劣るので、９５０〜１１
００℃程度の温度でリフローさせる必要がある。一方、
塗布法によるシリカ系被膜は、一般に、アルコキシシラ
ンの加水分解物を含有する有機溶剤溶液からなる塗布液
を基板上に塗布し、焼成することにより形成され、平坦
性に優れることから、平坦化膜や絶縁膜などとして利用
されている。2. Description of the Related Art Conventionally, a silica-based coating is usually used for a flattening film and an interlayer insulating film used in the manufacture of semiconductor devices and liquid crystal devices. As a method of forming a silica-based coating for such use, for example, a chemical vapor deposition method (CVD method) or a coating method is known.
The silica-based film formed by the CVD method is formed by depositing and growing silica or silica containing phosphorus or boron as necessary on a substrate surface by using a special apparatus, such as an insulating film or a planarizing film. In particular, when used as a flattening film, the conformability is good, but the flatness is poor.
It is necessary to reflow at a temperature of about 00 ° C. on the other hand,
A silica-based film formed by a coating method is generally formed by applying a coating solution composed of an organic solvent solution containing a hydrolyzate of an alkoxysilane onto a substrate and baking it. It is used as an insulating film.

【０００３】このようなＣＶＤ法や塗布法により形成さ
れるシリカ系被膜は、今日においては、それぞれの長所
を生かして、半導体素子製造分野において利用されてい
る。例えば、アルミニウムを主成分とする配線上にＣＶ
Ｄ法により設けられた層間絶縁膜は、コンフォーマルな
形状であるので、平坦化が必要であるが、一般に、この
ようなアルミニウムを主成分とする配線は約４７０℃で
溶融するため、平坦化のためのリフロー処理を施すこと
ができない。したがって、該層間絶縁膜上には、塗布法
によりシリカ系被膜を約４５０℃で焼成して、平坦化膜
が形成されている。このように、一般にアルミニウムを
主成分とする耐熱性の低い配線層に対しては塗布法が利
用されている。[0003] Silica-based coatings formed by such a CVD method or a coating method are nowadays utilized in the field of semiconductor device production, taking advantage of their respective advantages. For example, CV is applied on a wiring mainly composed of aluminum.
Since the interlayer insulating film provided by the method D has a conformal shape, it needs to be flattened. Generally, such a wiring containing aluminum as a main component melts at about 470 ° C. Cannot be reflowed. Therefore, a flattening film is formed on the interlayer insulating film by firing the silica-based coating at about 450 ° C. by a coating method. As described above, a coating method is generally used for a wiring layer containing aluminum as a main component and having low heat resistance.

【０００４】一方、多結晶シリコンは上記のような高温
のリフロー処理に耐えうるので、これを配線層に用いた
場合には、ＣＶＤ法によりＰＳＧ（Ｐｈｏｓｐｈｏｓｉ
ｌｉｃａｔｅ Ｇｌａｓｓ）膜を形成したのち、１００
０℃程度でリフロー処理して、平坦化絶縁膜を形成す
る。ここでいう、ＰＳＧ膜は、リンを１０重量％程度含
有させることにより、リフロー温度を１０００℃程度ま
で低下させたシリカ系被膜のことである。このように、
リフロー処理を伴うＣＶＤ法で平坦化絶縁膜を形成する
方法は、一般に多結晶シリコンのような高耐熱性の配線
層上について利用されている。On the other hand, since polycrystalline silicon can withstand the high-temperature reflow treatment as described above, when it is used for a wiring layer, PSG (Phosphosiphonic) is formed by a CVD method.
(Liquid Glass) film, and then 100
By performing a reflow treatment at about 0 ° C., a planarization insulating film is formed. Here, the PSG film is a silica-based film in which the reflow temperature is reduced to about 1000 ° C. by adding about 10% by weight of phosphorus. in this way,
A method of forming a planarization insulating film by a CVD method involving a reflow process is generally used on a wiring layer having high heat resistance such as polycrystalline silicon.

【０００５】しかしながら、このようなリフロー処理を
伴うＣＶＤ法で平坦化絶縁膜を形成する場合、微細化が
より進むと高温のリフロー処理により、ソース層及びド
レイン層の拡散距離が過度に進み、電子特性に悪影響を
及ぼすので、リフロー温度を下げる必要がある。このた
めに、ＣＶＤ法によりＢＰＳＧ（Ｂｏｒｏ ｐｈｏｓｐ
ｈｏｓｉｌｉｃａｔｅ Ｇｌａｓｓ）膜が形成され、そ
して、９５０℃程度でリフロー処理され、平坦化絶縁膜
が形成されている。ここでいうＢＰＳＧ膜はリンとホウ
素を含有させて、一層リフロー温度を低下させたシリカ
系被膜である。However, when the planarization insulating film is formed by a CVD method involving such a reflow process, the diffusion distance between the source layer and the drain layer excessively increases due to the high-temperature reflow process as the miniaturization proceeds further, and the electron It is necessary to lower the reflow temperature because it adversely affects the characteristics. For this purpose, BPSG (Boro phosp) is formed by the CVD method.
(Hosilicate Glass) film is formed, and is subjected to a reflow treatment at about 950 ° C. to form a flattening insulating film. The BPSG film referred to here is a silica-based film containing phosphorus and boron to further lower the reflow temperature.

【０００６】しかしながら、今後ますます半導体素子の
微細化が進み、２５６メガ、１ギガという超高集積回路
が製造される場合、このような高温のリフロー処理を伴
うＣＶＤ法では、ソース層及びドレイン層の拡散距離の
制御がより厳しくなり、電子特性に悪影響を及ぼすこと
から高温のリフロー処理を伴わずに平坦化膜又は絶縁膜
が形成できる方法が要望されている。このような点で
は、ソース層及びドレイン層の過度の拡散が起こらない
８００℃以下でシリカ系被膜が形成できる塗布法が有利
であるし、同様に、１ギガディーラム以降のキャパシタ
材料として高誘電率特性に優れるＴａ2Ｏ5やバリウム・
ストロンチウム・チタン酸（ＢＳＴ）が有望であるが、
これらの材料で半導体素子を製造する場合も、電子特性
に悪影響を及ぼさない、８００℃以下でシリカ系被膜を
形成できる塗布法が有利である。しかしながら、これま
で塗布法に用いられてきたシリカ系被膜形成用塗布液で
は、クラック限界すなわちクラックが発生しない最大膜
厚が小さいため、このようなプロセスに代用できなかっ
たのが実状である。However, in the case where semiconductor devices are increasingly miniaturized in the future and ultra-high-integration circuits of 256 megahertz and 1 gigabit are manufactured, the CVD method involving such a high-temperature reflow process requires a source layer and a drain layer. Therefore, there is a demand for a method capable of forming a flattening film or an insulating film without a high-temperature reflow treatment since the control of the diffusion distance becomes more severe and adversely affects electronic characteristics. From such a point, a coating method capable of forming a silica-based coating at 800 ° C. or less, at which excessive diffusion of the source layer and the drain layer does not occur, is advantageous. Ta 2 O 5 and barium
Strontium titanate (BST) is promising,
Even when a semiconductor element is manufactured from these materials, a coating method capable of forming a silica-based coating at 800 ° C. or lower, which does not adversely affect electronic characteristics, is advantageous. However, the coating liquid for forming a silica-based coating film which has been used in the coating method until now has a small crack limit, that is, a maximum film thickness at which no crack occurs, and therefore cannot be substituted for such a process.

【０００７】[0007]

【発明が解決しようとする課題】本発明は、このような
事情のもとで、これまで高耐熱性配線層上にＣＶＤ法で
形成されていた平坦化膜や絶縁膜に代えて、ソース層及
びドレイン層の過度の拡散が起こらない８００℃以下
で、クラック限界の高いシリカ系被膜から成る平坦化膜
や絶縁膜を、塗布法により形成する方法を提供すること
を目的としてなされたものである。SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a source layer instead of a flattening film or an insulating film which has been formed on a high heat resistant wiring layer by a CVD method. It is another object of the present invention to provide a method of forming a flattening film or an insulating film made of a silica-based film having a high crack limit at 800 ° C. or less at which excessive diffusion of the drain layer does not occur by a coating method. .

【０００８】[0008]

【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、トリアルコキ
シシランの酸加水分解生成物を含有する塗布液を、高耐
熱配線層上に、塗布、乾燥したのち、８００℃以下の特
定の温度で塗膜中のＳｉ−Ｈ結合が認められなくなるま
で焼成することにより、その目的を達成しうることを見
出し、この知見に基づいて本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that a coating solution containing an acid hydrolysis product of trialkoxysilane is coated on a high heat-resistant wiring layer. After coating and drying, it was found that the object could be achieved by firing at a specific temperature of 800 ° C. or less until no Si—H bond was observed in the coating film. The invention has been completed.

【０００９】すなわち、本発明は、基板上に５００℃以
上の融点をもつ材料から成る配線層を設け、次いでその
上にトリアルコキシシランの酸加水分解生成物を含有す
る有機溶剤溶液からなる塗布液を塗布、乾燥したのち、
５５０〜８００℃の範囲の温度で、塗膜中にＳｉ−Ｈ結
合が認められなくなるまで焼成することを特徴とするＳ
ｉＯ2被膜の形成方法を提供するものである。That is, the present invention provides a coating solution comprising an organic solvent solution containing an acid hydrolysis product of trialkoxysilane, on which a wiring layer made of a material having a melting point of 500 ° C. or higher is provided on a substrate. After applying and drying,
S is characterized by firing at a temperature in the range of 550 to 800 ° C. until no Si—H bond is found in the coating film.
It is intended to provide a method for forming an iO 2 coating.

【００１０】なお、水素シルセスキオキサン樹脂溶液を
基板に塗布し、１５０〜１０００℃の温度で加熱するこ
とにより、シリカ系被膜を形成する方法が提案されてい
る（特公平６−４２４７７号公報）。しかしながら、こ
の公報では、１５０〜１０００℃の温度で加熱すると記
載されているが、実施例ではいずれも４００℃で約１時
間加熱処理が行われている。このような温度では、ある
程度Ｓｉ−Ｈ結合が残存するのを免れず、完全なＳｉＯ
2被膜は得られない。これに対し、本発明は、塗膜中の
Ｓｉ−Ｈ結合が認められなくなるまで焼成して、完全な
ＳｉＯ2被膜を形成させるものである。A method of forming a silica-based coating by applying a hydrogen silsesquioxane resin solution to a substrate and heating the substrate at a temperature of 150 to 1000 ° C. has been proposed (Japanese Patent Publication No. 6-42477). ). However, this publication describes that heating is performed at a temperature of 150 to 1000 ° C., but in each of the examples, the heat treatment is performed at 400 ° C. for about 1 hour. At such a temperature, it is inevitable that some Si-H bonds remain, and complete SiO
2 No coating is obtained. On the other hand, in the present invention, a complete SiO 2 coating is formed by baking until no Si—H bond in the coating is observed.

【００１１】[0011]

【発明の実施の形態】本発明方法においては、ＳｉＯ2
被膜を形成させるための塗布液として、トリアルコキシ
シランの酸加水分解生成物を含有する有機溶剤溶液が用
いられる。前記トリアルコキシシランとしては、例えば
トリメトキシシラン、トリエトキシシラン、トリプロポ
キシシラン、トリブトキシシラン、ジエトキシモノメト
キシシラン、モノメトキシジプロポキシシラン、ジブト
キシモノメトキシシラン、エトキシメトキシプロポキシ
シラン、モノエトキシジメトキシシラン、モノエトキシ
ジプロポキシシラン、ブトキシエトキシプロポキシシラ
ン、ジメトキシモノプロポキシシラン、ジエトキシモノ
プロポキシシラン、モノブトキシジメトキシシランなど
を挙げることができる。これらの中で実用上好ましい化
合物は、トリメトキシシラン、トリエトキシシラン、ト
リプロポキシシラン、トリブトキシシランであり、中で
も特にトリメトキシシラン、トリエトキシシランが好ま
しい。これらのトリアルコキシシランは単独で用いても
よいし、２種以上を組み合わせて用いてもよい。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the method of the present invention, SiO 2
As a coating solution for forming a film, an organic solvent solution containing an acid hydrolysis product of trialkoxysilane is used. Examples of the trialkoxysilane include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, diethoxymonomethoxysilane, monomethoxydipropoxysilane, dibutoxymonomethoxysilane, ethoxymethoxypropoxysilane, and monoethoxydimethoxy. Examples thereof include silane, monoethoxydipropoxysilane, butoxyethoxypropoxysilane, dimethoxymonopropoxysilane, diethoxymonopropoxysilane, and monobutoxydimethoxysilane. Among these, practically preferred compounds are trimethoxysilane, triethoxysilane, tripropoxysilane and tributoxysilane, and among them, trimethoxysilane and triethoxysilane are particularly preferred. These trialkoxysilanes may be used alone or in combination of two or more.

【００１２】また、前記有機溶剤としては特に制限はな
く、様々な溶剤を用いることができるが、特にアルキレ
ングリコールジアルキルエーテルが好ましい。このもの
を用いることにより、低級アルコールを溶媒として用い
た従来方法におけるトリアルコキシシランのＨ−Ｓｉ基
の分解反応や中間に生成するシラノールの水酸基がアル
コキシ基に置換する反応を抑制することができ、ゲル化
を防止することができる。The organic solvent is not particularly limited, and various solvents can be used, and alkylene glycol dialkyl ether is particularly preferable. By using this, it is possible to suppress the decomposition reaction of the H-Si group of the trialkoxysilane and the reaction in which the hydroxyl group of the silanol generated in the middle is replaced with the alkoxy group in the conventional method using the lower alcohol as the solvent, Gelling can be prevented.

【００１３】このアルキレングリコールジアルキルエー
テルとしては、例えばエチレングリコールジメチルエー
テル、エチレングリコールジエチルエーテル、エチレン
グリコールジプロピルエーテル、エチレングリコールジ
ブチルエーテル、ジエチレングリコールジメチルエーテ
ル、ジエチレングリコールジエチルエーテル、ジエチレ
ングリコールジプロピルエーテル、ジエチレングリコー
ルジブチルエーテル、プロピレングリコールジメチルエ
ーテル、プロピレングリコールジエチルエーテル、プロ
ピレングリコールジプロピルエーテル、プロピレングリ
コールジブチルエーテルなどのアルキレングリコールの
ジアルキルエーテル類を挙げることができる。これらの
中で好ましいのはエチレングリコール又はプロピレング
リコールのジアルキルエーテル特にジメチルエーテルで
ある。これらの有機溶剤は、単独で用いてもよいし２種
以上組み合わせて用いてもよい。その使用量について
は、トリアルコキシシランの１モルに対し、通常１０〜
３０モル倍量の割合で用いられる。Examples of the alkylene glycol dialkyl ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and propylene glycol. Examples thereof include dialkyl ethers of alkylene glycol such as dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether. Preferred among these are dialkyl ethers of ethylene glycol or propylene glycol, especially dimethyl ether. These organic solvents may be used alone or in combination of two or more. The amount used is usually 10 to 1 mole of trialkoxysilane.
It is used in a ratio of 30 mole times.

【００１４】本発明で用いる塗布液は、これらの有機溶
剤中に前記トリアルコキシシランの酸加水分解生成物を
含有するものであるが、特に、溶媒除去後の被膜形成成
分が、熱重量測定（ＴＧ）において、重量増加を示すも
のが好ましい。また、このような塗布液は、赤外吸収ス
ペクトルにおいて、通常３０００ｃｍ-1付近にピークを
有していない。従来の塗布液、例えば特開平４−２１６
８２７号公報記載の塗布液の場合は熱重量測定に際し、
重量減少を示すし、赤外吸収スペクトルにおいて、３０
００ｃｍ-1付近にピークを有し、残存アルコキシ基が存
在していることを示している。The coating liquid used in the present invention contains the acid hydrolysis product of the trialkoxysilane in these organic solvents. In TG), those showing an increase in weight are preferred. Further, such a coating liquid does not usually have a peak near 3000 cm -1 in an infrared absorption spectrum. Conventional coating liquid, for example, JP-A-4-216
In the case of the coating liquid described in JP-A-827,
Shows a weight loss, and in the infrared absorption spectrum, 30
It has a peak near 00 cm -1 , indicating that a residual alkoxy group is present.

【００１５】このような塗布液は、例えば以下に示す方
法により、好ましく調製することができる。まず、前記
アルキレングリコールジアルキルエーテル中に、トリア
ルコキシシランを、ＳｉＯ2換算で１〜５重量％、好ま
しくは２〜４重量％の濃度になるように溶解する。これ
は反応系におけるＳｉＯ2換算濃度が多くなりすぎると
ゲル化が起こり保存安定性が劣化するおそれがあるから
である。その詳細な原因については不明であるが、反応
系におけるＳｉＯ2換算濃度が小さい方が加水分解の反
応がゆるやかに進み、Ｈ−Ｓｉ基が分解されにくいこと
から、ラダー構造を形成しやすいためと思われる。Such a coating solution can be preferably prepared, for example, by the following method. First, in the alkylene glycol dialkyl ethers, trialkoxysilanes, 1-5 wt% in terms of SiO 2, preferably dissolved to a concentration of 2-4 wt%. This is because if the concentration in terms of SiO 2 in the reaction system becomes too large, gelation may occur and storage stability may be deteriorated. Although the detailed cause is unknown, the lower the concentration in terms of SiO 2 in the reaction system, the more easily the hydrolysis reaction proceeds and the less easily H-Si groups are decomposed, so that a ladder structure is easily formed. Seem.

【００１６】次に、トリアルコキシシランに水を反応さ
せて加水分解を行うが、この水は、トリアルコキシシラ
ン１モルに対し２．５〜３．０モル、好ましくは２．８
〜３．０モルの範囲内の量で用いることが加水分解度を
高めるために、有利である。この範囲より水が少ないと
保存安定性は高くなるものの、加水分解度が低くなり加
水分解物中の有機基の含有量が多くなるため、被膜形成
時のガスの発生が起こりやすくなるし、また、水が多す
ぎると保存安定性が悪くなる。Next, water is reacted with trialkoxysilane for hydrolysis, and this water is used in an amount of 2.5 to 3.0 mol, preferably 2.8, per mol of trialkoxysilane.
It is advantageous to use an amount in the range of ~ 3.0 mol to increase the degree of hydrolysis. When the amount of water is less than this range, the storage stability increases, but the degree of hydrolysis decreases, and the content of organic groups in the hydrolyzate increases, so that gas is easily generated during film formation, and On the other hand, if there is too much water, the storage stability will be poor.

【００１７】本発明方法においては、この加水分解は酸
触媒の存在下で行われるが、その際に用いる酸触媒とし
ては、従来、この種のシラン系被膜形成用塗布液製造に
慣用されている有機酸又は無機酸を用いることができ
る。この有機酸の例としては、酢酸、プロピオン酸、酪
酸などを、また無機酸の例としては、塩酸、硝酸、硫
酸、リン酸などを挙げることができるが、特に硝酸が好
ましい。In the method of the present invention, the hydrolysis is carried out in the presence of an acid catalyst. The acid catalyst used at that time is conventionally used in the production of this type of coating liquid for forming a silane-based film. Organic or inorganic acids can be used. Examples of the organic acid include acetic acid, propionic acid, and butyric acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and nitric acid is particularly preferable.

【００１８】この場合、酸触媒を塗布液中の酸の濃度
が、通常１〜２００ｐｐｍ、好ましくは、１〜４０ｐｐ
ｍの範囲になるように加えるか、又は酸と加える水を混
合し、酸水溶液として加えて、加水分解させる。In this case, the concentration of the acid in the coating solution is usually 1 to 200 ppm, preferably 1 to 40 pp.
m or a mixture of an acid and water to be added, and the mixture is added as an aqueous acid solution to be hydrolyzed.

【００１９】加水分解反応は、通常５〜１００時間程度
で完了する。また、室温ないし７０℃を超えない温度
で、アルコキシシラン化合物を含むアルキレングリコー
ルジアルキルエーテルの中から選ばれる少なくとも１種
の溶媒に水と酸触媒を滴下して反応させることにより、
短い反応時間で反応を完了させることもできる。The hydrolysis reaction is usually completed in about 5 to 100 hours. At room temperature to a temperature not exceeding 70 ° C., water and an acid catalyst are added dropwise to and reacted with at least one solvent selected from alkylene glycol dialkyl ethers containing an alkoxysilane compound,
The reaction can be completed in a short reaction time.

【００２０】本発明方法においては、溶媒にアルコール
を用いずアルキレングリコールジアルキルエーテルの中
から選ばれる少なくとも１種を用いたとしてもアルコキ
シシランの加水分解においてはアルコキシ基に相当する
アルコールが必ず生成してくるので、反応系からこの生
成してくるアルコールを除去しなければならない。そし
て、通常このアルコールは塗布液中１５重量％以下、好
ましくは８重量％以下まで除去される。このアルコール
分は少なければ少ないほど好ましく、アルコール分が１
５重量％を超えて残存していると、Ｈ−Ｓｉ基と生成し
たアルコールが反応し、ＲＯ−Ｓｉ基が生成し、クラッ
ク限界が低下するし、被膜形成時にガスが発生し、前記
したトラブルの原因となる。このアルコールの除去方法
としては、真空度３０〜３００ｍｍＨｇ、好ましくは、
５０〜２００ｍｍＨｇ、温度２０〜５０℃で２〜６時間
減圧蒸留するのが有利である。In the method of the present invention, even if at least one selected from alkylene glycol dialkyl ethers is used without using an alcohol as a solvent, an alcohol corresponding to an alkoxy group is always formed in the hydrolysis of alkoxysilane. Therefore, the produced alcohol must be removed from the reaction system. Usually, this alcohol is removed to 15% by weight or less, preferably 8% by weight or less in the coating solution. The lower the alcohol content is, the more preferable it is.
If the residual amount exceeds 5% by weight, the H-Si group reacts with the generated alcohol to generate an RO-Si group, which lowers the crack limit and generates gas at the time of forming a film. Cause. As a method for removing the alcohol, a degree of vacuum of 30 to 300 mmHg, preferably
It is advantageous to carry out vacuum distillation at 50 to 200 mmHg and at a temperature of 20 to 50 ° C. for 2 to 6 hours.

【００２１】本発明方法においては、基板上に、５００
℃以上の融点をもつ材料から成る配線層を設け、次いで
この上に前記のようにして調製した塗布液を塗布し、乾
燥する。この際用いられる基板としては、例えばシリコ
ンウエーハが用いられる。また、このような配線層とし
ては、多結晶シリコンが一般的であるが、５００℃以上
の融点をもつ材料であれば特に限定されない。従来のア
ルミニウムを主成分とする配線層の多くは約４７０℃付
近で溶融するが、中には５００℃以上の融点をもつもの
もあるので、このような配線層に対してももちろん用い
ることができる。In the method of the present invention, 500
A wiring layer made of a material having a melting point of not less than ° C. is provided, and then the coating solution prepared as described above is applied thereon and dried. As the substrate used at this time, for example, a silicon wafer is used. Polycrystalline silicon is generally used as such a wiring layer, but is not particularly limited as long as it has a melting point of 500 ° C. or higher. Most of the conventional wiring layers mainly composed of aluminum melt at about 470 ° C., but some of them have a melting point of 500 ° C. or more. it can.

【００２２】このように配線層を設けた基板上に、該塗
布液を塗布する方法としては、例えばスプレー法、スピ
ンコート法、ディップコート法、ロールコート法など、
任意の方法を用いることができるが、半導体素子製造に
は、通常スピンコート法が用いられる。また、乾燥処理
は、塗布液中の溶媒が揮散して塗膜が形成されればよ
く、その手段、温度、時間などについては特に制限はな
いが、一般的には、８０〜３００℃程度のホットプレー
ト上で１〜６分間程度加熱すればよい。好ましくは、３
段階以上、段階的に昇温するのが有利である。具体的に
は、大気中又は窒素などの不活性ガス雰囲気下、８０〜
１２０℃程度のホットプレート上で３０秒〜２分間程度
第１回目の乾燥処理を行ったのち、１３０〜２２０℃程
度で３０秒〜２分間程度第２回目の乾燥処理を行い、さ
らに２３０〜３００℃程度で３０秒〜２分間程度第３回
目の乾燥処理を行う。このように３段階以上、好ましく
は３〜６段階程度の段階的な乾燥処理を行うことによ
り、形成された塗膜の表面が均一なものとなる。The method of applying the coating solution on the substrate provided with the wiring layer as described above includes, for example, a spray method, a spin coating method, a dip coating method and a roll coating method.
Although any method can be used, a spin coating method is usually used for manufacturing a semiconductor device. Further, the drying treatment may be performed as long as the solvent in the coating solution is volatilized to form a coating film, and the means, temperature, time, and the like are not particularly limited, but are generally about 80 to 300 ° C. What is necessary is just to heat on a hot plate for about 1 to 6 minutes. Preferably, 3
It is advantageous to increase the temperature stepwise, in stages. Specifically, in the air or under an inert gas atmosphere such as nitrogen, 80 to
After performing a first drying process on a hot plate at about 120 ° C. for about 30 seconds to 2 minutes, a second drying process is performed at about 130 to 220 ° C. for about 30 seconds to 2 minutes, and a further 230 to 300 minutes A third drying process is performed at about 30 ° C. for about 2 seconds to about 2 minutes. By performing the stepwise drying treatment in three or more stages, preferably about three to six stages, the surface of the formed coating film becomes uniform.

【００２３】次に、このようにして形成された乾燥塗膜
を、５５０〜８００℃の範囲の温度において、塗膜中に
Ｓｉ−Ｈ結合が認められなくなるまで焼成処理する。こ
の焼成温度が５５０℃未満では焼成後の塗膜中にＳｉ−
Ｈ結合が残存するおそれがあるし、８００℃を超えると
ソース層及びドレイン層の過度の拡散が起こり、本発明
の目的が達せられない。また、この焼成処理は、大気中
又は水蒸気雰囲気中で実施するのが、完全にＳｉＯ2被
膜化しやすいので好ましい。このようにして、Ｓｉ−Ｈ
結合が完全に消失し、クラック限界の高い完全なＳｉＯ
2被膜が形成される。Next, the dried coating film thus formed is fired at a temperature in the range of 550 to 800 ° C. until no Si—H bond is observed in the coating film. If the firing temperature is lower than 550 ° C., Si-
H bonds may remain. If the temperature exceeds 800 ° C., excessive diffusion of the source layer and the drain layer occurs, and the object of the present invention cannot be achieved. This baking treatment is preferably performed in the air or in a water vapor atmosphere because it is easy to completely form a SiO 2 film. Thus, the Si-H
Bonds are completely lost and complete SiO with high crack limit
2 A coating is formed.

【００２４】[0024]

【発明の効果】本発明方法によれば、ソース層及びドレ
イン層の過度の拡散を起こすことなく、クラック限界の
高いＳｉＯ2被膜を効率よく形成させることができる。
本発明方法で形成されたＳｉＯ2被膜は、例えば半導体
素子や液晶素子などの製造に用いられる平坦化膜や層間
絶縁膜などとして好適に用いられる。According to the method of the present invention, an SiO 2 film having a high crack limit can be efficiently formed without causing excessive diffusion of the source layer and the drain layer.
The SiO 2 film formed by the method of the present invention is suitably used, for example, as a flattening film or an interlayer insulating film used for manufacturing a semiconductor device, a liquid crystal device, or the like.

【００２５】[0025]

【実施例】次に、本発明を実施例によりさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

【００２６】調製例１ ＳｉＯ2換算濃度３重量％のトリエトキシシラン７３．
９ｇ（０．４５モル）をエチレングリコールジメチルエ
ーテル８０２．０ｇ（９．０モル）に溶解し、かき混ぜ
た。次いで、これに純水２４．３ｇ（１．３５モル）と
濃硝酸５ｐｐｍを混合したものを、ゆっくりかき混ぜな
がら滴下したのち、約３時間かき混ぜ、その後室温で６
日間静置させて溶液を得た。この溶液を１２０〜１４０
ｍｍＨｇ、４０℃にて１時間減圧濃縮し、固形分濃度８
重量％、エタノールの濃度１重量％の塗布液を調製し
た。この塗布液から溶媒を除去し、残留物について熱重
量測定を行ったところ重量増加を示した。Preparation Example 1 Triethoxysilane having a concentration of 3% by weight in terms of SiO 2
9 g (0.45 mol) was dissolved in 802.0 g (9.0 mol) of ethylene glycol dimethyl ether, and the mixture was stirred. Next, a mixture of 24.3 g (1.35 mol) of pure water and 5 ppm of concentrated nitric acid was added dropwise thereto while stirring slowly, and the mixture was stirred for about 3 hours.
The solution was left standing for a day. 120-140 of this solution
The solution was concentrated under reduced pressure at 40 mm for 1 hour at a pressure of 40 mm.
A coating solution having a concentration of 1% by weight and a concentration of ethanol of 1% by weight was prepared. The solvent was removed from the coating solution, and the residue was subjected to thermogravimetry to show an increase in weight.

【００２７】調製例２ テトラメトキシシラン８０．７５ｇ（０．５３モル）を
エタノール２９８ｇ（６．４８モル）に溶解し、かき混
ぜた。次いで、純水７６．５ｇ（４．２５モル）と硝酸
２００ｐｐｍを混合したものを、ゆっくりかき混ぜなが
ら滴下したのち、約５時間かき混ぜ、その後室温で５日
間静置させて固形分濃度８重量％の溶液とした。この溶
液にシリコーン系界面活性剤であるＳＨ３０ＰＡ（東レ
・シリコーン社製）を１０００ｐｐｍ添加し、塗布液を
調製した。この塗布液から溶媒を除去し、残留物につい
て熱重量測定を行ったところ重量増加を示さなかった。Preparation Example 2 80.75 g (0.53 mol) of tetramethoxysilane was dissolved in 298 g (6.48 mol) of ethanol and stirred. Next, a mixture of 76.5 g (4.25 mol) of pure water and 200 ppm of nitric acid was added dropwise while stirring slowly, and the mixture was stirred for about 5 hours. The solution was used. To this solution, 1000 ppm of SH30PA (manufactured by Toray Silicone Co., Ltd.) as a silicone-based surfactant was added to prepare a coating solution. The solvent was removed from the coating solution, and the residue was subjected to thermogravimetry, and showed no increase in weight.

【００２８】実施例１ （１） 調製例１で得た塗布液を、シリコンウエーハ上
に配線層である多結晶シリコン層のパターンを有する基
板上に、スピンナーにより塗布し、次いでホットプレー
ト上で１００℃で１分間、２００℃で１分間、３００℃
で１分間ずつ順次乾燥させ塗膜を得た。この塗布時（ａ
ｓ Ｃｏａｔ）、１００℃における乾燥時、２００℃に
おける乾燥時、３００℃における乾燥時における赤外吸
収スペクトルを図１に示す。これより塗布から３００℃
までの乾燥においては、８４０ｃｍ-1付近と２２５０ｃ
ｍ-1付近のＳｉ−Ｈに起因するピークが強く現われてい
ることが分かる。 （２） 次いで、基板温度を室温まで下げ、（１）で得
た塗膜に、紫外線照射処理装置Ｄｅｅｐ ＵＶプロセッ
サー（日本電池社製）を用いて、大気中１８５〜２５４
ｎｍの遠紫外線を含む紫外線を１分間照射した。 （３） 次に、調製例１で得た塗布液を（２）の紫外線
照射後の塗膜上にスピンナーにより塗布し、次いでホッ
トプレート上で１００℃で１分間、２００℃で１分間、
３００℃で１分間ずつ順次乾燥させた。 （４） 最後に、大気中にて６００℃で３０分間焼成
し、ＳｉＯ2被膜を得た。この際の膜厚は４５００Åで
あり、クラックの有無をＳＥＭ（走査型電子顕微鏡）に
て観察したところ、クラックの発生はなかった。また、
この焼成後の赤外吸収スペクトルを図２に示す。これよ
り焼成後においては８４０ｃｍ-1付近と２２５０ｃｍ-1
付近のＳｉ−Ｈに起因するピークが消失し、完全にＳｉ
Ｏ2被膜に変化していることが分かる。Example 1 (1) The coating liquid obtained in Preparation Example 1 was applied on a substrate having a pattern of a polycrystalline silicon layer as a wiring layer on a silicon wafer by a spinner, and then applied on a hot plate for 100 minutes. 1 minute at 200 ° C, 1 minute at 200 ° C, 300 ° C
For 1 minute to obtain a coating film. At the time of this application (a
s Coat), when dried at 100 ° C., when dried at 200 ° C., and when dried at 300 ° C., are shown in FIG. 300 ° C from application
To 840 cm -1 and 2250 c
It can be seen that a peak around m −1 due to Si—H appears strongly. (2) Next, the temperature of the substrate was lowered to room temperature, and the coating film obtained in (1) was exposed to the air using an ultraviolet irradiation apparatus Deep UV processor (manufactured by Nippon Battery Co., Ltd.) in the atmosphere of 185 to 254.
Ultraviolet rays including far ultraviolet rays of 1 nm were irradiated for 1 minute. (3) Next, the coating solution obtained in Preparation Example 1 was applied to the coating film after the irradiation of the ultraviolet light of (2) by a spinner, and then was placed on a hot plate at 100 ° C. for 1 minute and at 200 ° C. for 1 minute.
Drying was sequentially performed at 300 ° C. for 1 minute. (4) Finally, firing was performed at 600 ° C. for 30 minutes in the air to obtain a SiO 2 coating. At this time, the film thickness was 4500 °, and the presence or absence of cracks was observed by an SEM (scanning electron microscope). As a result, no cracks occurred. Also,
FIG. 2 shows the infrared absorption spectrum after firing. 840 cm -1 in after firing than that near the 2250 cm -1
The peak due to nearby Si-H disappears, and the Si
It can be seen that the film has changed to an O 2 film.

【００２９】実施例２ 実施例１と同様に（４）の工程を水蒸気雰囲気に代えた
以外は、実施例１と同様にしてＳｉＯ2被膜を得た。こ
の際の膜厚は４５００Åであり、クラックの有無をＳＥ
Ｍ（走査型電子顕微鏡）にて観察したところ、クラック
の発生はなかった。Example 2 An SiO 2 coating was obtained in the same manner as in Example 1 except that the step (4) was replaced with a steam atmosphere. The film thickness at this time was 4500 ° and the presence or absence of cracks was determined by SE
Observation with an M (scanning electron microscope) revealed no cracks.

【００３０】比較例 実施例１において、塗布液を調製例２のものに代え、実
施例１で用いた同じ基板上にスピンナーにより塗布し、
次いでホットプレート上で乾燥させた後、大気中にて４
００℃で３０分間焼成し、ＳｉＯ2被膜を得た。この際
の膜厚は４５００Åであり、クラックの有無をＳＥＭ
（走査型電子顕微鏡）にて観察したところ、クラックが
発生していたので、これ以上高温で焼成するまでもなか
った。COMPARATIVE EXAMPLE In Example 1, the coating solution was changed to that of Preparation Example 2 and applied to the same substrate used in Example 1 by a spinner.
Then, after drying on a hot plate,
It was baked at 00 ° C. for 30 minutes to obtain a SiO 2 coating. The film thickness at this time was 4500 °, and the presence or absence of cracks was determined by SEM.
Observation with a (scanning electron microscope) revealed that cracks had occurred, and there was no need for firing at a higher temperature.

【図面の簡単な説明】[Brief description of the drawings]

【図１】 実施例１における焼成前の塗膜の赤外吸収ス
ペクトル図。FIG. 1 is an infrared absorption spectrum of a coating film before firing in Example 1.

【図２】 実施例１における焼成後のＳｉＯ2被膜の赤
外吸収スペクトル図。FIG. 2 is an infrared absorption spectrum diagram of a baked SiO 2 film in Example 1.

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 基板上に５００℃以上の融点をもつ材料
から成る配線層を設け、次いでその上にトリアルコキシ
シランの酸加水分解生成物を含有する有機溶剤溶液から
なる塗布液を塗布、乾燥したのち、５５０〜８００℃の
範囲の温度で、塗膜中にＳｉ−Ｈ結合が認められなくな
るまで焼成することを特徴とするＳｉＯ2被膜の形成方
法。1. A wiring layer made of a material having a melting point of 500 ° C. or more is provided on a substrate, and a coating solution comprising an organic solvent solution containing an acid hydrolysis product of trialkoxysilane is applied thereon, followed by drying. After the, at a temperature in the range of 550 to 800 ° C., SiO 2 film-forming method, characterized by baking the coating film to Si-H bonds can not be recognized. 【請求項２】 塗布液が、溶媒除去後の被膜形成成分が
熱重量測定において重量増加を示すものである請求項１
記載のＳｉＯ2被膜の形成方法。2. The coating liquid according to claim 1, wherein the film-forming component after removal of the solvent shows an increase in weight in thermogravimetry.
A method for forming a SiO 2 coating according to the above. 【請求項３】 塗布液が、トリアルコキシシランをＳｉ
Ｏ2換算１〜５重量％の濃度でアルキレングリコールジ
アルキルエーテル中に溶解し、この溶液中にトリアルコ
キシシラン１モル当り２．５〜３．０モルの水を加え、
酸触媒の存在下に加水分解処理したのち、生成したアル
コールの含有量を１５重量％以下に調整した溶液である
請求項１又は２記載のＳｉＯ2被膜の形成方法。3. The coating liquid is obtained by converting trialkoxysilane to Si.
It is dissolved in an alkylene glycol dialkyl ether at a concentration of 1 to 5% by weight in terms of O 2, and 2.5 to 3.0 mol of water is added to this solution per mol of trialkoxysilane,
3. The method for forming a SiO2 film according to claim 1, wherein the solution is a solution in which the content of the produced alcohol is adjusted to 15% by weight or less after hydrolysis treatment in the presence of an acid catalyst. 【請求項４】 ５００℃以上の融点をもつ材料から成る
配線層が多結晶シリコン層である請求項１，２又は３記
載のＳｉＯ2被膜の形成方法。4. 500 ° C. or more wiring layer made of a material having a melting point of polycrystalline silicon layer according to claim 1, 2 or 3 SiO 2 film forming method according.
JP12068597A 1997-05-12 1997-05-12 Method for forming SiO2 film Expired - Fee Related JP3635443B2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP12068597A JP3635443B2 (en) 1997-05-12 1997-05-12 Method for forming SiO2 film
KR1019980016692A KR100303895B1 (en) 1997-05-12 1998-05-11 Method of Forming Silica Film on Substrate Surface

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP12068597A JP3635443B2 (en) 1997-05-12 1997-05-12 Method for forming SiO2 film

Publications (2)

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JPH10313002A true JPH10313002A (en) 1998-11-24
JP3635443B2 JP3635443B2 (en) 2005-04-06

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KR (1) KR100303895B1 (en)

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JPH10330486A (en) * 1997-05-28 1998-12-15 Nippon Steel Corp Low-permittivity material
US7235500B2 (en) 2003-12-10 2007-06-26 Tokyo Ohka Kogyo Co., Ltd. Material for forming silica based film
US7601396B2 (en) 2005-04-20 2009-10-13 Tokyo Ohka Kogyo Co., Ltd. Coating film forming method
KR101136397B1 (en) 2009-05-20 2012-04-18 대한화인세라믹 주식회사 Instlating inorganic painting composites with thermal conductivity, its manufacturing method using it and PCB using the same thereof

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KR100329558B1 (en) * 1999-03-31 2002-03-20 김순택 Surface treating layer, preparing method and display device
US20030069347A1 (en) * 2001-09-28 2003-04-10 Hideki Oishi Calcined silica particle and manufacturing method of same

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JPH09137121A (en) * 1995-11-16 1997-05-27 Tokyo Ohka Kogyo Co Ltd Coating liquid for silica coating and reparation thereof
JPH10310872A (en) * 1997-05-09 1998-11-24 Tokyo Ohka Kogyo Co Ltd Formation of thick silica film

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JP3073313B2 (en) * 1992-05-12 2000-08-07 触媒化成工業株式会社 Semiconductor device and manufacturing method thereof
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JPH04216827A (en) * 1990-02-22 1992-08-06 Dow Corning Corp Precursor polymer for ceramic coating
JPH07335639A (en) * 1994-06-07 1995-12-22 Kawasaki Steel Corp Manufacture of semiconductor device
JPH09137121A (en) * 1995-11-16 1997-05-27 Tokyo Ohka Kogyo Co Ltd Coating liquid for silica coating and reparation thereof
JPH10310872A (en) * 1997-05-09 1998-11-24 Tokyo Ohka Kogyo Co Ltd Formation of thick silica film

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10330486A (en) * 1997-05-28 1998-12-15 Nippon Steel Corp Low-permittivity material
US7235500B2 (en) 2003-12-10 2007-06-26 Tokyo Ohka Kogyo Co., Ltd. Material for forming silica based film
DE102004058042B4 (en) * 2003-12-10 2010-12-02 Tokyo Ohka Kogyo Co., Ltd., Kawasaki Material for forming films based on silica and its use
US7601396B2 (en) 2005-04-20 2009-10-13 Tokyo Ohka Kogyo Co., Ltd. Coating film forming method
KR101136397B1 (en) 2009-05-20 2012-04-18 대한화인세라믹 주식회사 Instlating inorganic painting composites with thermal conductivity, its manufacturing method using it and PCB using the same thereof

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JP3635443B2 (en) 2005-04-06
KR19980086911A (en) 1998-12-05

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