JPH0995646A - Coating composition for silica-based coating film and base material with silica-based coating film - Google Patents
Coating composition for silica-based coating film and base material with silica-based coating filmInfo
- Publication number
- JPH0995646A JPH0995646A JP25160195A JP25160195A JPH0995646A JP H0995646 A JPH0995646 A JP H0995646A JP 25160195 A JP25160195 A JP 25160195A JP 25160195 A JP25160195 A JP 25160195A JP H0995646 A JPH0995646 A JP H0995646A
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- Japan
- Prior art keywords
- silica
- coating
- polysilazane
- based coating
- forming
- 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.)
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- Silicon Compounds (AREA)
Abstract
Description
【0001】[0001]
【発明の技術分野】本発明は、シリカ系被膜形成用コー
ティング組成物およびシリカ系被膜付基材に関し、さら
に詳しくは、残留するストレスが小さく、かつ緻密で耐
クラック性に優れ、しかも被塗布面の凹凸を高度に平坦
化できるシリカ系被膜を形成できるシリカ系被膜形成用
コーティング組成物と、上記のような特徴を有するシリ
カ系被膜が形成された被膜付基材に関する。TECHNICAL FIELD The present invention relates to a coating composition for forming a silica-based coating and a substrate with a silica-based coating. More specifically, the residual stress is small, and it is dense and has excellent crack resistance, and moreover, the surface to be coated. The present invention relates to a coating composition for forming a silica-based coating capable of forming a silica-based coating capable of highly flattening the unevenness, and a coated substrate having the silica-based coating having the above characteristics.
【0002】[0002]
【発明の技術的背景】従来より、シリカ系被膜は、様々
な分野で用いられている。たとえば、半導体装置では、
半導体基板とアルミニウム配線層などの金属配線層との
間や、あるいは金属配線層間に、絶縁膜として用いられ
ている。さらに半導体基板上に設けられているPN接合
半導体、およびコンデンサー素子、抵抗素子などの各種
素子の保護膜としても利用されている。BACKGROUND OF THE INVENTION Silica-based coatings have hitherto been used in various fields. For example, in semiconductor devices,
It is used as an insulating film between a semiconductor substrate and a metal wiring layer such as an aluminum wiring layer, or between metal wiring layers. Further, it is also used as a PN junction semiconductor provided on a semiconductor substrate and as a protective film for various elements such as a capacitor element and a resistance element.
【0003】また、半導体基板上に金属配線層などを設
けると、金属配線層などによって半導体基板上に凹凸が
生じる。この凹凸面上にさらに金属配線層などを形成し
ようとしても、凹凸段差で断線が生じることがある。こ
のため、上記のようにシリカ系絶縁膜を金属配線層およ
び各種素子によって生じた凹凸面に形成することで平坦
化する役割も果たしている。Further, when a metal wiring layer or the like is provided on a semiconductor substrate, unevenness occurs on the semiconductor substrate due to the metal wiring layer or the like. Even if a metal wiring layer or the like is further formed on this uneven surface, disconnection may occur due to uneven steps. Therefore, as described above, the silica-based insulating film is also formed on the uneven surface formed by the metal wiring layer and the various elements to play a role of flattening.
【0004】上記のような分野で用いられているシリカ
系被膜は、一般にCVD法、スパッタリング法などの気
相成長法またはシリカ系被膜形成用コーティング組成物
を用いてシリカ系被膜を形成する塗布法によって基板上
に形成されている。The silica-based coating used in the above fields is generally a vapor phase growth method such as a CVD method or a sputtering method, or a coating method for forming a silica-based coating using a coating composition for forming a silica-based coating. Formed on the substrate.
【0005】このうち、気相成長法によってシリカ系被
膜を形成する方法は、手間がかかるとともに大きな設備
が必要であり、また、凹凸面上にシリカ系被膜を形成し
た場合には、シリカ系被膜によって該凹凸面を平坦化す
ることができない。Of these, the method of forming the silica-based coating by the vapor phase growth method is labor-intensive and requires a large facility, and when the silica-based coating is formed on the uneven surface, the silica-based coating is required. Therefore, the uneven surface cannot be flattened.
【0006】これに対して、塗布法によってシリカ系被
膜を形成すると上記のような問題点が解決できるため、
近年、塗布法によってシリカ系被膜を形成することが広
く行われている。On the other hand, when the silica-based coating is formed by the coating method, the above problems can be solved.
In recent years, forming a silica-based coating film by a coating method has been widely performed.
【0007】このようなシリカ系被膜を形成するための
塗布液としては、アルコキシシランやハロゲン化シラン
などの部分加水分解物からなる塗布液が挙げられる。近
年、半導体基板上の多層配線層の配線段差が大きくなっ
てきたことから、これを平坦化するためには膜厚を厚く
せざるを得ない。ところが、上記のような従来のシリカ
系被膜は厚膜化が困難であった。As a coating liquid for forming such a silica-based coating film, a coating liquid containing a partial hydrolyzate such as alkoxysilane or halogenated silane can be mentioned. In recent years, the wiring step of the multi-layer wiring layer on the semiconductor substrate has become large, and therefore the film thickness must be increased in order to flatten it. However, it has been difficult to increase the thickness of the conventional silica coating as described above.
【0008】これに対し、シクロシラザン重合物または
ポリシラザンを含有してなるシリカ系被膜形成用塗布液
を用いてシリカ系被膜を形成すれば厚膜化が可能であり
緻密で平坦性の良好な絶縁膜を形成することができる。
しかし、厚膜化に伴い、Si−N結合やSi−R結合を
酸化してSi−O結合とするときに被膜の収縮ストレス
が残留し、このために得られるシリカ系被膜にクラッ
ク、ボイドが発生することがあった。。例えば、アルミ
ニウム配線層の上に従来のシリカ系被膜を形成した場
合、配線のストレスマイグレーションによる断線が起こ
ったり、ウエハーの反りが発生するなどの問題点は依然
残っていた。On the other hand, if a silica-based coating is formed by using a coating liquid for forming a silica-based coating containing a cyclosilazane polymer or polysilazane, a thick film can be formed, and an insulation having a fine and flat surface can be obtained. A film can be formed.
However, as the film becomes thicker, shrinkage stress of the coating remains when the Si—N bond or Si—R bond is oxidized to form the Si—O bond, and thus the silica-based coating obtained has cracks and voids. It happened. . For example, when a conventional silica-based coating is formed on an aluminum wiring layer, problems such as disconnection due to stress migration of wiring and warpage of the wafer still remain.
【0009】本発明者らは、上記の問題点を解決するた
めに種々の検討の結果、ポリシラザンと特定のホウ素化
合物を反応させて得られる特定の改質ポリシラザンを含
む組成物を用いてシリカ系被膜を形成すれば、厚膜化し
ても残留ストレスが低く、平坦性、緻密性に優れたシリ
カ系被膜が得られることを見出した。As a result of various investigations for solving the above problems, the present inventors have found that a silica-based composition containing a specific modified polysilazane obtained by reacting polysilazane with a specific boron compound is used. It has been found that if a film is formed, a residual stress is low even if the film is thickened, and a silica-based film excellent in flatness and compactness can be obtained.
【0010】なお、特開平6−326082号公報に
は、ボロシラザンポリマーを含む塗布液を用いて電子基
板にボロシリケート被膜を形成する方法が開示されてい
るが、被膜の残留ストレスを低くするための方法につい
ては記載されていない。JP-A-6-326082 discloses a method of forming a borosilicate film on an electronic substrate by using a coating solution containing a borosilazane polymer, but to reduce residual stress of the film. Method is not described.
【0011】[0011]
【発明の目的】本発明は、上記のような従来技術におけ
る問題点を解決しようとするものであって、被膜の残留
ストレスが小さく、しかも被塗布面との密着性、機械的
強度、耐アルカリ性などの耐薬品性を有し、かつ緻密で
耐クラック性に優れ、被塗布面の凹凸を高度に平坦化し
得うるような膜厚を有するシリカ系被膜を得ることがで
きるシリカ系被膜形成用コーティング組成物と、基材と
この上に上記のシリカ被膜が形成されたシリカ系被膜付
基材を提供するものである。SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems in the prior art. The residual stress of the coating is small, and the adhesion to the surface to be coated, the mechanical strength and the alkali resistance are high. A coating for forming a silica-based coating that has chemical resistance such as, and is dense and excellent in crack resistance, and that can obtain a silica-based coating having a film thickness capable of highly flattening the irregularities of the coated surface. The present invention provides a composition, a substrate, and a silica-based coated substrate having the above silica coating formed thereon.
【0012】[0012]
【発明の概要】本発明に係るシリカ系被膜形成用コーテ
ィング組成物は、下記一般式[I]で表される繰り返し
単位を有する1種または2種以上のポリシラザンと、SUMMARY OF THE INVENTION A coating composition for forming a silica-based film according to the present invention comprises one or more polysilazanes having a repeating unit represented by the following general formula [I],
【0013】[0013]
【化2】 Embedded image
【0014】(式中、R1 、R2 およびR3 はそれぞれ
独立して、水素原子または炭素数1〜8のアルキル基、
アリール基から選ばれる基である。) 下記一般式[II]で表されるホウ素化合物とを反応させ
て得られる改質ポリシラザンを含有することを特徴とす
る。(In the formula, R 1 , R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
It is a group selected from an aryl group. ) It is characterized by containing a modified polysilazane obtained by reacting with a boron compound represented by the following general formula [II].
【0015】 R4 n B(OR5 )3-n …[II] (式中、R4 は、水素原子または炭素数1〜8のアルキ
ル基、アリール基から選ばれる基であり、R5 は水素原
子または炭素数1〜8のアルキル基、アルコキシアルキ
ル基およびアシル基から選ばれる基であり、nは、0〜
2である。) 本発明に係るシリカ系被膜形成用コーティング組成物で
は、前記改質ポリシラザン中に、ホウ素原子の重量が全
改質ポリシラザンに対して0.1〜20重量%となる量
で、上記ホウ素化合物が含有されていることを特徴とす
る。また前記改質ポリシラザンの15N−NMRスペクト
ルの、ケミカルシフト60〜90ppmの範囲で観測され
るピーク面積の合計が、ケミカルシフト10〜90ppm
の範囲で観測されるピーク面積の合計の20%以下であ
ることが好ましく、さらに、前記改質ポリシラザンが、
ゲルクロマトグラフィー法で測定されるポリスチレン換
算数平均分子量が1000〜10000であり、分子量
700以下の改質ポリシラザンのピーク面積の合計が、
全改質ポリシラザンのピーク面積の合計に対して10%
以下で、かつ分散度(重量平均分子量/数平均分子量)
が3.5以下であることが好ましい。R 4 n B (OR 5 ) 3-n ... [II] (wherein R 4 Is a hydrogen atom or a group selected from an alkyl group having 1 to 8 carbon atoms and an aryl group, and R 5 Is a hydrogen atom or a group selected from an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group and an acyl group, and n is 0 to
2. ) In the coating composition for forming a silica-based coating film according to the present invention, the boron compound is contained in the modified polysilazane in an amount of 0.1 to 20% by weight based on the total modified polysilazane. It is characterized in that it is contained. The total peak area observed in the chemical shift range of 60 to 90 ppm in the 15 N-NMR spectrum of the modified polysilazane is 10 to 90 ppm.
Is preferably 20% or less of the total peak area observed in the range of
The polystyrene reduced number average molecular weight measured by gel chromatography is 1,000 to 10,000, and the total peak area of the modified polysilazane having a molecular weight of 700 or less is
10% of the total peak area of all modified polysilazanes
Below, and dispersity (weight average molecular weight / number average molecular weight)
Is preferably 3.5 or less.
【0016】また、本発明に係るシリカ系被膜付基材
は、基材と、その上に形成されている残留ストレスが 2
×109 dyne/cm2未満であるシリカ系被膜とからなること
を特徴としている。Further, the silica-coated base material according to the present invention has a residual stress formed on the base material.
It is characterized by comprising a silica-based coating film having a density of less than × 10 9 dyne / cm 2 .
【0017】[0017]
【発明の具体的な説明】以下、本発明に係るシリカ系被
膜形成用コーティング組成物およびシリカ系被膜付基材
について具体的に説明する。 〈シリカ系被膜形成用コーティング組成物〉本発明に係
るシリカ系被膜形成用コーティング組成物は、下記一般
式[I]で表される繰り返し単位を有する1種または2
種以上のポリシラザンと、DETAILED DESCRIPTION OF THE INVENTION The coating composition for forming a silica-based coating and the substrate with a silica-based coating according to the present invention will be specifically described below. <Silica-based film-forming coating composition> The silica-based film-forming coating composition according to the present invention is one or two having a repeating unit represented by the following general formula [I].
With more than one species of polysilazane,
【0018】[0018]
【化3】 Embedded image
【0019】(式中、R1 、R2 およびR3 はそれぞれ
独立して、水素原子または炭素数1〜8のアルキル基、
アリール基から選ばれる基である。) 下記一般式[II]で表されるホウ素化合物とを反応させ
て得られる改質ポリシラザンを含有している。(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
It is a group selected from an aryl group. ) It contains a modified polysilazane obtained by reacting with a boron compound represented by the following general formula [II].
【0020】 R4 n B(OR5 )3-n …[II] (式中、R4 は、水素原子または炭素数1〜8のアルキ
ル基、アリール基から選ばれる基であり、R5 は水素原
子または炭素数1〜8のアルキル基、アルコキシアルキ
ル基およびアシル基から選ばれる基であり、nは、0〜
2である。) 一般式[I]中のR1 、R2 およびR3 は、アルキル基
としてはメチル基、エチル基およびプロピル基から選ば
れる一種が好ましく、特に、R1 、R2 およびR3 がい
ずれも水素原子である場合が好ましい。この場合には、
後述する改質ポリシラザンを焼成してシリカ系被膜を形
成する際、分解するアルキル基、アリール基などがない
ので、膜の収縮が少く、得られる膜の残留ストレスがさ
らに小さくなり、その結果としてクラックのない被膜が
得られる。[0020] R 4 n B (OR 5) 3-n ... [II] ( wherein, R 4 Is a hydrogen atom or a group selected from an alkyl group having 1 to 8 carbon atoms and an aryl group, and R 5 Is a hydrogen atom or a group selected from an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group and an acyl group, and n is 0 to
2. ) R 1 in the general formula [I] , R 2 And R 3 Is preferably one selected from a methyl group, an ethyl group and a propyl group as the alkyl group, and particularly R 1 , R 2 And R 3 Is preferably a hydrogen atom. In this case,
When the modified polysilazane described below is fired to form a silica-based coating, there is no alkyl group or aryl group that decomposes, so there is less shrinkage of the film and the residual stress of the resulting film is even smaller, resulting in cracks. A free coating is obtained.
【0021】また、上記一般式[I]で表される繰返し
単位を有するボリシラザンは、直鎖状であっても環状で
あってもよく、直鎖状ポリシラザンと環状ポリシラザン
を混合して使用してもよい。The boricilazane having the repeating unit represented by the above general formula [I] may be linear or cyclic, and a mixture of linear polysilazane and cyclic polysilazane is used. Good.
【0022】一般式[I]で表されるポリシラザンの15
N−NMRスペクトルにおいては、ケミカルシフト10
〜60ppmの範囲にピークが観測されるが、10〜33p
pmの範囲のピーク面積の合計が10〜60ppmの範囲の
ピーク面積の合計の30%以下であることが好ましい。 15 of the polysilazane represented by the general formula [I]
In the N-NMR spectrum, a chemical shift of 10
Peak is observed in the range of ~ 60ppm, but 10 ~ 33p
The total peak area in the pm range is preferably 30% or less of the total peak area in the 10-60 ppm range.
【0023】なお、本発明の15N−NMRスペクトルの
測定は、ヘキサメチルシラザンを測定用基準物質とし、
この物質のスペクトルのピークのケミカルシフトを28
ppmとした。In the measurement of the 15 N-NMR spectrum of the present invention, hexamethylsilazane was used as a reference substance for measurement.
The chemical shift of the peak of the spectrum of this substance is 28
ppm was set.
【0024】さらに、上記のポリシラザンのSi/N比
は、1.00〜1.30であることが好ましい。一般式
[II]中のR4は水素原子、メチル基、エチル基および
プロピル基から選ばれる一種が好ましく、R5はメチル
基、エチル基およびプロピル基から選ばれる一種が好ま
しい。Further, the Si / N ratio of the above polysilazane is preferably 1.00 to 1.30. R 4 in the general formula [II] is preferably one selected from a hydrogen atom, a methyl group, an ethyl group and a propyl group, and R 5 is preferably one selected from a methyl group, an ethyl group and a propyl group.
【0025】具体的な例としては、ジヒドロキシメトキ
シボラン、ヒドロキシジメトキシボラン、ジメチルメト
キシボラン、メチルジメトキシボラン、トリメトキシボ
ラン、エチルジメトキシボラン、ジエチルメトキシボラ
ン、トリエトキシボラン、エチルジエトキシボラン、ジ
エチルエトキシボラン、プロピルジメトキシボランなど
が挙げられる。この中では、特にトリメトキシボラン、
トリエトキシボランが好ましい。Specific examples include dihydroxymethoxyborane, hydroxydimethoxyborane, dimethylmethoxyborane, methyldimethoxyborane, trimethoxyborane, ethyldimethoxyborane, diethylmethoxyborane, triethoxyborane, ethyldiethoxyborane, diethylethoxyborane. , Propyldimethoxyborane and the like. Among these, especially trimethoxyborane,
Triethoxyborane is preferred.
【0026】本発明の改質ポリシラザンの製造方法とし
ては、例えば、上記ポリシラザンとホウ素化合物の所定
量を有機溶媒に溶解し反応させる方法が挙げられる。反
応温度は0〜200℃、好ましくは100〜200℃で
ある。この結果、ポリシラザンのN架橋部分とホウ素化
合物のアルコキシ基が反応し改質ポリシラザンが得られ
ると考えられる。Examples of the method for producing the modified polysilazane of the present invention include a method in which a predetermined amount of the above polysilazane and a boron compound are dissolved in an organic solvent and reacted. The reaction temperature is 0 to 200 ° C, preferably 100 to 200 ° C. As a result, it is considered that the N-bridged portion of polysilazane reacts with the alkoxy group of the boron compound to obtain a modified polysilazane.
【0027】このような改質ポリシラザンのホウ素化合
物の含有量は、ホウ素化合物のホウ素原子の重量が全改
質ポリシラザンの0.1〜20重量%となる量であり、
好ましくは1〜10重量%でとなる量である。0.1重
量%未満では得られる被膜の残留ストレスが小さくなら
ないことがあり、一方20重量%を超えると成膜性が悪
くなり膜厚を厚くした場合に緻密な被膜が得られないこ
とがある。The content of the boron compound in the modified polysilazane is such that the weight of boron atoms in the boron compound is 0.1 to 20% by weight of the total modified polysilazane.
The amount is preferably 1 to 10% by weight. If it is less than 0.1% by weight, the residual stress of the resulting coating may not be reduced, whereas if it exceeds 20% by weight, the film-forming property may be poor and a dense coating may not be obtained when the film thickness is increased. .
【0028】上記の方法で得られる改質ポリシラザンの
15N−NMRスペクトルを測定すると、ケミカルシフト
10〜90ppmの範囲にピークが観測される。本発明に
おいては、このうち60〜90ppmの範囲のピーク面積
の合計が少ないほど残留ストレスの小さい被膜が得られ
る。すなわち、ケミカルシフト60〜90ppmの範囲の
ピーク面積の合計が10〜90ppmの範囲のピーク面積
の合計の20%以下であることが好ましい。Of the modified polysilazane obtained by the above method
When the 15 N-NMR spectrum is measured, peaks are observed in the chemical shift range of 10 to 90 ppm. In the present invention, the smaller the total peak area in the range of 60 to 90 ppm, the smaller the residual stress. That is, it is preferable that the total peak area in the range of 60 to 90 ppm of chemical shift is 20% or less of the total peak area in the range of 10 to 90 ppm.
【0029】このような改質ポリシラザンの分子量は、
ゲルクロマトグラフィー法によるポリスチレン換算の数
平均分子量で1000〜10000であり、かつ分子量
700以下の改質ポリシラザンのピーク面積の合計が、
全改質ポリシラザンのピーク面積の合計に対して10%
以下であり、しかも、分散度(重量平均分子量/数平均
分子量)が3.5以下であることが好ましい。The molecular weight of such modified polysilazane is
The total peak area of the modified polysilazane having a polystyrene-reduced number average molecular weight of 1,000 to 10,000 and a molecular weight of 700 or less by gel chromatography is
10% of the total peak area of all modified polysilazanes
It is preferable that the dispersity (weight average molecular weight / number average molecular weight) is 3.5 or less.
【0030】このような、分子量分布の改質ポリシラザ
ンを用いれば、平坦性に優れた被膜を形成することがで
きる。本発明に係るシリカ系被膜形成用コーティング組
成物は、好ましくは、上記改質ポリシラザンを固形分濃
度が3〜40重量%になるように有機溶媒に溶解するこ
とによって調製される。この場合に用いられる有機溶媒
としては、改質ポリシラザンを分散または溶解し、塗布
液に流動性を付与するものであれば特に制限はないが、
具体的には、シクロヘキサン、トルエン、キシレン等の
炭化水素類、エチルエーテル、エチルブチルエーテル、
ジブチルエーテル、ジオキサン、テトラヒドロフラン等
のエーテル類、酢酸シクロヘキシル等のエステル類が挙
げられる。これらの有機溶媒は単独でもしくは2種以上
を混合して用いられる。By using such a modified polysilazane having a molecular weight distribution, a coating having excellent flatness can be formed. The coating composition for forming a silica-based coating film according to the present invention is preferably prepared by dissolving the modified polysilazane in an organic solvent so that the solid content concentration is 3 to 40% by weight. The organic solvent used in this case is not particularly limited as long as it disperses or dissolves the modified polysilazane and imparts fluidity to the coating liquid,
Specifically, hydrocarbons such as cyclohexane, toluene, xylene, ethyl ether, ethyl butyl ether,
Examples thereof include ethers such as dibutyl ether, dioxane and tetrahydrofuran, and esters such as cyclohexyl acetate. These organic solvents are used alone or in combination of two or more.
【0031】また、本発明に係るシリカ系被膜形成用コ
ーティング組成物に用いられる上記有機溶媒としては、
水の溶解度が0.5重量%以下であることが好ましい。
このような有機溶媒を塗布液に用いることにより、塗布
液中の改質ポリシラザンなどの加水分解を防ぐことが可
能であり、これによりポットライフの長いシリカ系被膜
形成用コーティング組成物が得られる。 〈シリカ系被膜付基材〉本発明に係るシリカ系被膜付基
材は、残留ストレスが2×109dyne/cm2未満、好まし
くは1×109dyne/cm2未満のシリカ系被膜が表面に形
成されている。シリカ系被膜の残留ストレスが2×10
9dyne/cm2未満であれば、乾燥時あるいは加熱時のクラ
ック発生もほとんどなく緻密性に優れた被膜が得られ
る。Further, as the above-mentioned organic solvent used in the coating composition for forming a silica-based coating film according to the present invention,
The water solubility is preferably 0.5% by weight or less.
By using such an organic solvent in the coating liquid, it is possible to prevent hydrolysis of the modified polysilazane and the like in the coating liquid, and thereby a silica-based coating film forming coating composition having a long pot life can be obtained. <Silica-based film-coated substrate> The silica-based film-coated substrate according to the present invention has a silica-based film having a residual stress of less than 2 × 10 9 dyne / cm 2 , preferably less than 1 × 10 9 dyne / cm 2 on the surface. Is formed in. Residual stress of silica coating is 2 × 10
When it is less than 9 dyne / cm 2 , cracks are hardly generated during drying or heating, and a film having excellent denseness can be obtained.
【0032】また、膜厚は通常0.05〜2μm,好ま
しくは0.1〜1μmである。このようなストレスの小
さい被膜は、たとえば上記の本発明に係るシリカ系被膜
形成用コーティング組成物を用いて形成することができ
る。上記のシリカ系被膜形成用コーティング組成物を目
的に応じて金属板や、種々の素子等が実装された基板等
の被塗布面に、スプレー法、スピンコート法、ディッピ
ング法、ロールコート法、スクリーン印刷法、転写印刷
法などの各種方法で塗布し、次いで得られた塗膜を乾燥
後、空気中での焼成等の加熱硬化処理により得ることが
できる。なお、塗膜の加熱硬化処理に際して、加湿雰囲
気またはアンモニア雰囲気中での硬化処理、紫外線また
は電子線照射による硬化処理を併用してもよい。The film thickness is usually 0.05 to 2 μm, preferably 0.1 to 1 μm. Such a film having a small stress can be formed by using, for example, the above-mentioned coating composition for forming a silica-based film according to the present invention. Depending on the purpose, the coating composition for forming a silica-based coating film may be applied to a surface to be coated such as a metal plate or a substrate on which various elements are mounted by spraying, spin coating, dipping, roll coating, or screen. It can be obtained by applying by various methods such as a printing method and a transfer printing method, then drying the obtained coating film, and then performing heat curing treatment such as baking in air. When the coating film is heat-cured, a curing process in a humidified atmosphere or an ammonia atmosphere, or a curing process using ultraviolet rays or electron beams may be used together.
【0033】このようなシリカ系被膜付基材としては、
たとえば、半導体基板と金属配線層の間の絶縁膜や、半
導体基板上に設けられたPN接合半導体、コンデンサー
素子、抵抗素子などの各種素子などの保護膜としてシリ
カ系被膜が形成ざれた半導体装置、さらには多層配線構
造を有するLSI素子およびプリント回路基板、ハイブ
リッドIC,アルミナ基板などの電子部品、三層レジス
トなどが挙げられる。As such a silica-based coated substrate,
For example, a semiconductor device in which a silica-based coating is formed as a protective film for an insulating film between a semiconductor substrate and a metal wiring layer, a PN junction semiconductor provided on a semiconductor substrate, various elements such as a capacitor element and a resistance element, Further, an LSI element having a multilayer wiring structure and a printed circuit board, a hybrid IC, an electronic component such as an alumina substrate, a three-layer resist, and the like can be mentioned.
【0034】さらに、透明電極板の透明基板とITO膜
との間に、さらに透明電極上に配向膜を有する透明電極
板の透明電極と配向膜の間にシリカ系被膜が形成された
液晶表示装置、また、電極板の画素電極上および対向電
極板のカラーフィルター上にシリカ系被膜が形成された
カラー液晶表示装置における液晶表示セルが挙げられ
る。Further, a liquid crystal display device in which a silica-based coating is formed between the transparent substrate of the transparent electrode plate and the ITO film, and between the transparent electrode and the alignment film of the transparent electrode plate having the alignment film on the transparent electrode. Further, a liquid crystal display cell in a color liquid crystal display device in which a silica-based coating is formed on the pixel electrode of the electrode plate and the color filter of the counter electrode plate can be mentioned.
【0035】[0035]
【発明の効果】本発明に係るシリカ系被膜形成用コーテ
ィング組成物を用いれば、被膜の残留ストレスが小さ
く、被塗布面との密着性、機械的強度、耐アルカリ性な
どの耐薬品性を有し、かつ緻密で耐クラック性に優れ、
しかも被塗布面の凹凸を高度に平坦化し得うるような膜
厚を有するシリカ系被膜を得ることができる。EFFECT OF THE INVENTION By using the coating composition for forming a silica-based coating film according to the present invention, the residual stress of the coating film is small, and it has chemical resistance such as adhesion to the surface to be coated, mechanical strength and alkali resistance. And, it is dense and has excellent crack resistance,
Moreover, it is possible to obtain a silica-based coating having a film thickness capable of highly flattening the unevenness of the surface to be coated.
【0036】本発明に係るシリカ系被膜付基材は、残留
ストレスが小さいシリカ系被膜がその表面に形成されて
いる。そのため、ストレスに起因する被膜のクラックの
発生がなく、ボイドもほとんどなく、緻密で各種基板と
の密着性に優れ、被塗布面の凹凸が高度に平坦化された
被膜付基材である。したがって、このようなシリカ系被
膜付基材を用いれば、ストレスマイグレーションによる
断線の発生やウエハーの反りを防止した半導体装置等が
得られる。The silica-based coated substrate according to the present invention has a silica-based coating with a small residual stress formed on its surface. Therefore, the film-coated substrate has no cracks due to stress, has almost no voids, is dense, has excellent adhesion to various substrates, and has unevenness on the surface to be coated that is highly flattened. Therefore, by using such a silica-based coated substrate, it is possible to obtain a semiconductor device or the like in which wire breakage due to stress migration and wafer warpage are prevented.
【0037】[0037]
【実施例】以下本発明を実施例により説明するが、本発
明はこれら実施例に限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【0038】[0038]
1)ポリシラザンAの合成 特公昭63−16325号公報記載の製造法に準じて次
のような製造法でポリシラザンAを合成した。1) Synthesis of polysilazane A Polysilazane A was synthesized by the following production method according to the production method described in JP-B-63-16325.
【0039】温度が0℃の恒温槽内に設置した反応器内
にピリジン600mlをいれ、攪拌しながらジクロロシ
ラン28.3gを加えて錯体(ピリジンアダクツ)を形
成させた。次いでこのピリジンアダクツを含む液中にア
ンモニアを2時間吹き込んで沈澱を生じさせた。この沈
澱を濾過して除去した後、濾液を80℃で5時間加熱
し、次いで減圧して濾液からキピリジンを除去すること
により、反応器内に樹脂状のポリシラザンを得た。この
ポリシラザンをキシレンに溶解して、数平均分子量14
00、濃度20重量%のポリシラザンAを得た。600 ml of pyridine was placed in a reactor installed in a thermostat whose temperature was 0 ° C., and 28.3 g of dichlorosilane was added with stirring to form a complex (pyridine adduct). Next, ammonia was blown into the liquid containing the pyridine adduct for 2 hours to cause precipitation. After removing this precipitate by filtration, the filtrate was heated at 80 ° C. for 5 hours and then depressurized to remove xylidine from the filtrate to obtain a resinous polysilazane in the reactor. This polysilazane was dissolved in xylene to give a number average molecular weight of 14
A polysilazane A having a concentration of 20% by weight was obtained.
【0040】2)ポリシラザンBの合成 ポリシラザンAの合成法と同様に、温度が0℃の恒温槽
内に設置した反応器内にピリジン600mlをいれ、攪
拌しながらジクロロシラン28.3gを加えて錯体(ピ
リジンアダクツ)を形成させた。次いでこのピリジンア
ダクツを含む液中にアンモニアを2時間吹き込んで沈澱
を生じさせた。この沈澱を濾過して除去した後、濾液を
80℃で12時間加熱し、次いで減圧して濾液からピリ
ジンを除去することにより、反応器内に樹脂状のポリシ
ラザンを得た。このポリシラザンをキシレンに溶解し
て、数平均分子量2000、濃度20重量%のポリシラ
ザンBを得た。2) Synthesis of polysilazane B In the same manner as in the method of synthesizing polysilazane A, 600 ml of pyridine was placed in a reactor installed in a thermostat at a temperature of 0 ° C., and 28.3 g of dichlorosilane was added with stirring to obtain a complex. (Pyridine adduct) was formed. Next, ammonia was blown into the liquid containing the pyridine adduct for 2 hours to cause precipitation. After removing this precipitate by filtration, the filtrate was heated at 80 ° C. for 12 hours and then decompressed to remove pyridine from the filtrate to obtain a resinous polysilazane in the reactor. This polysilazane was dissolved in xylene to obtain polysilazane B having a number average molecular weight of 2000 and a concentration of 20% by weight.
【0041】3)ポリシラザンCの合成 塩化メチレン300mlを入れた1リットルの四つ口フ
ラスコを−5℃に冷却した。次いでこの四つ口フラスコ
内にメチルジクロロシラン34.2gを加え、攪拌しな
がらさらにアンモニアを2時間吹き込んで液中に沈澱を
生じさせた。この沈澱を濾過して除去した後、濾液を減
圧して濾液から塩化メチレンを除去することにより、樹
脂状のポリシラザンを得た。このポリシラザンをキシレ
ンに溶解して、数平均分子量500、濃度20重量%の
ポリシラザンCを得た。3) Synthesis of polysilazane C A 1 liter four-necked flask containing 300 ml of methylene chloride was cooled to -5 ° C. Next, 34.2 g of methyldichlorosilane was added to the four-necked flask, and ammonia was further blown into the four-necked flask for 2 hours while stirring to cause precipitation in the liquid. After removing this precipitate by filtration, the filtrate was decompressed to remove methylene chloride from the filtrate to obtain a resinous polysilazane. This polysilazane was dissolved in xylene to obtain polysilazane C having a number average molecular weight of 500 and a concentration of 20% by weight.
【0042】4)ポリシラザンDの合成 ポリシラザンAの合成法と同様に、温度が0℃の恒温槽
内に設置した反応器内にピリジン600mlを入れ、攪
拌しながらジクロロシラン28.3gを加えて錯体(ピ
リジンアダクツ)を形成させた。次いでこのピリジンア
ダクツを含む液中にアンモニアを2時間吹き込んで沈澱
を生じさせた。この沈澱を濾過して除去した後、濾液を
80℃で2時間加熱し、次いで減圧して濾液からピリジ
ンを除去することにより、反応器内に樹脂状のポリシラ
ザンを得た。このポリシラザンをキシレンに溶解して、
数平均分子量が1000、濃度20重量%のポリシラザ
ンDを得た。4) Synthesis of polysilazane D In the same manner as in the method of synthesizing polysilazane A, 600 ml of pyridine was placed in a reactor installed in a thermostat at a temperature of 0 ° C., and 28.3 g of dichlorosilane was added with stirring to obtain a complex. (Pyridine adduct) was formed. Next, ammonia was blown into the liquid containing the pyridine adduct for 2 hours to cause precipitation. After removing this precipitate by filtration, the filtrate was heated at 80 ° C. for 2 hours and then decompressed to remove pyridine from the filtrate to obtain a resinous polysilazane in the reactor. Dissolve this polysilazane in xylene,
Polysilazane D having a number average molecular weight of 1000 and a concentration of 20% by weight was obtained.
【0043】上記のポリシラザンA、B、C、Dの元素
分析結果およびゲルクロマトグラフィーによる分子量解
析データ、15N−NMRスペクトルデータを表1に示し
た。なおこれらの分子量は、ゲルクロマトグラフ法で測
定したポリスチレン換算値である。Table 1 shows the results of elemental analysis of the above polysilazanes A, B, C and D, molecular weight analysis data by gel chromatography, and 15 N-NMR spectrum data. In addition, these molecular weights are polystyrene conversion values measured by gel chromatography.
【0044】[0044]
【表1】 [Table 1]
【0045】[0045]
【実施例1】ポリシラザンA100gにトリメトキシボ
ラン20g(モル比で1/6.7)を加え、50℃で1
時間反応させた。この反応液をピリジンで5重量%に希
釈し、耐圧反応装置内に充填し、120℃で10時間加
熱重合を行った。ついでピリジンを減圧蒸留によって除
去することにより樹脂状の改質ポリシラザンEを得た。
得られた改質ポリシラザンEの分子量データを表2に示
した。Example 1 To 100 g of polysilazane A was added 20 g of trimethoxyborane (molar ratio: 1 / 6.7), and the mixture was mixed at 50 ° C. for 1 hour.
Allowed to react for hours. This reaction liquid was diluted to 5% by weight with pyridine, filled in a pressure resistant reactor, and heat-polymerized at 120 ° C. for 10 hours. Then, pyridine was removed by distillation under reduced pressure to obtain a resin-like modified polysilazane E.
The molecular weight data of the obtained modified polysilazane E is shown in Table 2.
【0046】上記のようにして得られた樹脂状改質ポリ
シラザンEをキシレンに溶解し、固形分濃度が20重量
%であるシリカ系被膜形成用コーティング組成物を得
た。このシリカ系被膜形成用コーティング組成物を、6
インチウエファーに形成された半導体基板上にスピンコ
ート法で塗布した。得られた塗膜を250℃で2分間乾
燥した後、空気中において、400℃で1時間焼成し、
シリカ系被膜付基材としての半導体装置を得た。The resinous modified polysilazane E obtained as described above was dissolved in xylene to obtain a coating composition for forming a silica-based film having a solid content concentration of 20% by weight. This silica-based coating composition for forming a coating film is
It was applied on a semiconductor substrate formed on an inch wafer by a spin coating method. After drying the obtained coating film at 250 ° C for 2 minutes, it is baked in air at 400 ° C for 1 hour,
A semiconductor device as a silica-coated base material was obtained.
【0047】上記の半導体装置について以下の各項目の
評価を行った。 シリカ系被膜のストレス:薄膜ストレス測定装置(サイ
エンティフィックメジャメント システム社製)により
測定した。The following items were evaluated for the above semiconductor device. Silica-based film stress: Measured with a thin film stress measuring device (manufactured by Scientific Measurement System Co.).
【0048】ストレス起因クラック:基材断面の走査型
電子顕微鏡写真を観察した。 ストレスマイグレーション:配線層の断線の有無を確認
した。 エッチングレート:HF・NH4F系バッファードフッ酸に基
材を浸漬し、浸漬前後の被膜の厚さの差を求めエッチン
グレートとした。Stress-induced crack: A scanning electron micrograph of the cross section of the substrate was observed. Stress migration: The presence or absence of disconnection of the wiring layer was confirmed. Etching rate: The substrate was immersed in HF / NH 4 F-based buffered hydrofluoric acid, and the difference in the thickness of the coating before and after the immersion was calculated as the etching rate.
【0049】平坦性:基材断面の走査型電子顕微鏡写真
を観察した。 これらの結果について表3に示した。Flatness: A scanning electron micrograph of the cross section of the substrate was observed. The results are shown in Table 3.
【0050】[0050]
【実施例2】ポリシラザンB100gにトリメトキシボ
ラン50g(モル比で1/16.8)を加え、50℃で
2時間反応させた。実施例1と同様にピリジンで5重量
%に希釈し、耐圧反応装置内で100℃で10時間加熱
重合を行い、減圧蒸留でピリジンを除去して、改質ポリ
シラザンFを得た。得られた改質ポリシラザンFの分子
量データを表2に示した。Example 2 To 100 g of polysilazane B, 50 g of trimethoxyborane (molar ratio 1 / 16.8) was added and reacted at 50 ° C. for 2 hours. Diluted to 5% by weight with pyridine in the same manner as in Example 1, heat-polymerized in a pressure resistant reactor at 100 ° C. for 10 hours, and then removed by pyridine under reduced pressure to obtain modified polysilazane F. The molecular weight data of the obtained modified polysilazane F is shown in Table 2.
【0051】上記のようにして得られた樹脂状改質ポリ
シラザンを酢酸シクロヘキシルに溶解し、固形分濃度が
20重量%であるシリカ系被膜形成用コーティング組成
物を得た。The resinous modified polysilazane obtained as described above was dissolved in cyclohexyl acetate to obtain a coating composition for forming a silica-based film having a solid content of 20% by weight.
【0052】実施例1と同様に半導体基板上に塗布・焼
成し、シリカ系被膜付基材としての半導体装置を得た。
上記の半導体装置について実施例1と同様に評価を行い
その結果を表3に示した。A semiconductor device was obtained by coating and baking on a semiconductor substrate in the same manner as in Example 1 to obtain a silica-based coated substrate.
The above semiconductor device was evaluated in the same manner as in Example 1 and the results are shown in Table 3.
【0053】[0053]
【実施例3】ポリシラザンC100gにトリエトキシボ
ラン50g(モル比で1/8.6)を加え、50℃で5
時間反応させた。実施例1と同様にピリジンで5重量%
に希釈し、耐圧反応装置内で100℃で20時間加熱重
合を行い、減圧蒸留でピリジンを除去して、改質ポリシ
ラザンGを得た。得られた改質ポリシラザンGの分子量
データを表2に示した。Example 3 To 100 g of polysilazane C was added 50 g of triethoxyborane (molar ratio: 1 / 8.6), and the mixture was mixed at 50 ° C. for 5 hours.
Allowed to react for hours. 5% by weight of pyridine as in Example 1
Was diluted with water, heated and polymerized at 100 ° C. for 20 hours in a pressure resistant reactor, and pyridine was removed by distillation under reduced pressure to obtain modified polysilazane G. The molecular weight data of the obtained modified polysilazane G is shown in Table 2.
【0054】上記のようにして得られた樹脂状改質ポリ
シラザンを酢酸シクロヘキシルに溶解し、固形分濃度が
20重量%であるシリカ系被膜形成用コーティング組成
物を得た。The resinous modified polysilazane obtained as described above was dissolved in cyclohexyl acetate to obtain a coating composition for forming a silica-based film having a solid content of 20% by weight.
【0055】実施例1と同様に半導体基板上に塗布・焼
成することによりシリカ系被膜付基材としての半導体装
置を得た。上記の半導体装置について実施例1と同様に
評価を行いその結果を表3に示した。By coating and baking on a semiconductor substrate in the same manner as in Example 1, a semiconductor device as a silica-based coated substrate was obtained. The above semiconductor device was evaluated in the same manner as in Example 1 and the results are shown in Table 3.
【0056】[0056]
【比較例1】ポリシラザンD100gをピリジンで5重
量%に希釈し、耐圧反応装置内で80℃で5時間加熱重
合を行った。実施例1と同様にしてピリジンを除去し、
ポリシラザンHを得た。得られたポリシラザンHの分子
量データを表2に示した。Comparative Example 1 100 g of polysilazane D was diluted to 5% by weight with pyridine and heat-polymerized at 80 ° C. for 5 hours in a pressure resistant reactor. Pyridine was removed in the same manner as in Example 1,
Polysilazane H was obtained. The molecular weight data of the obtained polysilazane H are shown in Table 2.
【0057】上記のようにして得られた樹脂状ポリシラ
ザンをキシレンに溶解し、固形分濃度が20重量%であ
るシリカ系被膜形成用コーティング組成物を得た。実施
例1と同様に半導体基板上に塗布・焼成することにより
シリカ系被膜付基材としての半導体装置を得た。The resinous polysilazane obtained as described above was dissolved in xylene to obtain a coating composition for forming a silica-based film having a solid content of 20% by weight. By coating and baking on a semiconductor substrate in the same manner as in Example 1, a semiconductor device as a silica-based coated substrate was obtained.
【0058】上記の半導体装置について実施例1と同様
に評価を行いその結果を表3に示した。The above semiconductor device was evaluated in the same manner as in Example 1 and the results are shown in Table 3.
【0059】[0059]
【比較例2】ポリシラザンD100gにトリメトキシボ
ラン50g(モル比で1/16.8)を加え、50℃で
2時間反応させた。実施例1と同様にピリジンで5重量
%に希釈し、耐圧反応装置内で100℃で10時間加熱
重合を行い、減圧蒸留でピリジンを除去して、改質ポリ
シラザンIを得た。得られた改質ポリシラザンIの分子
量データを表2に示す。Comparative Example 2 To 100 g of polysilazane D, 50 g of trimethoxyborane (molar ratio 1 / 16.8) was added and reacted at 50 ° C. for 2 hours. Diluted to 5% by weight with pyridine in the same manner as in Example 1, heat-polymerized in a pressure resistant reactor at 100 ° C. for 10 hours, and removed pyridine by vacuum distillation to obtain modified polysilazane I. Table 2 shows the molecular weight data of the obtained modified polysilazane I.
【0060】上記のようにして得られた樹脂状改質ポリ
シラザンを酢酸シクロヘキシルに溶解し、固形分濃度が
20重量%であるシリカ系被膜形成用コーティング組成
物を得た。The resinous modified polysilazane obtained as described above was dissolved in cyclohexyl acetate to obtain a coating composition for forming a silica-based film having a solid content concentration of 20% by weight.
【0061】実施例1と同様に半導体基板上に塗布・焼
成し、シリカ系被膜付基材としての半導体装置を得た。
上記の半導体装置について実施例1と同様に評価を行い
その結果を表3に示した。A semiconductor device was obtained by coating and baking on a semiconductor substrate in the same manner as in Example 1 to obtain a silica-coated base material.
The above semiconductor device was evaluated in the same manner as in Example 1 and the results are shown in Table 3.
【0062】[0062]
【表2】 [Table 2]
【0063】[0063]
【表3】 [Table 3]
Claims (6)
を有する1種または2種以上のポリシラザンと、 【化1】 (式中、R1 、R2 およびR3 はそれぞれ独立して、水
素原子または炭素数1〜8のアルキル基、アリール基か
ら選ばれる基である。) 下記一般式[II]で表されるホウ素化合物とを反応させ
て得られる改質ポリシラザンを含有することを特徴とす
るシリカ系被膜形成用コーティング組成物。 R4 n B(OR5 )3-n …[II] (式中、R4 は、水素原子または炭素数1〜8のアルキ
ル基、アリール基から選ばれる基であり、R5 は水素原
子または炭素数1〜8のアルキル基、アルコキシアルキ
ル基およびアシル基から選ばれる基であり、nは、0〜
2である。)1. One or more kinds of polysilazanes having a repeating unit represented by the following general formula [I]; (In the formula, R 1 , R 2 and R 3 are each independently a hydrogen atom or a group selected from an alkyl group having 1 to 8 carbon atoms and an aryl group.) Represented by the following general formula [II]. A coating composition for forming a silica-based coating, which comprises a modified polysilazane obtained by reacting with a boron compound. R 4 n B (OR 5 ) 3-n ... [II] (wherein R 4 Is a hydrogen atom or a group selected from an alkyl group having 1 to 8 carbon atoms and an aryl group, and R 5 Is a hydrogen atom or a group selected from an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group and an acyl group, and n is 0 to
2. )
量が全改質ポリシラザンに対して0.1〜20重量%と
なる量で、ホウ素化合物が含有されていることを特徴と
する請求項1記載のシリカ系被膜形成用コーティング組
成物。2. The modified polysilazane contains a boron compound in an amount such that the weight of boron atoms is 0.1 to 20% by weight based on the total modified polysilazane. The coating composition for forming a silica-based film as described above.
クトルの、ケミカルシフト60〜90ppmの範囲で観測
されるピーク面積の合計が、ケミカルシフト10〜90
ppmの範囲で観測されるピーク面積の合計の20%以下
であることを特徴とする請求項1ないし請求項2記載の
シリカ系被膜形成用コーティング組成物。3. The total peak area observed in the chemical shift range of 60 to 90 ppm in the 15 N-NMR spectrum of the modified polysilazane is 10 to 90 chemical shifts.
The coating composition for forming a silica-based coating film according to claim 1 or 2, which has a total peak area of 20% or less in the ppm range.
ラフィー法で測定されるポリスチレン換算数平均分子量
が、1000〜10000であり、分子量700以下の
改質ポリシラザンのピーク面積の合計が、全改質ポリシ
ラザンのピーク面積の合計に対して10%以下で、かつ
分散度(重量平均分子量/数平均分子量)が3.5以下
であること特徴とする請求項1ないし請求項3記載のシ
リカ系被膜形成用コーティング組成物。4. The modified polysilazane has a polystyrene reduced number average molecular weight measured by gel chromatography of 1,000 to 10,000, and the total peak area of the modified polysilazanes having a molecular weight of 700 or less is the total modified polysilazane. 4. The silica-based coating film forming method according to claim 1, which has a polydispersity (weight average molecular weight / number average molecular weight) of 3.5 or less with respect to the total of the peak areas. Coating composition.
9dyne/cm2未満のシリカ系被膜が形成されていることを
特徴とするシリカ系被膜付基材。5. A base material and residual stress of 2 × 10 on the base material.
A silica-based coated substrate, wherein a silica-based coating of less than 9 dyne / cm 2 is formed.
4記載のシリカ系被膜形成用コーティング組成物により
形成されていることを特徴とする請求項5記載のシリカ
系被膜付基材。6. The substrate with a silica-based coating according to claim 5, wherein the silica-based coating is formed by the coating composition for forming a silica-based coating according to any one of claims 1 to 4.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101056838B1 (en) * | 2010-10-15 | 2011-08-12 | 테크노세미켐 주식회사 | Polysilazane solution and method of manufacturing the same |
WO2013119806A1 (en) * | 2012-02-07 | 2013-08-15 | Kansas State University Research Foundation | Boron-modified silazanes for synthesis of sibnc ceramics |
JP2016022602A (en) * | 2014-07-16 | 2016-02-08 | コニカミノルタ株式会社 | Gas barrier film |
-
1995
- 1995-09-28 JP JP25160195A patent/JP4248609B2/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101056838B1 (en) * | 2010-10-15 | 2011-08-12 | 테크노세미켐 주식회사 | Polysilazane solution and method of manufacturing the same |
WO2013119806A1 (en) * | 2012-02-07 | 2013-08-15 | Kansas State University Research Foundation | Boron-modified silazanes for synthesis of sibnc ceramics |
US9453111B2 (en) | 2012-02-07 | 2016-09-27 | Kansas State University Research Foundation | Boron-modified silazanes for synthesis of SiBNC ceramics |
JP2016022602A (en) * | 2014-07-16 | 2016-02-08 | コニカミノルタ株式会社 | Gas barrier film |
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