KR100303895B1 - Method of Forming Silica Film on Substrate Surface - Google Patents
Method of Forming Silica Film on Substrate Surface Download PDFInfo
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- KR100303895B1 KR100303895B1 KR1019980016692A KR19980016692A KR100303895B1 KR 100303895 B1 KR100303895 B1 KR 100303895B1 KR 1019980016692 A KR1019980016692 A KR 1019980016692A KR 19980016692 A KR19980016692 A KR 19980016692A KR 100303895 B1 KR100303895 B1 KR 100303895B1
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- 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
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- 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
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- 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
Abstract
본 발명에 의하면, 반도체소자제법에 있어서 기판의 표면상에 평탄화막이나 층간절연막으로서 기능하는 실리카피막을 형성하는 방법이 제공되며, 이 방법은, 기판이 내열성이 낮은 회로배선층을 지닐 경우에도 적용가능하며, 또한 800℃이상의 고온에서 처리할 필요가 없다. 보다 구체적으로는, 본 발명은, (a) 유기용제, 바람직하게는 알킬렌글리콜 디알킬에테르중에 트리알콕시실란화합물, 예를 들면 트리에톡시실란의 부분가수분해축합생성물을 함유하는 도포액을 기판의 표면에 도포하는 공정; (b) 얻어진 도포층을 300℃이하의 온도에서 가열함으로써 건조시키는 공정; 및 (c) 상기 건조된 도포막을 적외흡수스펙트럼에 의해 관측되는 바와 같은 도포막중의 규소에 결합된 수소원자가 완전히 소실될 때까지 550∼800℃의 온도에서 소성처리하는 공정을 구비한 것을 특징으로 한다.According to the present invention, there is provided a method of forming a silica coating functioning as a planarization film or an interlayer insulating film on the surface of a substrate in the semiconductor device manufacturing method, which method can be applied even when the substrate has a low heat resistance circuit wiring layer. In addition, there is no need to process at a high temperature of more than 800 ℃. More specifically, the present invention provides a substrate comprising a coating liquid containing (a) a partial hydrolysis condensation product of a trialkoxysilane compound, for example triethoxysilane, in an organic solvent, preferably an alkylene glycol dialkyl ether. Applying to the surface of the film; (b) drying the obtained coating layer by heating at a temperature of 300 ° C. or lower; And (c) calcining the dried coating film at a temperature of 550 to 800 ° C. until hydrogen atoms bonded to silicon in the coating film are completely lost as observed by the infrared absorption spectrum. .
Description
본 발명은 반도체소자나 액정표시패널의 제법에 있어서 평탄화막이나 층간절연막 등으로서 기능하는 균열한계가 높은 실리카피막을, 기판표면상에 도포액에 의한 도포에 의해 소스층 및 드레인층의 과도한 확산이 일어나지 않도록 효율좋게 형성시키는 방법에 관한 것이다.According to the present invention, excessive diffusion of the source layer and the drain layer is prevented by applying a coating film with a coating liquid on a substrate surface, which has a high cracking limit, which functions as a flattening film or an interlayer insulating film in the manufacturing method of a semiconductor device or a liquid crystal display panel. It relates to a method for forming efficiently so as not to occur.
종래, 반도체소자나 액정표시패널의 제법에 있어서 평탄화막이나 층간 절연막으로서 실리카계피막이 이용되고 있다. 이러한 실리카계피막을 형성시키는 데 유용한 방법으로서는, 기판표면상에 실리카를 화학적 기상퇴적시키는 방법(CVD법) 및 기판표면을 도포액으로 도포한 후 그 도포층을 실리카계피막으로 변화시키는 방법이 있다.Conventionally, silica coating films have been used as planarization films and interlayer insulating films in the production of semiconductor devices and liquid crystal display panels. As a useful method for forming such a silica coating film, there are a method of chemical vapor deposition of silica on a substrate surface (CVD method) and a method of applying the substrate surface with a coating liquid and then changing the coating layer to a silica coating film.
CVD법에 의한 실리카계피막은, 특수한 장치를 사용해서, 기판표면에 실리카를 증착시키거나, 또는 필요에 따라 기판표면에 인이나 붕소를 기상으로부터 도핑시켜 도포막을 형성하여 절연막이나 평탄화막으로서 이용되고 있으나, 이 CVD법에 의해 형성된 실리카계피막이 단차가 있는 기판표면상의 평탄화막으로서 이용되는 경우에는, 기판표면에 대한 일치성(conformability)은 양호하나, 평탄화성이 나쁘므로, 950∼1100℃정도의 온도에서 피막을 리플로(re-flow)시키기 위한 열처리가 필요하다.Silica coating film by CVD method is used as an insulating film or a planarizing film by depositing silica on the surface of the substrate using a special device, or forming a coating film by doping phosphorus or boron from the gas phase on the surface of the substrate if necessary. When the silica-based coating film formed by this CVD method is used as a planarization film on a stepped substrate surface, the conformability to the substrate surface is good, but the planarization property is poor, and thus the temperature of about 950 to 1100 ° C. Heat treatment is needed to re-flow the coating.
한편, 액도포법에 의한 실리카계피막은, 일반적으로, 유기용제중에 알콕시실란의 부분가수분해축합물을 함유하는 도포액을 기판표면에 도포한 후 열처리 또는 소성처리함으로써 도포층을 실리카계피막으로 변환시키고 있다. 이 방법에 의해 얻어진 피막은 평탄성이 양호하므로, 평탄화막이나 절연막으로서 이용되고 있다.On the other hand, the silica coating film by the liquid coating method generally converts the coating layer into a silica coating film by applying a coating liquid containing a partial hydrolysis-condensation product of an alkoxysilane in an organic solvent onto the substrate surface, followed by heat treatment or baking. I'm making it. Since the film obtained by this method has good flatness, it is used as a flattening film or an insulating film.
이와 같은 CVD법이나 액도포법에 의해 형성된 실리카계피막은, 각각의 특성을 이용해서 반도체소자의 제조방법에 있어서의 각종 분야에서 이용되고 있다. 예를 들면, 알루미늄을 주성분으로 하는 회로배선층상에 CVD법에 의해 형성된 실리카계층간절연막은, 그 위에 평탄화를 필요로 하는 하부면과 일치성은 양호하나, 알루미늄계 회로배선층의 전기특성을 일반적으로 470℃이상에서의 가열에 의해 악영향을 받으므로, 평탄화에 필수불가결한 리플로처리를 실시하는 것이 불가능하다. 따라서, 이러한 층간절연막상에는, 도포층을 약 450℃에서 소성처리하는 액도포법에 의해 실리카계평탄화막이 형성되고 있다. 이와 같이 하부층의 내열성이 알루미늄 등으로 이루어진 회로배선층에 있어서와 같이 충분히 높지 않을 경우에는, 실리카계피막형성에 액도포법이 유용하다.The silica coating film formed by such a CVD method or a liquid coating method is utilized in various fields in the manufacturing method of a semiconductor element using each characteristic. For example, the silica interlayer dielectric film formed by the CVD method on the circuit wiring layer mainly composed of aluminum has good agreement with the lower surface requiring planarization thereon, but the electrical characteristics of the aluminum circuit wiring layer are generally 470. Since it is adversely affected by the heating at a temperature higher than or equal to C, it is impossible to perform a reflow treatment which is indispensable for flattening. Therefore, a silica-based planarization film is formed on such an interlayer insulating film by the liquid coating method which bakes a coating layer at about 450 degreeC. As described above, when the heat resistance of the lower layer is not sufficiently high as in the circuit wiring layer made of aluminum or the like, the liquid coating method is useful for forming the silica-based coating film.
한편, 다결정실리콘은 상기와 같은 고온의 리플로처리에 견딜 수 있으므로, CVD법에 의해 PSG(phosphosilicate glass)를 증착시킨 후 1000℃정도에서 리플로처리해서 평탄화막을 형성함으로써 다결정실리콘으로부터 회로배선층을 형성할 경우 CVD법을 적용가능하다.On the other hand, since the polysilicon can withstand the high temperature reflow treatment as described above, PSG (phosphosilicate glass) is deposited by CVD and then reflowed at about 1000 DEG C to form a planarization film to form a circuit wiring layer from the polysilicon. In this case, the CVD method can be applied.
상기에서 말하는 PSG막이란, 인을 10중량%정도 함유시킴으로써 융점을 1000℃정도까지 저하시킨 실리카계피막을 의미한다.The PSG film mentioned above means the silica-based coating film which reduced melting | fusing point to about 1000 degreeC by containing about 10 weight% of phosphorus.
이와 같이, 리플로처리를 수반하는 CVD법은, 다결정실리콘으로 이루어진 회로배선층에 있어서와 같이 하부층이 고내열성을 지닐 경우 실리카계평탄화막이나 절연막의 형성에 적용가능하다.As described above, the CVD method involving the reflow treatment can be applied to the formation of a silica-based planarization film or an insulating film when the lower layer has high heat resistance as in a circuit wiring layer made of polycrystalline silicon.
그러나, CVD법에 의해 형성된 실리카계평탄화절연막이 리플로처리를 수반할 경우, 이 방법은, 리플로처리를 위한 고온에서 소스층 및 드레인층의 확산이 과도하게 진행되어 전자소자의 특성에 악영향을 미치므로 고미세화를 향한 포토리소그래피패터닝의 추세에 응할 수 없게 된다. 이 문제점은, PSG막을, 인과 붕소를 조합해서 함유하는 실리카계막인 BPSG(borophosphosilicate glass)막으로 대체함으로써 리플로처리온도를 950℃정도로 감소할 경우 부분적으로 완화될 수 있다.However, when the silica-based planarization insulating film formed by the CVD method involves a reflow treatment, this method causes excessive diffusion of the source layer and the drain layer at a high temperature for the reflow treatment, thereby adversely affecting the characteristics of the electronic device. As a result, they cannot respond to the trend of photolithography patterning towards high-definition. This problem can be partially alleviated when the PSG film is replaced with a borophosphosilicate glass (BPSG) film, which is a silica-based film containing phosphorus and boron in combination.
하지만, 금후 반도체소자의 미세화가 더욱 진행되어, 256메가 또는 1기가 DRAM에 이르는 초고집적도의 집적회로가 제조되는 경우, 소스층 및 드레인층의 확산의 더욱 정밀한 제어가 중요하게 되어, 이러한 고온의 리플로처리를 수반하는 CVD법은 하여튼 반도체소자의 전자특성에 악영향을 미치지 않으므로, 고온의 리플로처리를 수반함이 없이 실리카계평탄화막 또는 절연막을 형성하는 방법의 개발이 강하게 요망되고 있다.However, when semiconductor devices are further miniaturized and ultra-high density integrated circuits of up to 256 megabytes or 1 Gigabit DRAM are manufactured, more precise control of the diffusion of the source and drain layers becomes important, such a high temperature ripple. Since the CVD method involving the furnace treatment does not adversely affect the electronic characteristics of the semiconductor device, there is a strong demand for the development of a method of forming a silica-based planarization film or an insulating film without involving a high temperature reflow treatment.
실리카계피막의 형성방법에 있어서 상기 온도를 소스층 및 드레인층의 과도한 확산이 일어나지 않는 800℃이하까지 낮추는 점에서는, 액도포법이 CVD법에 비해서 유망한 동시에 바람직하다. 마찬가지로, 1기가 DRAM이후의 미세한 커패시터의 재료로서 높은 유전률특성을 지닌 산화탄탈(Ta2O5) 또는 바륨스트론튬티탄산(BST)을 이용해서 반도체소자를 제조할 경우, 소자의 전자특성에 악영향을 미치지 않는 800℃이하의 온도에서 실리카계피막을 형성할 수 있으므로 액도포법이 유망하다.In the method of forming a silica-based coating film, the liquid coating method is promising and preferable as compared with the CVD method in that the temperature is lowered to 800 ° C. or less in which excessive diffusion of the source layer and the drain layer does not occur. Likewise, when a semiconductor device is manufactured using tantalum oxide (Ta 2 O 5 ) or barium strontium titanate (BST) having high dielectric constant as a material of a fine capacitor after 1 giga DRAM, the electronic characteristics of the device are not adversely affected. The liquid coating method is promising because a silica coating film can be formed at a temperature not higher than 800 ° C.
그러나, 종래의 도포액에서는 균열발생에 기인한 문제가 없는 피막의 최대두께인 충분히 높은 균열한계를 지닌 피막을 얻을 수 없으므로, 이제까지 개발된 액도포법은, 실리카계피막형성에 이러한 종래의 도포액을 이용하는 전술한 프로세스에 실제로 적용할 수 없었다.However, in the conventional coating liquid, a coating having a sufficiently high crack limit, which is the maximum thickness of the coating without problems due to cracking, cannot be obtained, and thus the liquid coating method developed so far is such a conventional coating liquid for forming a silica based coating. It could not actually be applied to the above-described process using.
따라서, 본 발명은, 회로배선층상에 평탄화 및 절연용의 실리카피막을 형성하기 위해 고온에서의 리플로처리를 수반하는 종래의 CVD법대신에, 소스층 및 드레인층에 과도한 확산의 문제가 없는 800℃이하의 처리온도에서 행할 수 있는 균열한계가 높은 실리카피막을 형성하는 신규의 액도포법을 제공하는 것을 목적으로 한다.Accordingly, the present invention provides an 800-free process of overdiffusion in the source and drain layers instead of the conventional CVD method involving the reflow treatment at high temperature to form a silica coating film for planarization and insulation on the circuit wiring layer. It is an object of the present invention to provide a novel liquid coating method for forming a silica coating having a high cracking limit that can be performed at a processing temperature of not more than 占 폚.
따라서, 본 발명의 기판표면상에의 실리카피막의 형성방법은, 800℃까지의 온도에서의 가열에 견딜 수 있는 내열성을 가진 재료로 형성된 회로배선층을 제공할 수 있도록, 하기의 공정, 즉Therefore, the method of forming the silica coating on the surface of the substrate of the present invention provides a circuit wiring layer formed of a material having heat resistance that can withstand heating at temperatures up to 800 ° C.
(a) 유기용제중에 트리알콕시실란화합물의 산촉매에 의한 부분가수분해축합생성물을 함유하는 용액인 도포액을 기판의 표면에 도포해서 도포층을 형성하는 공정;(a) applying a coating liquid, which is a solution containing a partial hydrolysis-condensation product by an acid catalyst of a trialkoxysilane compound in an organic solvent, to a surface of a substrate to form a coating layer;
(b) 상기 도포층을 80∼300℃범위의 온도에서 가열함으로써 건조시켜, 트리알콕시실란화합물의 부분가수분해축합생성물의 건조된 도포막을 형성하는 공정; 및(b) drying the coating layer by heating at a temperature in the range of 80 to 300 ° C. to form a dried coating film of the partial hydrolysis-condensation product of the trialkoxysilane compound; And
(c) 상기 건조된 도포막을 550∼800℃범위의 온도에서, 바람직하게는 트리알콕시실란화합물의 부분가수분해축합생성물에 있어서 규소원자에 직접 결합된 수소원자, 즉 규소에 결합된 수소원자 Si-H의 거의 전부를 분해시키는데 충분한 시간, 예를 들면, 0.5∼60분간 수증기의 존재하에 소성처리하는 공정을 구비한 액도포법을 특징으로 한다.(c) the dried coating film at a temperature in the range of 550-800 ° C., preferably a hydrogen atom directly bonded to a silicon atom in the partial hydrolysis condensation product of the trialkoxysilane compound, that is, a hydrogen atom Si- bonded to silicon; It is characterized by a liquid application method comprising a step of calcining in the presence of steam for a time sufficient to decompose almost all of H, for example, 0.5 to 60 minutes.
도 1은 실시예 1의 각종 건조단계에서의 도포막의 적외흡수스펙트럼도1 is an infrared absorption spectrum diagram of a coating film in various drying steps of Example 1;
도 2는 실시예 1에서 형성된 실리카피막의 적외흡수스펙트럼도2 is an infrared absorption spectrum diagram of a silica film formed in Example 1
일본국 특공평 6-42477호 공보에는, 수소실세스퀴옥산수지를 함유하는 도포액을 기판표면에 도포하고, 약 150∼1000℃범위의 온도에서 열처리함으로써 기판표면에 실리카계피막을 형성하는 방법이 제안되어 있다. 이 공보에서는, 상기 범위의 온도에서 가열처리를 행하는 것으로 기재되어 있으나, 그 각 실시예에 기재된 실제의 가열처리는 400℃에서 1시간 행해지고 있다. 이러한 조건하에서 열처리를 행하면, 얻어지는 피막은 어느 정도 규소에 결합된 수소원자가 잔존하는 것을 피할 수 없으므로, 형성된 피막은 완전한 실리카피막이 아니다. 이에 대해서 본 발명은 규소에 결합된 수소원자가 남지 않도록 소성처리를 행하는 것이다.Japanese Unexamined Patent Publication No. 6-42477 discloses a method of forming a silica coating film on the surface of a substrate by applying a coating liquid containing hydrogen silsesquioxane resin to the surface of the substrate and heat-treating at a temperature in the range of about 150 to 1000 ° C. It is proposed. In this publication, it is described that heat treatment is performed at a temperature in the above range, but the actual heat treatment described in each of the examples is performed at 400 ° C. for 1 hour. If the heat treatment is performed under such conditions, the resulting film cannot avoid the hydrogen atoms bound to silicon to some extent, and thus the formed film is not a complete silica film. In the present invention, on the other hand, the firing treatment is carried out so that hydrogen atoms bonded to silicon do not remain.
본 발명의 액도포법에서 사용되는 도포액은, 유기용제중의 트리알콕시실란화합물의 산촉매에 의한 부분가수분해축합생성물을 함유하는 용액이다. 상기 도포액의 제조에 이용가능한 트리알콕시실란화합물의 예로서는, 트리메톡시실란, 트리에톡시실란, 트리프로폭시실란, 트리부톡시실란, 디에톡시모노메톡시실란, 디프로폭시모노메톡시실란, 디부톡시모노메톡시실란, 에톡시메톡시프로폭시실란, 디메톡시모노에톡시실란, 디프로폭시모노에톡시실란, 부톡시에톡시프로폭시실란, 디메톡시모노프로폭시실란, 디에톡시모노프로폭시실란, 디메톡시모노부톡시실란 등을 들 수 있고, 이들 중에서, 트리메톡시실란, 트리에톡시실란, 트리프로폭시실란 및 트리부톡시실란이 바람직하며, 특히, 트리메톡시실란 및 트리에톡시실란이 실용상의 견지에서 가장 바람직하다. 이들 트리알콕시실란화합물은 단독으로 이용해도 되고, 필요에 따라 2종이상을 조합해서 이용해도 된다.The coating liquid used by the liquid coating method of this invention is a solution containing the partial hydrolysis-condensation product by the acid catalyst of the trialkoxysilane compound in the organic solvent. As an example of the trialkoxysilane compound which can be used for manufacture of the said coating liquid, a trimethoxysilane, a triethoxysilane, a tripropoxysilane, a tributoxysilane, a diethoxy monomethoxysilane, a dipropoxy monomethoxysilane, Dibutoxy monomethoxysilane, ethoxymethoxypropoxysilane, dimethoxy monoethoxysilane, dipropoxy monoethoxysilane, butoxyethoxypropoxysilane, dimethoxy monopropoxysilane, diethoxy monopropoxy Silane, dimethoxy monobutoxysilane, and the like, among which trimethoxysilane, triethoxysilane, tripropoxysilane and tributoxysilane are preferable, and trimethoxysilane and triethoxy are particularly preferred. Silanes are most preferred from a practical point of view. These trialkoxysilane compounds may be used independently or may be used in combination of 2 or more type as needed.
또, 트리알콕시실란화합물이 가수분해된 상기 유기용제로서는 특히 제한은 없고, 알킬렌글리콜디알킬에테르가 바람직하다. 이런 유형의 유기용제는, 트리알콕시실란화합물로부터 종래의 도포액을 제조하는데 이용되는 알콜용제와는 달리, 출발하는 트리알콕시실란화합물중의 Si-H결합의 분해반응 및 트리알콕시실란화합물의 가수분해에 의해 형성된 실란올의 Si-OH기가 알콕시기로 되돌아가는 반응을 억제하여 용액의 겔화에 의한 트러블을 저감할 수 있다.Moreover, there is no restriction | limiting in particular as said organic solvent in which the trialkoxysilane compound was hydrolyzed, Alkylene glycol dialkyl ether is preferable. This type of organic solvent, unlike the alcoholic solvents used to prepare conventional coating liquids from trialkoxysilane compounds, decomposes Si-H bonds in the starting trialkoxysilane compound and hydrolysis of the trialkoxysilane compound. The reaction by which the Si-OH group of the silanol formed by returning to the alkoxy group can be suppressed, and the trouble by gelling of a solution can be reduced.
도포액의 용제로서 적합한 알킬렌글리콜 디알킬에테르의 예로서는, 에틸렌글리콜디메틸에테르, 에틸렌글리콜디에틸에테르, 에틸렌글리콜디프로필에테르, 에틸렌글리콜디부틸에테르, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜디프로필에테르, 디에틸렌글리콜디부틸에테르, 프로필렌글리콜디메틸에테르, 프로필렌글리콜디에틸에테르, 프로필렌글리콜디프로필에테르, 프로필렌글리콜디부틸에테르 등을 들 수 있고, 이들 중에서 에틸렌글리콜 또는 프로필렌글리콜의 디알킬에테르가 바람직하며, 특히 에틸렌글리콜 또는 프로필렌글리콜의 디메틸에테르가 가장 바람직하다. 이들 용제는 단독으로 이용해도 되고, 또는 필요에 따라 2종이상을 혼합해서 이용해도 된다. 또, 도포액의 제조에 사용되는 용제의 양은 트리알콕시실란화합물 1몰당, 통상 10∼30몰의 범위이다.Examples of alkylene glycol dialkyl ethers suitable as solvents for coating solutions include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. And diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether and the like, and ethylene glycol or propylene glycol among these. The dialkyl ether of is preferable, especially the dimethyl ether of ethylene glycol or propylene glycol is the most preferable. These solvents may be used independently, or may mix and use 2 or more types as needed. Moreover, the quantity of the solvent used for manufacture of a coating liquid is the range of 10-30 mol normally per 1 mol of trialkoxysilane compounds.
본 발명의 방법에 이용되는 도포액은, 상기 유기용제중에 용해된 트리알콕시실란화합물의 부분가수분해축합생성물용액이지만, 특히 용매제거후의 용액중에 함유된 막형성용 고형물이 열중량분석에 있어서 독특한 중량증가거동을 나타내는 것이 바람직하다. 또, 특징적으로, 본 발명의 방법에 이용되는 도포액중의 고형물은 적외흡수스펙트럼에 있어서 파수 3000㎝-1근방에 적외흡수띠가 없다. 이들 특징은, 열중량분석에 있어서 중량감소의 거동을 나타내는 동시에, 적외흡수스펙트럼에 있어서 잔존 알콕시기의 실질적인 양의 존재를 표시하는 파수 3000㎝-1근방에 적외흡수띠를 지니는 예를 들면 일본국 특개평 4-216827호 공보에 개시된 바와 같은 종래의 도포액과는 현저하게 다르다.The coating liquid used in the method of the present invention is a partial hydrolysis condensation product solution of the trialkoxysilane compound dissolved in the organic solvent, but the film-forming solids contained in the solution after removal of the solvent have a unique weight in thermogravimetric analysis. It is desirable to exhibit increasing behavior. In addition, the solids in the coating liquid used in the method of the present invention do not have an infrared absorption band near the wave number 3000 cm -1 in the infrared absorption spectrum. These characteristics, for example, include an infrared absorption band in the vicinity of the wavenumber 3000 cm -1 indicating the weight loss behavior in the thermogravimetric analysis and indicating the presence of the substantial amount of the remaining alkoxy group in the infrared absorption spectrum. It is remarkably different from the conventional coating liquid as disclosed in Japanese Patent Application Laid-Open No. 4-216827.
본 발명의 방법에 이용되는 도포액의 바람직한 제조방법은 다음과 같다.The preferable manufacturing method of the coating liquid used for the method of this invention is as follows.
우선, 상기 알킬렌글리콜디알킬에테르용제중에, 트리알콕시실란화합물을 SiO2로 환산해서 1∼5중량%, 바람직하게는 2∼4중량%의 양으로 용해한다. 이와 같이 해서 제조한 반응혼합물중의 트리알콕시실란의 농도가 너무 높게 되면, 얻어진 도포액에 필연적으로 겔화가 일어나 보존안정성이 나빠진다. 이 현상의 메카니즘은, 명확하지는 않지만, 반응혼합물중의 트리알콕시실란의 농도가 낮은 경우 가수분해반응이 완만한 속도로 진행하여, Si-H결합의 과도한 분해를 방지하여, 폴리실록산의 소위 사다리구조의 형성을 용이하게 하기 때문인 것으로 추정된다.First, the trialkoxysilane compound is dissolved in an amount of 1 to 5% by weight, preferably 2 to 4% by weight, in terms of SiO 2 in the alkylene glycol dialkyl ether solvent. When the concentration of the trialkoxysilane in the reaction mixture thus produced is too high, gelation inevitably occurs in the obtained coating liquid, resulting in poor storage stability. The mechanism of this phenomenon is not clear, but when the concentration of the trialkoxysilane in the reaction mixture is low, the hydrolysis reaction proceeds at a moderate rate, preventing excessive decomposition of Si-H bonds, thereby preventing the so-called ladder structure of polysiloxane. It is assumed that this is because it facilitates the formation.
다음에, 상기 반응혼합물에 물을 첨가하여 트리알콕시실란의 가수분해반응을 행한다. 이때, 반응혼합물에의 물의 첨가량은 트리알콕시실란화합물 1몰당 2.5∼3.0몰, 바람직하게는 2.8∼3.0몰로 하는 것이 가수분해반응을 고속으로 행할 수 있으므로 유리하다. 상기 물의 첨가량이 너무 적으면, 도포액의 보존안정성이 충분히 높더라도, 가수분해반응이 충분히 진행될 수 없어, 가수분해생성물중의 유기성분의 잔류량이 과도하게 많아져서, 실리카피막형성시의 가스발생량이 증가하게 된다. 또, 반응혼합물에의 물의 첨가량이 너무 많으면, 도포액의 보존안정성이 저하된다.Next, water is added to the reaction mixture to hydrolyze the trialkoxysilane. At this time, the amount of water added to the reaction mixture is advantageously 2.5 to 3.0 mol, preferably 2.8 to 3.0 mol per mol of the trialkoxysilane compound, since the hydrolysis reaction can be performed at high speed. If the addition amount of the water is too small, even if the storage stability of the coating liquid is sufficiently high, the hydrolysis reaction cannot proceed sufficiently, and the residual amount of organic components in the hydrolysis product is excessively increased, so that the amount of gas generated at the time of forming the silica coating Will increase. If the amount of water added to the reaction mixture is too large, the storage stability of the coating liquid is lowered.
또, 반응혼합물중의 트리알콕시실란화합물의 가수분해반응은 산촉매의 존재하에 행하나, 이때, 촉매로서의 산성화합물은 특히 한정되지 않고, 종래의 실리카계도포액제조에 사용되는 유기산이나 무기산으로부터 선택할 수 있다. 적절한 산성 화합물의 예로서는, 유기산으로서, 아세트산, 프로피온산, 부티르산 등을 들 수 있고, 무기산으로서는, 염산, 질산, 황산, 인산 등을 들 수 있으나, 특히 질산이 바람직하다.The hydrolysis reaction of the trialkoxysilane compound in the reaction mixture is carried out in the presence of an acid catalyst. At this time, the acidic compound as the catalyst is not particularly limited, and may be selected from organic acids and inorganic acids used in conventional silica-based coating liquid production. have. Examples of suitable acidic compounds include acetic acid, propionic acid, butyric acid, and the like, and inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the like, and nitric acid is particularly preferable.
상기 반응혼합물에의 산첨가량은 1∼200중량ppm, 바람직하게는 1∼40중량ppm이다. 이때, 산은 반응혼합물에 별도로 첨가하거나, 또는 물과 혼합해서 첨가하여 가수분해반응시킨다.The acid addition amount to the reaction mixture is 1 to 200 ppm by weight, preferably 1 to 40 ppm by weight. At this time, the acid is added to the reaction mixture separately, or mixed with water to add a hydrolysis reaction.
트리알콕시실란화합물의 가수분해반응은, 실온에서부터 70℃까지 범위의 온도에서, 알킬렌클리콜디알킬에테르중의 트리알콕시실란화합물용액속에 산을 함유하는 가수분해용 물을 적하해서 첨가함으로써 행하는 것이 바람직하며, 이 가수분해반응은 통상 5∼100시간이내에서 완료한다.The hydrolysis reaction of the trialkoxysilane compound is preferably carried out by dropwise addition of water for hydrolysis containing an acid to the trialkoxysilane compound solution in the alkylene glycol dialkyl ether at a temperature ranging from room temperature to 70 ° C. This hydrolysis reaction is usually completed within 5 to 100 hours.
물론, 트리알콜시실란화합물의 가수분해반응의 부산물로서 알콜이 생성된다. 따라서, 가수분해반응후의 반응혼합물은, 가수분해반응전의 초기에는 알킬렌글리콜디알킬에테르단독이지만, 트리알콕시실란화합물의 가수분해생성물에 대해 용매의 일부로서 알콜을 반드시 함유한다. 반응혼합물중의 알콜은, 본 발명의 방법에서 이용하는 도포액에 있어서 15중량%이하, 바람직하게는 8중량%이하가 되도록 가능한 한 완전히 제거하는 것이 중요하다. 반응혼합물로부터의 알콜의 제거는, 진공도 30∼300㎜Hg, 바람직하게는 50∼200㎜Hg, 온도 20∼50℃에서 2∼6시간 감압증류시킴으로써 행한다. 알콜의 잔류함량이 도포액중에 너무 많으면, Si-H결합이 알콜과 반응해서 알콕시기를 재생하여, 실리카피막형성도중에 가스방출량이 증가하므로 균열형성한계가 저하된다.Of course, alcohol is produced as a byproduct of the hydrolysis of the trialcohol silane compound. Therefore, the reaction mixture after the hydrolysis reaction is alkylene glycol dialkyl ether alone at the beginning before the hydrolysis reaction, but always contains alcohol as part of the solvent for the hydrolysis product of the trialkoxysilane compound. It is important that the alcohol in the reaction mixture be removed as completely as possible so that the coating liquid used in the method of the present invention is 15% by weight or less, preferably 8% by weight or less. Removal of alcohol from the reaction mixture is carried out by distillation under reduced pressure at a vacuum degree of 30 to 300 mmHg, preferably 50 to 200 mmHg at a temperature of 20 to 50 ° C for 2 to 6 hours. If the residual content of alcohol is too much in the coating liquid, the Si-H bond reacts with the alcohol to regenerate the alkoxy group, and the gas release amount increases during the silica film formation, so that the crack formation limit is lowered.
본 발명의 방법을 실시하는 데 있어서, 800℃까지의 온도에 견딜 수 있는 내성을 지닌 재료로 형성된 회로배선층을 지닌 반도체실리콘웨이퍼 등의 기판의 표면에는 상기와 같이 해서 제조한 도포액을 도포하고 열처리하여 도포층의 건조를 행한다. 회로배선층을 형성하기 위한 재료는 다결정실리콘이 바람직하나, 특히 이것으로 한정되는 것은 아니다. 또, 알루미늄을 주성분으로 하는 회로배선층은 본 발명의 방법의 도중에 있어서 나쁜 영향을 미치므로 실리카피막을 본 발명의 방법에 의해 형성하고자 할 경우에는 이러한 회로배선층은 기판표면에 형성할 수 없다.In carrying out the method of the present invention, a coating liquid prepared as described above is applied to a surface of a substrate such as a semiconductor silicon wafer having a circuit wiring layer formed of a material having a resistance to temperatures up to 800 ° C. To dry the coating layer. The material for forming the circuit wiring layer is preferably polycrystalline silicon, but is not particularly limited thereto. In addition, since the circuit wiring layer containing aluminum as a main component has a bad effect in the middle of the method of the present invention, such a circuit wiring layer cannot be formed on the substrate surface when a silica film is to be formed by the method of the present invention.
도포액에 의한 도포조작방법은, 특히 제한되지 않고, 예를 들면, 스핀도포, 스프레이도포, 침지도포, 롤러도포법 등을 들 수 있으나, 전자소자의 제조에 있어서 종래의 방법에서는 스핀도포법이 가장 적합하다.The coating operation method using the coating liquid is not particularly limited, and examples thereof include spin coating, spray coating, immersion coating, roller coating, and the like. However, in the manufacturing of electronic devices, the spin coating method is a conventional method. Most suitable.
도포층을 건조하기 위한 가열처리는, 해당 도포층속의 용제를 적당한 속도로 증발시켜 기판표면상에 건조된 도포막을 형성할 수 있으면 되고, 그 온도 및 시간 등에 대해서는 특히 제한은 없지만, 일반적으로, 건조처리는 80∼300℃의 온도의 핫플레이트상에서, 대기중 또는 질소 등의 불활성 기체분위기하에서 1∼6분간 행하면 된다. 건조를 위한 가열처리는 3단계이상 단계적으로 승온하는 것이 유리하다. 예를 들면, 가열처리는, 전형적으로는, 1회째는 80∼120℃에서 30초∼2분간, 2회째는 130∼220℃에서 30초∼2분간, 최후로는 230∼300℃에서 30초∼2분간 순차 행한다.The heat treatment for drying the coating layer may be carried out by evaporating the solvent in the coating layer at a suitable rate to form a dried coating film on the substrate surface, and the temperature and time are not particularly limited. The treatment may be performed on a hot plate at a temperature of 80 to 300 ° C. for 1 to 6 minutes in the atmosphere or in an inert gas atmosphere such as nitrogen. Heat treatment for drying is advantageously stepped up in three or more stages. For example, the heat treatment is typically 30 seconds to 2 minutes at 80 to 120 ° C for the first time, 30 seconds to 2 minutes at 130 to 220 ° C for the second time, and 30 seconds at 230 to 300 ° C for the last time. It carries out for 2 minutes sequentially.
본 발명의 방법의 (c)공정에 있어서는, 이와 같이 해서 얻어진 기판표면상의 건조된 도포막을, 550∼800℃범위의 온도에서, 이렇게 해서 얻어진 실리카피막중에 규소에 결합된 수소원자가 실질적으로 잔존하지 않을 때까지 소성처리한다. 이때, 소성처리는, 60분이내, 통상 온도에 따라 0.5∼60분범위내에서 완료한다. 온도가 너무 낮으면 소성시간이 충분히 길더라도 규소에 결합된 수소원자의 분해가 거의 완결될 수 없어 균열한계가 높은 만족할만한 실리카피막을 얻을 수 없는 한편, 온도가 너무 높으면, 소스층 및 드레인층의 과도한 확산에 기인해서 반도체소자의 본질적인 성능에 악영향을 미친다. 소성처리를 행하는데 있어서, 필수는 아니지만, 소성로에 넣은 소성처리대상도포막의 온도는, 보다 향상된 특성의 실리카피막을 얻기 위하여 가능한 한 신속하게 소성온도, 예를 들면 600℃에 이르도록 하는 것이 중요하다. 예를 들면, 소성로에 넣은 도포막의 소성온도는 3분이내에 도달하는 것이 바람직하다.In the step (c) of the method of the present invention, the dried coated film on the substrate surface thus obtained is substantially free of hydrogen atoms bonded to silicon in the silica film thus obtained at a temperature in the range of 550 to 800 ° C. Firing until At this time, the baking process is completed within 60 minutes and within a range of 0.5 to 60 minutes depending on the normal temperature. If the temperature is too low, even if the firing time is long enough, decomposition of the hydrogen atoms bonded to silicon can hardly be completed, and a satisfactory silica film with a high cracking limit cannot be obtained. On the other hand, if the temperature is too high, excessive source and drain layers Due to diffusion, the intrinsic performance of the semiconductor device is adversely affected. In carrying out the firing process, although not essential, it is important that the temperature of the coating film to be subjected to the firing treatment to reach the firing temperature as quickly as possible, for example, 600 ° C., in order to obtain a silica coating with improved properties. Do. For example, it is preferable that the baking temperature of the coating film put into the kiln reaches within 3 minutes.
다음에, 본 발명의 방법에 대해서는, 도포액의 제조방법을 먼저 설명하고, 이어서 실시예 및 비교예를 통해 보다 상세히 설명하나, 본 발명은 이들 예에 의해서 그 범위가 한정되는 것은 아니다.Next, the method of the present invention will be described first by the production method of the coating liquid, and then described in more detail through Examples and Comparative Examples, but the scope of the present invention is not limited by these examples.
(제조예 1)(Manufacture example 1)
SiO2로 환산해서 3중량%의 농도에 해당하는 트리에톡시실란 73.9g(0.45몰)을 에틸렌글리콜디메틸에테르 802.0g(9.0몰)에 교반하에 용해해서 반응혼합물을 제조하고, 이 반응혼합물에, 진한 질산 5중량ppm으로 산성화한 물 24.3g(1.35몰)을 서서히 교반하에 적하한 후, 약 3시간 계속 교반하고 나서, 실온에서 6일간 방치하였다.73.9 g (0.45 mol) of triethoxysilane corresponding to a concentration of 3% by weight in SiO 2 was dissolved in 802.0 g (9.0 mol) of ethylene glycol dimethyl ether under stirring to prepare a reaction mixture, and to the reaction mixture, 24.3 g (1.35 mol) of water acidified with 5 ppm by weight of concentrated nitric acid was slowly added dropwise under stirring, and the stirring was continued for about 3 hours, followed by standing at room temperature for 6 days.
다음에, 이 반응혼합물을 120∼140㎜Hg, 40℃에서 1시간 감압증류하여, 불활성 물질 8중량%와 에틸알콜 1중량%를 함유하는 도포액을 얻었다.Next, this reaction mixture was distilled under reduced pressure at 120 to 140 mmHg at 40 ° C. for 1 hour to obtain a coating liquid containing 8% by weight of the inert substance and 1% by weight of ethyl alcohol.
이와 같이 해서 얻어진 도포액의 일부를, 120℃에서 가열함으로써 건조하고, 얻어진 고형물을 분말로 분쇄하고, 열중량분석을 행한 바, 중량증가를 나타내었다.Thus, a part of the coating liquid obtained was dried by heating at 120 degreeC, the obtained solid substance was grind | pulverized into powder, and the thermogravimetric analysis showed the weight increase.
(제조예 2)(Manufacture example 2)
테트라에톡시실란 80.75g(0.53몰)을 에틸알콜 298g(6.48몰)에 교반하에 용해하여 제조한 반응혼합물에, 질산 200중량ppm으로 산성화한 물 76.5g(4.25몰)을 천천히 교반하에 적하한 후, 약 5분간 더욱 교반하고, 5일간 실온에서 방치시키고 나서, 실리콘계 계면활성제(SH30PA, 토레이 실리콘사제품)0.1중량%를 첨가해서 도포액을 얻었다.80.75 g (0.53 mol) of tetraethoxysilane was dissolved in 298 g (6.48 mol) of ethyl alcohol under stirring, and 76.5 g (4.25 mol) of water acidified with 200 ppm by weight of nitric acid was slowly added dropwise to the reaction mixture. After further stirring for about 5 minutes, and allowed to stand at room temperature for 5 days, 0.1 wt% of a silicone surfactant (SH30PA, manufactured by Toray Silicone Co., Ltd.) was added to obtain a coating solution.
이와 같이 해서 얻어진 도포액의 일부를, 120℃에서 가열함으로써 건조하고, 얻어진 고형물을 분말로 분쇄하고, 열중량분석을 행한 바, 중량증가를 나타내지 않았다.Thus, a part of the coating liquid obtained was dried by heating at 120 degreeC, and the obtained solid substance was grind | pulverized into powder and thermogravimetric analysis did not show the weight increase.
(실시예 1)(Example 1)
상기 제조예 1에서 제조한 도포액을, 다결정실리콘으로 형성된 패턴화된 회로배선층을 지닌 반도체실리콘웨이퍼상에, 스피너에 의해 도포하고, 이 웨이퍼를 핫플레이트상에서 처음에는 100℃에서 1분간, 다음에는 200℃에서 1분간, 최후로는 300℃에서 1분간 가열함으로써 건조시켜 건조된 도포막을 얻었다.The coating liquid prepared in Preparation Example 1 was applied by a spinner on a semiconductor silicon wafer having a patterned circuit wiring layer formed of polycrystalline silicon, and the wafer was first applied at 100 ° C. on a hot plate for 1 minute, and then It dried by heating at 200 degreeC for 1 minute and finally at 300 degreeC for 1 minute, and obtained the dried coating film.
상기 가열전과, 100℃, 200℃ 및 300℃에 있어서의 가열후의 건조과정에서의 도포층의 적외흡수스펙트럼의 측정을 행한 바, 각각 Ⅰ,Ⅱ,Ⅲ 및 Ⅳ의 스펙트럼으로 도 1에 표시한 결과가 얻어졌다. 이들 각 스펙트럼은, 파수 2250㎝-1부근에서 Si-H결합에 기인하는 강한 흡수띠를 지니고 있다.The infrared absorption spectrum of the coating layer was measured before the heating and during the drying process at 100 ° C., 200 ° C. and 300 ° C., and the results shown in FIG. 1 by the spectra of I, II, III and IV, respectively. Was obtained. Each of these spectra has a strong absorption band attributable to Si-H bonds near the wave number 2250 cm -1 .
다음에, 상기 웨이퍼를 건조로에서 꺼내어 실온까지 냉각하고, 해당 웨이퍼상의 건조된 도포막에, 자외선조사장치(Deep UV Processor; 닛뽄덴찌사제품)에 의해 파장 185∼254㎚의 원자외선을 포함하는 자외선을, 1200J/㎝2의 조사량이 되도록 대기중에서 1분간 조사하였다.Next, the wafer is taken out of the drying furnace and cooled to room temperature, and ultraviolet rays containing ultraviolet rays having a wavelength of 185 to 254 nm are applied to the dried coated film on the wafer by a deep UV processor (manufactured by Nippon Denchi Co., Ltd.). Was irradiated for 1 minute in the air so that the irradiation amount of 1200 J / cm <2> .
그후, 상기와 동일한 도포액을, 상기 자외선조사된 도포막상에 스피너에 의해 도포하여, 얻어진 제 2도포막을 상기와 마찬가지로 가열처리하여 건조시켰다.Then, the same coating liquid as above was apply | coated with the spinner on the said ultraviolet-ray irradiated coating film, and the obtained 2nd coating film was heated and dried similarly to the above.
최후로, 이와 같이 해서 얻어진 도포막을 대기중, 600℃에서 30분간 소성처리하여 두께 450㎚의 실리카피막을 얻었다. 이와 같이 해서 얻어진 피막을 주사형전자현미경에 의해 관찰한 바, 표면에서 균열발생을 검출할 수 없었다. 도 2는 이 피막의 적외흡수스펙트럼이며, 이것으로부터, 파수 2250㎝-1근방에서 Si-H결합에 기인하는 흡수띠가 완전히 소실되어, 피막이 완전히 실리카자체로부터 형성되었음을 알 수 있다.Finally, the coating film thus obtained was calcined at 600 ° C. for 30 minutes in the air to obtain a silica film having a thickness of 450 nm. The film thus obtained was observed with a scanning electron microscope, whereby cracking could not be detected on the surface. Fig. 2 shows the infrared absorption spectrum of this film. From this, it can be seen that the absorption band due to the Si-H bond disappeared completely near the wave number 2250 cm -1 , and the film was completely formed from the silica itself.
(실시예 2)(Example 2)
실시예 1에 있어서 600℃에서의 소성처리를 대기대신에 수증기분위기중에서 행한 것을 제외하고 실시예 1과 마찬가지로 해서 실리카피막을 형성하였다. 이와 같이 해서 얻어진 피막은 두께가 450㎚였고, 주사형전자현미경에 의한 관찰결과 균열발생은 없었다.In Example 1, a silica coating was formed in the same manner as in Example 1 except that the firing treatment at 600 ° C. was performed in a steam atmosphere instead of the atmosphere. The film thus obtained had a thickness of 450 nm and no crack was observed as a result of the observation with a scanning electron microscope.
(비교예)(Comparative Example)
실시예 1에 있어서, 도포액으로서 제조예 2에서 제조한 도포액을 이용하고, 도포막의 소성처리를 대기중, 600℃가 아니라 400℃에서 30분간 행한 것을 제외하고 실시예 1과 마찬가지로 해서 얻어진 실리카피막은, 그 두께가 450㎚였고, 주사형전자현미경에 의한 관찰결과 균열이 있었으므로, 소성시간의 연장이나 소성온도의 증가는 무의미하다는 것을 시사하였다.In Example 1, a silica obtained in the same manner as in Example 1, except that the coating liquid prepared in Production Example 2 was used as the coating liquid, and the baking treatment of the coating film was performed for 30 minutes at 400 ° C instead of 600 ° C in the air. The thickness of the film was 450 nm, and the results of the observation by the scanning electron microscope revealed cracks, suggesting that the extension of the firing time and the increase of the firing temperature were insignificant.
이상, 본 발명의 방법에 의하면, 반도체소자나 액정표시패널의 제조에 있어서 평탄화막이나 층간절연막 등으로서 기능하는 균열한계가 높은 실리카피막을, 도포액에 의한 도포에 의해 소스층 및 드레인층의 과도한 확산이 일어나지 않도록 효율좋게 형성하는 것이 가능하다.As described above, according to the method of the present invention, in the manufacture of a semiconductor device or a liquid crystal display panel, a silica film having a high cracking limit functioning as a flattening film or an interlayer insulating film or the like is excessively applied to the source layer and the drain layer by coating with a coating liquid. It is possible to form efficiently so that diffusion does not occur.
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| JP3977896B2 (en) * | 1997-05-28 | 2007-09-19 | 新日本製鐵株式会社 | Low dielectric constant material |
| 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 |
| JP5128044B2 (en) * | 2003-12-10 | 2013-01-23 | 東京応化工業株式会社 | Method for producing a silica-based coating material for coating a silicon substrate provided with a silicon substrate or a metal wiring pattern |
| JP4437456B2 (en) | 2005-04-20 | 2010-03-24 | 東京応化工業株式会社 | Coating 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05315319A (en) * | 1992-05-12 | 1993-11-26 | Catalysts & Chem Ind Co Ltd | Semiconductor device and its manufacture |
| JPH0766188A (en) * | 1993-08-26 | 1995-03-10 | Catalysts & Chem Ind Co Ltd | Semiconductor device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2035367A1 (en) * | 1990-02-22 | 1991-08-23 | Ronald H. Baney | Precursor polymer for ceramic coatings |
| JPH07335639A (en) * | 1994-06-07 | 1995-12-22 | Kawasaki Steel Corp | Manufacture of semiconductor device |
| JP3192947B2 (en) * | 1995-11-16 | 2001-07-30 | 東京応化工業株式会社 | Method for producing coating liquid for forming silica-based coating |
| JP3909912B2 (en) * | 1997-05-09 | 2007-04-25 | 東京応化工業株式会社 | Silica-based thick film coating method |
-
1997
- 1997-05-12 JP JP12068597A patent/JP3635443B2/en not_active Expired - Fee Related
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05315319A (en) * | 1992-05-12 | 1993-11-26 | Catalysts & Chem Ind Co Ltd | Semiconductor device and its manufacture |
| JPH0766188A (en) * | 1993-08-26 | 1995-03-10 | Catalysts & Chem Ind Co Ltd | Semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10313002A (en) | 1998-11-24 |
| KR19980086911A (en) | 1998-12-05 |
| JP3635443B2 (en) | 2005-04-06 |
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