JP2011168420A - Alumina sintered compact and substrate holding board formed by alumina sintered compact - Google Patents
Alumina sintered compact and substrate holding board formed by alumina sintered compact Download PDFInfo
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Abstract
Description
本発明は、アルミナを主成分とする焼結体（以下、アルミナ系セラミックスともいう）に関するものであり、更に詳しくは、光反射率が低い、黒色のアルミナ系セラミックスに関する。 The present invention relates to a sintered body containing alumina as a main component (hereinafter also referred to as alumina-based ceramics), and more particularly, to a black alumina-based ceramic with low light reflectance.
この黒色アルミナ系セラミックスは、液晶ディスプレイや半導体素子を製造する際に用いる露光装置等の基板保持盤などに用いることができる。露光装置の基板保持盤に黒色アルミナ系セラミックスを用いると、光反射率が低いことにより、液晶基板等を透過した光が反射することで露光、アライメント或いはフォーカス調整を損なうことがない。 This black alumina-based ceramic can be used for a substrate holder such as an exposure apparatus used when manufacturing a liquid crystal display or a semiconductor element. When black alumina-based ceramics is used for the substrate holding plate of the exposure apparatus, light, which has passed through the liquid crystal substrate or the like is reflected by the low light reflectance, so that exposure, alignment or focus adjustment is not impaired.
また、黒色アルミナ系セラミックスは、露光装置等の基板保持盤以外にも、低光反射率や黒色であることが要求される冶具、部材、産業機械の部品、或いは、事務用品、理化学用品、生体用材料、医療用具などに用いることができる。 Black alumina ceramics are used for jigs, members, parts of industrial machines, office supplies, physics and chemistry supplies, biological materials that are required to have low light reflectivity and blackness, in addition to substrate holders such as exposure apparatuses. It can be used for medical materials and medical devices.
なお、本明細書においては、光反射率とは正反射量でなく全反射量を対象とした全反射率であって、ある面に照射された光の入射束に対する反射束の比である。
全反射率は、ＪＩＳ Ｚ８７２２−２０００に準じて、例えば、コニカミノルタ製の分光測色計（ＳＰＥＣＴＲＯＰＨＯＴＯＭＥＴＥＲ ＣＭ−３７００ｄ）などの装置を用いて測定することができる。
In the present specification, the light reflectance is the total reflectance for the total reflection amount, not the regular reflection amount, and is the ratio of the reflection bundle to the incident bundle of light irradiated on a certain surface.
The total reflectance can be measured according to JIS Z8722-2000, for example, using a device such as a spectrocolorimeter (SPECTROTOPOMETER CM-3700d) manufactured by Konica Minolta.
従来、黒色で光反射率が低いアルミナ系セラミックスとしては、下記の特許文献１〜３に記載されたものなどがある。 Conventionally, examples of alumina ceramics that are black and have low light reflectance include those described in Patent Documents 1 to 3 below.
特許文献１には、Ａｌ２Ｏ３を主成分とし、「（ａ）Ｍｎ２Ｏ３およびＦｅ２Ｏ3」、「（ｂ）Ｆｅ２Ｏ3およびＣｏＯ」並びに「（ｃ）Ｃｒ２Ｏ３、Ｍｎ２Ｏ３、Ｆｅ２Ｏ3およびＣｏＯから選ばれる３種又は４種」から選ばれる成分を２〜５重量％含有する黒色アルミナ焼結体が記載されている。 Patent Document 1 includes Al 2 O 3 as a main component, and “(a) Mn 2 O 3 and Fe 2 O 3 ”, “(b) Fe 2 O 3 and CoO”, and “(c) Cr 2 O 3”. A black alumina sintered body containing 2 to 5% by weight of a component selected from “3 or 4 types selected from Mn 2 O 3 , Fe 2 O 3 and CoO” is described.
特許文献２には、比剛性が８０ＧＰａ・ｃｍ３／ｇ以上の黒色系セラミックスから形成されるとともに、上記支持面の算術平均粗さが０．３〜１．２μｍの範囲としたことを特徴とする液晶基板保持盤が記載されている。また、前記黒色系セラミックスの具体的な組成としては、ＴｉＯ２、ＣｏＯ、ＭｎＯ２、またはＦｅ２Ｏ３のいずれか１種以上を含有したアルミナであること、アルミナの純度が９０％以上であることが記載されている。 Patent Document 2 is characterized in that it is formed from black ceramics having a specific rigidity of 80 GPa · cm 3 / g or more, and the arithmetic average roughness of the support surface is in the range of 0.3 to 1.2 μm. A liquid crystal substrate holder is described. The specific composition of the black ceramic is alumina containing at least one of TiO 2 , CoO, MnO 2 , and Fe 2 O 3 , and the purity of the alumina is 90% or more. It is described.
特許文献３には、少なくとも基板保持側表面がセラミックスからなり、該基板保持側表面の彩度指数ｂ＊がプラスであり、明度指数Ｌ＊が７０以下で、かつ面粗度Ｒａが０．６μｍ以下であることを特徴とする露光処理用基板保持盤が記載されている。また、前記セラミックスの具体的な組成としては、アルミナを主成分として、Ｆｅ２Ｏ３、Ｍｎ２Ｏ３、Ｃｒ２Ｏ３、ＣｏＯ、ＴｉＯ２、ＣｕＯ、ＮｉＯ、ＴｉＣ、ＳｉＣおよびＣからなる群から選ばれた少なくとも１つの添加物を含むものが記載されている。 In Patent Document 3, at least the substrate holding side surface is made of ceramics, the saturation index b * of the substrate holding side surface is positive, the lightness index L * is 70 or less, and the surface roughness Ra is 0.6 μm. A substrate holder for exposure processing, which is characterized by the following, is described. In addition, the specific composition of the ceramic is a group consisting of alumina as a main component, Fe 2 O 3 , Mn 2 O 3 , Cr 2 O 3 , CoO, TiO 2 , CuO, NiO, TiC, SiC, and C. Those containing at least one additive selected from:
しかし、これらの特許文献に記載された組成のアルミナ系セラミックスは、セラミックスを焼成したままの未加工の焼成面は黒色であって光反射率が低いものの、研磨や切断等の加工をした面は、未加工面ほどの黒さはなく、未加工面ほどの低い光反射率を示さないという問題があった。 However, the alumina-based ceramics having the composition described in these patent documents have an unprocessed fired surface that has been fired as the ceramic is black and has a low light reflectance, but the surface that has been subjected to processing such as polishing or cutting is not There is a problem that the black surface is not as black as the unprocessed surface and the light reflectance is not as low as that of the unprocessed surface.
この問題を解決し、加工面においても低い光反射率を実現するために、特許文献３では、セラミックスの彩度指数ｂ＊がプラスであり、明度指数Ｌ＊が７０以下で、かつ面粗度Ｒａが０．６μｍ以下であることを必須としている。この方法でも、光反射率が低い加工面をえることはできたが、面粗度Ｒａが０．６μｍ以下とする加工には手間が掛かった。 In order to solve this problem and realize low light reflectance even on the processed surface, in Patent Document 3, the chroma index b * of ceramics is positive, the brightness index L * is 70 or less, and the surface roughness is high. It is essential that Ra is 0.6 μm or less. Even with this method, it was possible to obtain a processed surface with low light reflectivity, but it took time and effort to make the surface roughness Ra 0.6 μm or less.
一方、液晶ディスプレイや半導体素子を製造する際の露光処理に用いる露光装置においては、液晶基板等を透過した光を基板保持盤が反射することで露光、アライメント或いはフォーカス調整を損なうといった不具合がないように、光反射率が低い基板保持盤が求められていた。 On the other hand, in an exposure apparatus used for an exposure process when manufacturing a liquid crystal display or a semiconductor element, the substrate holding disk reflects the light transmitted through the liquid crystal substrate or the like so that the exposure, alignment, or focus adjustment is not impaired. In addition, a substrate holding plate having a low light reflectance has been demanded.
本発明者らは、容易な方法で、加工面の低光反射率を実現するために検討を重ね、アルミナ系セラミックスのアルミナ成分に対して、特定の金属酸化物を特定の添加量で添加することによって、未加工の焼成面だけでなく、加工面においても光反射率が低いアルミナ系セラミックスが得られることを見出し、本発明に至った。 The inventors of the present invention have repeatedly studied to realize a low light reflectance of the processed surface by an easy method, and add a specific metal oxide in a specific addition amount to the alumina component of the alumina-based ceramics. As a result, it was found that an alumina-based ceramic having a low light reflectivity not only on an unprocessed fired surface but also on a processed surface was obtained, and the present invention was achieved.
上記の課題を解決した本発明は、アルミナを主成分とする焼結体であって、アルミナを８０〜８８質量％含有し、且つＣｏ、Ｍｎ、Ｆｅ、及びＴｉの中から選ばれる１種以上を酸化物換算で８〜２０質量％含有することを特徴とするアルミナ焼結体である。 The present invention that has solved the above problems is a sintered body mainly composed of alumina, containing 80 to 88% by mass of alumina, and one or more selected from Co, Mn, Fe, and Ti. Is an alumina sintered body characterized by containing 8 to 20% by mass in terms of oxide.
なお、アルミナ焼結体は、Ｃｏ、Ｍｎ、Ｆｅ、およびＴｉを全て含むことが好ましい。そして、それらの含有量は、Ｃｏを酸化物換算で１〜５質量％、Ｍｎを酸化物換算で２〜１５質量％、Ｆｅを酸化物換算で２〜１５質量％、Ｔｉを酸化物換算で０．１〜１．５質量％であることが好ましい。 The alumina sintered body preferably contains all of Co, Mn, Fe, and Ti. And those contents are Co 1-5 mass% in conversion of oxide, Mn 2-15 mass% in conversion of oxide, Fe 2-15 mass% in conversion of oxide, Ti in conversion of oxide. It is preferable that it is 0.1-1.5 mass%.
このアルミナ焼結体は、露光処理に用いる露光装置の基板保持盤などに利用することができる。基板保持盤とは、液晶ディスプレイや半導体素子等の基板を乗せて保持する部材であって、基板を保持する支持面に複数の突起部を有するものなどがある。
This alumina sintered body can be used for a substrate holding plate of an exposure apparatus used for exposure processing. The substrate holding board is a member that holds a substrate such as a liquid crystal display or a semiconductor element and has a plurality of protrusions on a support surface that holds the substrate.
本発明のアルミナ焼結体は、焼成したままの未加工の焼成面だけでなく、研磨や切断等の加工をした加工面においても光反射率が低く、黒色を示す。 The alumina sintered body of the present invention has a low light reflectivity and exhibits a black color not only on an unfired fired surface that has been fired but also on a worked surface that has been processed such as polishing or cutting.
また、このアルミナ焼結体によって形成した基板保持盤は、光反射率が低いことにより、液晶基板等を透過した光が反射することによる露光装置の不具合を抑えることができる。
In addition, since the substrate holding disk formed of this alumina sintered body has a low light reflectance, it is possible to suppress problems of the exposure apparatus due to reflection of light transmitted through the liquid crystal substrate or the like.
本発明は、アルミナを主成分とする焼結体であって、アルミナを８０〜８８質量％含有し、且つＣｏ、Ｍｎ、Ｆｅ、およびＴｉの中から選ばれる１種以上を酸化物換算で８〜２０質量％含有することを特徴とするアルミナ焼結体である。 The present invention is a sintered body containing alumina as a main component, containing 80 to 88% by mass of alumina, and at least one selected from Co, Mn, Fe, and Ti in terms of oxide. It is an alumina sintered body characterized by containing -20 mass%.
アルミナ焼結体がＣｏ、Ｍｎ、Ｆｅ、およびＴｉの中から選ばれる１種以上の金属が上記の含有量で含有していることで、アルミナ焼結体は、未加工の焼成面だけでなく、加工面においても光反射率が低く、黒色を示す。 Since the alumina sintered body contains at least one metal selected from the group consisting of Co, Mn, Fe, and Ti in the above content, the alumina sintered body is not only a raw fired surface. Also on the processed surface, the light reflectance is low and black.
アルミナの含有量が８８質量％を超えるアルミナ焼結体は、焼成したままの未加工の焼成面は光反射率が低く、黒色を示すものの、その未加工面に研磨等の加工を施すと、加工された面は未加工面ほどの黒さがなく、未加工面と比較するとやや白っぽい仕上がりとなり、光反射率も高くなってしまう。 The alumina sintered body having an alumina content exceeding 88% by mass, the raw fired surface as it is fired has a low light reflectivity and shows black, but when the raw surface is subjected to processing such as polishing, The processed surface is not as black as the unprocessed surface, has a slightly whitish finish compared to the unprocessed surface, and increases the light reflectance.
また、アルミナの含有量が８０質量％未満のものは、十分な強度が得られず、例えば、このアルミナ焼結体を露光装置の基板保持盤に利用する場合などにおいて、アルミナ焼結体の加工時、又は基板保持盤としての使用時に材料の変形・欠損等の不具合を生じ易い。アルミナの含有量が８０質量％であれば、十分な強度を持つアルミナ焼結体を得ることができる。具体的にはヤング率が１８０ＧＰａ以上のアルミナ焼結体を容易に得ることができる。 In addition, when the alumina content is less than 80% by mass, sufficient strength cannot be obtained. For example, when the alumina sintered body is used for a substrate holding plate of an exposure apparatus, the alumina sintered body is processed. At times, or when used as a substrate holder, problems such as material deformation and defects are likely to occur. When the content of alumina is 80% by mass, an alumina sintered body having sufficient strength can be obtained. Specifically, an alumina sintered body having a Young's modulus of 180 GPa or more can be easily obtained.
なお、アルミナと、Ｃｏ、Ｍｎ、Ｆｅ、およびＴｉの中から選ばれる１種以上との含有量は、アルミナが８０〜８８質量％、且つＣｏ、Ｍｎ、Ｆｅ、およびＴｉの中から選ばれる１種以上を酸化物換算で１０〜２０質量％であることがより好ましく、アルミナが８０〜８６質量％、且つＣｏ、Ｍｎ、Ｆｅ、およびＴｉの中から選ばれる１種以上を酸化物換算で１２〜２０質量％であることが特に好まし。この範囲にあるものは、未加工面と加工面の光反射率の差が特に小さい。 The content of alumina and one or more selected from Co, Mn, Fe and Ti is 80 to 88% by mass of alumina and 1 selected from Co, Mn, Fe and Ti. It is more preferable that the amount of seeds or more is 10 to 20% by mass in terms of oxides, alumina is 80 to 86% by mass, and one or more types selected from Co, Mn, Fe, and Ti are 12 in terms of oxides. Particularly preferred is ~ 20% by weight. In this range, the difference in light reflectance between the unprocessed surface and the processed surface is particularly small.
また、Ｃｏ、Ｍｎ、Ｆｅ、およびＴｉの中から選ばれる金属は、ＦｅおよびＴｉを必須成分として３種類以上を含有することが好ましく、４種類全てを含有することが特に好ましい。これらのうちＦｅおよびＴｉを必須成分として３種類以上を含有することによって、未加工面がより黒く、光反射率が低いアルミナ焼結体を得ることができる。また、４種類全てを含有している場合は、未加工面と加工面の反射率の差が特に小さくすることができる。 In addition, the metal selected from Co, Mn, Fe, and Ti preferably contains three or more types, particularly preferably all four types, with Fe and Ti as essential components. Among these, by containing three or more of Fe and Ti as essential components, an alumina sintered body having a green surface and a low light reflectance can be obtained. Moreover, when all four types are contained, the difference in reflectance between the unprocessed surface and the processed surface can be particularly reduced.
このとき、Ｃｏ、Ｍｎ、Ｆｅ、およびＴｉのそれぞれの含有量は、Ｃｏを酸化物換算で１〜５質量％、Ｍｎを酸化物換算で２〜１５質量％、Ｆｅを酸化物換算で２〜１５質量％、Ｔｉを酸化物換算で０．１〜１．５質量％であることが好ましい。それぞれの含有量がこの範囲であれば、未加工の焼成面の光反射率が特に小さく、且つ未加工面と加工面の反射率の差が特に小さい。 At this time, the content of each of Co, Mn, Fe, and Ti is as follows: Co is 1 to 5% by mass in terms of oxide, Mn is 2 to 15% by mass in terms of oxide, and Fe is 2 to 2 in terms of oxide. It is preferable that 15 mass% and Ti are 0.1-1.5 mass% in terms of oxide. If the respective contents are within this range, the light reflectance of the raw fired surface is particularly small, and the difference in reflectance between the raw surface and the processed surface is particularly small.
本発明のアルミナ焼結体は、未加工の焼成面だけでなく、加工面においても光反射率が低く、黒色を示すという特徴があり、アルミナ焼結体を焼成した後に加工を施すことを前提としたものである。従って、加工時に材料の変形・欠損等の不具合を生じにくいものであることが好ましい。そのため、アルミナ焼結体の気孔率は、５％以下であることが好ましく、２％以下であることがより好ましく、１％以下であることが特に好ましい。前記気孔率が大きいものは、加工する際に、加工した部分の近辺に欠損や変形といった不具合を生じ易いため好ましくない。 The alumina sintered body of the present invention is characterized in that it has a low light reflectivity not only on an unprocessed fired surface but also on the processed surface and exhibits black color, and is premised on processing after firing the alumina sintered body. It is what. Therefore, it is preferable that the material does not easily cause problems such as deformation or defect of the material during processing. Therefore, the porosity of the alumina sintered body is preferably 5% or less, more preferably 2% or less, and particularly preferably 1% or less. A material having a high porosity is not preferred because it tends to cause defects such as defects and deformation in the vicinity of the processed part.
（製造方法）
以下に本発明のアルミナ焼結体の製造方法の一例を示す。なお、本発明のアルミナ焼結体の製造方法は下記の方法に限定されるものではなく、下記以外の製造方法で製造しても構わない。
(Production method)
An example of the manufacturing method of the alumina sintered body of the present invention is shown below. In addition, the manufacturing method of the alumina sintered compact of this invention is not limited to the following method, You may manufacture with the manufacturing methods other than the following.
アルミナ焼結体は、アルミナ（Ａｌ２Ｏ３）の粉末と、Ｃｏの酸化物（ＣｏＯ、ＣＯ２Ｏ3、ＣＯ3Ｏ4）の粉末、Ｍｎの酸化物（ＭｎＯ、ＭｎＯ２）の粉末、Ｆｅの酸化物（ＦｅＯ、Ｆｅ２Ｏ３、Ｆｅ3Ｏ4）の粉末、およびＴｉの酸化物（ＴｉＯ２）の粉末から選ばれる１種以上、バインダー、及び溶媒を含有するスラリーを焼成することで得ることができる。 The alumina sintered body includes alumina (Al 2 O 3 ) powder, Co oxide (CoO, CO 2 O 3 , CO 3 O 4 ) powder, Mn oxide (MnO, MnO 2 ) powder, Firing a slurry containing at least one selected from Fe oxide (FeO, Fe 2 O 3 , Fe 3 O 4 ) powder and Ti oxide (TiO 2 ) powder, a binder, and a solvent. Can be obtained at
また、Ｃｏ、Ｍｎ、Ｆｅ、およびＴｉを添加するには、上記したようなこれらの酸化物の粉末をスラリーに含有させる以外にも、これらを含む化合物のうち焼成によって酸化物を形成できる化合物の粉末をスラリーに含有させてもよい。 Further, in order to add Co, Mn, Fe, and Ti, in addition to the above-mentioned powder of these oxides contained in the slurry, among the compounds containing these, compounds that can form oxides by firing are included. Powder may be included in the slurry.
また、スラにーには本発明の効果を損なわない範囲において、上記以外の添加剤を含有させてもよい。添加剤は、セラミックスラリーに一般的に用いられるものを適宜選択すればよい。 Further, additives other than those described above may be incorporated into the slurry as long as the effects of the present invention are not impaired. What is necessary is just to select an additive generally used for a ceramic slurry suitably.
このようなスラリーは、例えば、成形型にスラリーを充填して乾燥してスラリーの乾燥体とし、それを１２００〜１６００℃の温度で焼成することでアルミナ焼結体となる。 Such a slurry is formed into an alumina sintered body by, for example, filling a molding die with the slurry and drying it to obtain a dried body of the slurry, which is fired at a temperature of 1200 to 1600 ° C.
（表面加工）
以上のように製造したアルミナ焼結体は、その用途に応じて、表面を加工することがある。加工の方法は特に限定されず、通常のアルミナ焼結体やその他のセラミックを加工する方法であればよく、例えば、ブラスト処理、研磨、研削、或いは切断等の加工を行えばよい。
(Surface processing)
The alumina sintered body produced as described above may have a surface processed depending on its use. The processing method is not particularly limited as long as it is a method for processing a normal alumina sintered body or other ceramics. For example, blasting, polishing, grinding, cutting, or the like may be performed.
本発明のアルミナ焼結体では、研磨面や切断面のように加工によって作られた加工面も、未加工の焼成面のように黒く、光反射率が低い。 In the alumina sintered body of the present invention, a processed surface made by processing such as a polished surface or a cut surface is black like an unprocessed fired surface and has low light reflectance.
更に、加工によって形成される面の算術平均粗さＲａが０．２８μｍ以下、特に好ましくは０．２５μｍ以下であれば、加工面をより黒くでき、光反射率を低く抑えることができる。また、面の加工が容易であることから算術平均粗さＲａは０．０１μｍ以上であることが好ましい。
なお、算術平均粗さＲａとは、ＪＩＳ Ｂ０６０１−２００１で定義された数値である。
Furthermore, if the arithmetic average roughness Ra of the surface formed by processing is 0.28 μm or less, particularly preferably 0.25 μm or less, the processed surface can be made blacker and the light reflectance can be kept low. In addition, since the surface processing is easy, the arithmetic average roughness Ra is preferably 0.01 μm or more.
The arithmetic average roughness Ra is a numerical value defined in JIS B0601-2001.
（使用例）
本発明のアルミナ焼結体は、液晶ディスプレイや半導体素子を製造する際の露光処理に用いる露光装置の基板保持盤等に好適に用いることができる。
(Example of use)
The alumina sintered body of the present invention can be suitably used for a substrate holding plate of an exposure apparatus used for an exposure process when manufacturing a liquid crystal display or a semiconductor element.
露光装置の基板保持盤については、先に示した特許文献２（特開２００５−２７５３４５号公報）、特許文献３（特開２００６−２１０５４６号公報）などにも記載されている。基板保持盤は、光反射率が大きいと露光装置に不具合を発生させてしまう場合があり、例えば、特許文献２に記載されたものは波長４５０ｎｍ以下の照射光で正反射率が１％以下、或いは、特許文献３に記載されたものは波長２５０〜５５０ｎｍの範囲における全反射率が１３％以下といったように、光反射率が低いことが要求される。 The substrate holding plate of the exposure apparatus is also described in Patent Document 2 (Japanese Patent Laid-Open No. 2005-275345), Patent Document 3 (Japanese Patent Laid-Open No. 2006-210546), and the like. If the substrate holding plate has a high light reflectance, it may cause a problem in the exposure apparatus. For example, the one described in Patent Document 2 has a regular reflectance of 1% or less with irradiation light having a wavelength of 450 nm or less, Alternatively, the device described in Patent Document 3 is required to have a low light reflectance such that the total reflectance in a wavelength range of 250 to 550 nm is 13% or less.
また、基板保持盤を製造するには、高精度で複雑な加工が必要であり、加工時に変形せず、また、基板保持盤に基板をのせた際に変形しないだけの十分な強度を備えている必要がある。また、基板保持盤は露光装置への付加が少なく、取り扱いが容易である軽量のものが好ましく、そのためには厚みが薄くする必要がある。基板保持盤の適正な厚みは、基板の大きさによってやや異なるが、１０ｍｍ以下であることが好ましく、８ｍｍ以下であることが特に好ましい。 In addition, manufacturing a substrate holding plate requires high-precision and complicated processing, and it has sufficient strength not to be deformed during processing and not to be deformed when the substrate is placed on the substrate holding plate. Need to be. In addition, the substrate holding plate is preferably a lightweight one that is less likely to be added to the exposure apparatus and is easy to handle. For this purpose, it is necessary to reduce the thickness. The appropriate thickness of the substrate holder is slightly different depending on the size of the substrate, but is preferably 10 mm or less, and particularly preferably 8 mm or less.
このように軽量で変形しにくい基板保持盤を得るためには、基板保持盤に使用するアルミナ焼結体は、ヤング率が１８０ＧＰａ以上であることが好ましい。 In order to obtain such a lightweight and difficult-to-deform substrate holding plate, the alumina sintered body used for the substrate holding plate preferably has a Young's modulus of 180 GPa or more.
また、基板保持盤は、基板保持盤と基板との接地面積を小さくするために、基板と接地する支持面に複数の突起部を設けて、突起部によって基板を支持することが好ましい。 Further, in order to reduce the ground contact area between the substrate holder and the substrate, the substrate holder is preferably provided with a plurality of protrusions on a support surface that contacts the substrate, and the substrate is supported by the protrusions.
また、基板保持盤は、露光装置への取り付けのために孔あけや研削等の加工を施される。このように、基板保持盤を形成する際には、焼結材を焼成した後に表面を加工することが多く、加工面においても光反射率が低い素材が求められる。 In addition, the substrate holding plate is subjected to processing such as drilling and grinding for attachment to the exposure apparatus. As described above, when forming the substrate holding disk, the surface is often processed after firing the sintered material, and a material having low light reflectivity is also required on the processed surface.
本発明のアルミナ焼結体は、基板保持盤として使用するのに十分なヤング率を持ち、未加工面であっても、加工面であっても光反射率を低く抑えることができるため、基板保持盤の素材として好適である。 The alumina sintered body of the present invention has a Young's modulus sufficient to be used as a substrate holding disk, and can suppress the light reflectance low even on an unprocessed surface or a processed surface. It is suitable as a material for the holding plate.
本発明のアルミナ焼結体を以下の手順で製造した。 The alumina sintered body of the present invention was produced by the following procedure.
まず、アルミナ焼結材の原料として、以下のセラミック粉末、バインダー、溶媒、添加剤を用いてスラリーを製造した。 First, a slurry was produced using the following ceramic powder, binder, solvent, and additive as a raw material for the alumina sintered material.
セラミック粉末として、高純度アルミナ粉末（純度９９質量％以上、平均粒径０．６μｍ）、Ｃｏ３Ｏ４粉末（純度約７５質量％、平均粒径２μｍ）、ＭｎＯ２粉末（純度約７５質量％、平均粒径２μｍ）、Ｆｅ２Ｏ３粉末（純度約７５質量％、平均粒径２μｍ）およびＴｉＯ２粉末（純度９９質量％以上、平均粒径０．２μｍ）を用いた。 As ceramic powder, high-purity alumina powder (purity 99% by mass or more, average particle size 0.6 μm), Co 3 O 4 powder (purity about 75% by mass, average particle size 2 μm), MnO 2 powder (purity about 75% by mass) , Average particle size 2 μm), Fe 2 O 3 powder (purity about 75 mass%, average particle size 2 μm) and TiO 2 powder (purity 99 mass% or more, average particle size 0.2 μm).
バインダーとしてポリエステル樹脂エマルション（固形分３０質量％）、溶媒として水（イオン交換水）を用いた。また、その他の添加剤として、分散剤、増粘剤等を用いた。 A polyester resin emulsion (solid content 30% by mass) was used as a binder, and water (ion-exchanged water) was used as a solvent. Moreover, a dispersant, a thickener, etc. were used as other additives.
スラリーを調整するにあたり、事前に上記した原料のうちＣｏ３Ｏ４粉末、ＭｎＯ２粉末、Ｆｅ２Ｏ３粉末およびＴｉＯ２粉末を、Ｃｏ３Ｏ４：ＭｎＯ２：Ｆｅ２Ｏ３：ＴｉＯ２の比率が質量比で４：４：４：１となるように混合して、混合粉末Ａを得た。 In preparing the slurry, Co 3 O 4 powder, MnO 2 powder, Fe 2 O 3 powder, and TiO 2 powder among the above-described raw materials were changed to Co 3 O 4 : MnO 2 : Fe 2 O 3 : TiO 2 . Mixing was performed so that the ratio was 4: 4: 4: 1 in terms of mass ratio, whereby mixed powder A was obtained.
この混合粉末Ａとアルミナ粉末、バインダー、溶媒、及び添加剤を以下に示す配合割合で混合,攪拌し、以下の各スラリーを調製した。 This mixed powder A, alumina powder, binder, solvent, and additive were mixed and stirred at the following blending ratios to prepare the following respective slurries.
（実施例１のスラリー配合）
アルミナ粉末：８３質量部、混合粉末Ａ：１７質量部、バインダー：５０質量部、溶媒：１５質量部、添加剤：２質量部。
(Slurry formulation of Example 1)
Alumina powder: 83 parts by mass, mixed powder A: 17 parts by mass, binder: 50 parts by mass, solvent: 15 parts by mass, additive: 2 parts by mass.
（実施例２のスラリー配合）
アルミナ粉末：８８質量部、混合粉末Ａ：１２質量部、バインダー：５０質量部、溶媒：１５質量部、添加剤：２質量部。
(Slurry formulation of Example 2)
Alumina powder: 88 parts by mass, mixed powder A: 12 parts by mass, binder: 50 parts by mass, solvent: 15 parts by mass, additive: 2 parts by mass.
（比較例１のスラリー配合）
アルミナ粉末：９３質量部、混合粉末Ａ：７質量部、バインダー：５０質量部、溶媒：１５質量部、添加剤：２質量部。
(Slurry formulation of Comparative Example 1)
Alumina powder: 93 parts by mass, mixed powder A: 7 parts by mass, binder: 50 parts by mass, solvent: 15 parts by mass, additive: 2 parts by mass.
次に、これらのスラリーを成形型に流し込み、乾燥して硬化させ、各スラリーからなる２０ｃｍ×２０ｃｍ×厚み５ｍｍのセラミックの未焼成体を作製した。 Next, these slurries were poured into a mold, dried and hardened, and a 20 cm × 20 cm × 5 mm thick ceramic unfired body made of each slurry was produced.
次に、これらの未焼成体を１４５０℃で約４時間焼成して、各スラリーからなるアルミナ焼結体を得た。各アルミナ焼結体の気孔率は１％以下であった。 Next, these unfired bodies were fired at 1450 ° C. for about 4 hours to obtain alumina sintered bodies made of the respective slurries. The porosity of each alumina sintered body was 1% or less.
なお、実施例１のアルミナ焼結体は、アルミナを８３質量％、ＣｏをＣｏ３Ｏ４換算、ＭｎをＭｎＯ２換算、ＦｅをＦｅ２Ｏ３換算、ＴｉをＴｉＯ２換算でそれらを合わせて１３．１質量％含有し、更にそれら以外の物質（主には、ＭｎＯ２等の粉末の不純物）を含有していた。 The alumina sintered body of Example 1 was obtained by combining 83% by mass of alumina, Co in terms of Co 3 O 4 , Mn in terms of MnO 2 , Fe in terms of Fe 2 O 3 , and Ti in terms of TiO 2. It contained 13.1% by mass and further contained other substances (mainly powder impurities such as MnO 2 ).
また、実施例２のアルミナ焼結体は、アルミナを８８質量％、ＣｏをＣｏ３Ｏ４換算、ＭｎをＭｎＯ２換算、ＦｅをＦｅ２Ｏ３換算、ＴｉをＴｉＯ２換算でそれらを合わせて９．２質量％含有し、更にそれら以外の物質を含有していた。 Further, the alumina sintered body of Example 2 is composed of 88% by mass of alumina, Co in terms of Co 3 O 4 , Mn in terms of MnO 2 , Fe in terms of Fe 2 O 3 , and Ti in terms of TiO 2. It contained 9.2% by mass and further contained other substances.
また、比較例１のアルミナ焼結体は、アルミナを９３質量％、ＣｏをＣｏ３Ｏ４換算、ＭｎをＭｎＯ２換算、ＦｅをＦｅ２Ｏ３換算、ＴｉをＴｉＯ２換算でそれらを合わせて５．４質量％含有し、更にそれら以外の物質を含有していた。 Moreover, the alumina sintered body of Comparative Example 1 is a combination of 93 mass% alumina, Co equivalent to Co 3 O 4 , Mn equivalent to MnO 2 , Fe equivalent to Fe 2 O 3 , and Ti equivalent to TiO 2. It contained 5.4% by mass and further contained other substances.
まず、これらのアルミナ焼結体の未加工の焼成面の算術平均粗さＲａと光反射率を測定した。なお、算術平均粗さＲａはＪＩＳ Ｂ０６０１−２００１に準じて測定し、光反射率はコニカミノルタ製の分光測色計ＣＭ−３７００ｄを用いてＪＩＳ Ｚ８７２２−２０００に準じて測定した。 First, the arithmetic average roughness Ra and the light reflectance of the raw fired surface of these alumina sintered bodies were measured. The arithmetic average roughness Ra was measured according to JIS B0601-2001, and the light reflectance was measured according to JIS Z8722-2000 using a spectrocolorimeter CM-3700d manufactured by Konica Minolta.
次に、これらのアルミナ焼結体の表面を、ダイヤモンド砥石を電着した研磨盤を用いて研磨し、研磨された面の算術平均粗さＲａと光反射率を測定した。
研磨盤は、ダイヤモンド砥石の粗さの違うものを実施例１では３種類、実施例２及び比較例１では２種類使用し、各研磨盤を用いて研磨した面の算術平均粗さＲａと光反射率をそれぞれ測定した。
Next, the surfaces of these alumina sintered bodies were polished using a polishing machine electrodeposited with a diamond grindstone, and the arithmetic average roughness Ra and light reflectance of the polished surface were measured.
As the polishing machine, three types of diamond grinding stones having different roughnesses were used in Example 1, and two types were used in Example 2 and Comparative Example 1. The arithmetic average roughness Ra and light of the surface polished by each polishing machine were used. Each reflectance was measured.
以上のように測定した未加工の焼成面と研磨した加工面の算術平均粗さＲａと光反射率の測定結果として、表１には実施例１のアルミナ焼結体の測定値、表２には実施例２のアルミナ焼結体の測定値、表３には比較例１のアルミナ焼結体の測定値を示す。 As measured results of the arithmetic average roughness Ra and the light reflectance of the raw fired surface and the polished processed surface measured as described above, Table 1 shows measured values of the alumina sintered body of Example 1, and Table 2 shows Shows measured values of the alumina sintered body of Example 2, and Table 3 shows measured values of the alumina sintered body of Comparative Example 1.
なお、表１〜３には、光反射率の測定結果として、波長４００ｎｍ、５００ｎｍ、６００ｎｍ、７００ｎｍの光に対する反射率を示す。
また、表１〜３には、Ｒａは少数点以下３桁で四捨五入した数値、光反射率は少数点以下２桁で四捨五入した数値を示す。
Tables 1 to 3 show the reflectance with respect to light having wavelengths of 400 nm, 500 nm, 600 nm, and 700 nm as the measurement results of the light reflectance.
In Tables 1 to 3, Ra is a numerical value rounded off to three decimal places, and light reflectance is a numerical value rounded to two decimal places.
表１〜３の結果をみると、実施例１，２は、未加工面の光反射率が比較例１のものと比べて低く、また、未加工面と加工面と光反射率の差も比較例１のものと比べて小さい。そして、加工面の算術平均粗さＲａが０．２４μｍ以下となるように研磨すれば、未加工面と加工面と光反射率の差はほとんどなくなる。 Looking at the results of Tables 1 to 3, in Examples 1 and 2, the light reflectance of the unprocessed surface is lower than that of Comparative Example 1, and the difference in light reflectance between the unprocessed surface and the processed surface is also large. Smaller than that of Comparative Example 1. And if it grind | polishes so that arithmetic mean roughness Ra of a processed surface may be 0.24 micrometer or less, the difference of a light reflectance with an unprocessed surface and a processed surface will almost disappear.
次に、実施例１〜２及び比較例１に加え、各成分を表４及び表５に示す量で含有するアルミナ焼結体（全て気孔率は１％以下）を製造して、各アルミナ焼結体の未加工面の黒色の程度、及び未加工面と加工面（Ｒａ＝０．２μｍ）の色の差を評価した。評価結果も表４に示す。 Next, in addition to Examples 1 and 2 and Comparative Example 1, an alumina sintered body (all the porosity is 1% or less) containing each component in the amounts shown in Tables 4 and 5 was manufactured. The degree of blackness of the unprocessed surface of the bonded body and the color difference between the unprocessed surface and the processed surface (Ra = 0.2 μm) were evaluated. The evaluation results are also shown in Table 4.
黒色の程度の評価は以下のように行った。
分光測色計ＣＭ−３７００ｄを用いて各アルミナ焼結体の測色を行い、Ｌ＊ａ＊ｂ＊表色系で示された数値のうち、明度指数Ｌ＊の値によって評価した。
○：Ｌ＊が３５未満
△：Ｌ＊が３５〜４０
×：Ｌ＊が４０を超える
Evaluation of the degree of black was performed as follows.
Each alumina sintered body was measured using a spectrocolorimeter CM-3700d, and evaluated by the value of the lightness index L * among the numerical values shown in the L * a * b * color system.
○: L * is less than 35 Δ: L * is 35-40
X: L * exceeds 40
未加工面と加工面の色の差の評価は以下のように行った。
分光測色計ＣＭ−３７００ｄを用いて各アルミナ焼結体の未加工面と加工面の測色を行い、それぞれのＬ＊ａ＊ｂ＊表色系で示された数値をもとに、ＪＩＳＺ８７３０に準じて求められる色差ΔＥ（ΔＥ*ab）の値によって評価した。
○：ΔＥが５未満
△：ΔＥが５〜１０
×：ΔＥが１０を超える
The color difference between the unprocessed surface and the processed surface was evaluated as follows.
Color measurement of the unprocessed surface and processed surface of each alumina sintered body was performed using a spectrocolorimeter CM-3700d, and JISZ8730 was based on the numerical values indicated by the respective L * a * b * color systems. The color difference ΔE (ΔE * ab) obtained according to the above was evaluated.
○: ΔE is less than 5 Δ: ΔE is 5-10
×: ΔE exceeds 10
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| EP2636655A1 (en) * | 2010-11-01 | 2013-09-11 | Showa Denko K.K. | Alumina sintered body, abrasive grains, and grindstone |
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| JPWO2018139673A1 (en) * | 2017-01-30 | 2019-11-07 | 京セラ株式会社 | Semiconductive ceramic member and wafer transfer holder |
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