200902475 九、發明說明： 【發明所屬之技術領域】 本發明是有關於適合應用於半導體製造裝置用構件的 氧化紀材料。 【先前技術】 般而5，鍾罩（bell jar)、腔室（chamber)、接受器 (' (CePt〇r)、夾環（clamp ring)、對焦環（focus ring) =半導體製造裝置用構件，多使用於*素系氣體環境或 问密度電裝氣體環境等的化學腐蝕性高的氣體環境中。基 於此種为景，習知以來，對於藉由耐姓性高、不易成為污 染源的氧化妃材料以形成半導體製造裝置用構件進行了檢 討。 【專利文獻1】特開平u_278935號公報 【專利文獻2】特開2001-1 79080號公報 k 【專利文獻3】特開2006-69843號公報 【發明内容】 [發明所要解決的課題] 然而，習知的氧化紀材料的3點-曲 腑a左右’破壞勃性為〇.8〜11MPa“左右：140〜 性差。因& ’應用於半導體製造裝置用構件時，在f械特 或使用時有可能會產生破損，而.白* 加工時 吸相因而在良率、操作性 靠性等.方面產生問題》 及了 2 0 81-94 7 8 -PF/Ahddub 5 200902475 本發明是為了解決上述課題而產生的，其目的是提供 一種機械特性優良的氧化釔材料。 [用以解決課題的手段] —本發，的發明者們’經由反覆銳意研究的結果，得知 了藉由在氧化釔(γ2〇3)中添加碳化矽(Sic)以及I化釔㈣ 夠使氧化紀材料強動化，在應用於半導體製造裝置構 牛夺的產率、操作性以及可靠性能夠提昇。200902475 IX. Description of the Invention: [Technical Field] The present invention relates to an oxidized material suitable for use in a member for a semiconductor manufacturing apparatus. [Prior Art] As usual, a bell jar, a chamber, a receiver ('(CePt〇r), a clamp ring, a focus ring) are members for a semiconductor manufacturing apparatus. It is used in a chemical environment with high chemical corrosivity such as a gas environment or a density gas environment. Based on this, it has been known to have high resistance to high oxidation and is not a source of pollution. The 妃 妃 以 形成 形成 2006 2006 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2006 2006 2006 2006 2006 2006 2006 2006 DISCLOSURE OF THE INVENTION [Problems to be Solved by the Invention] However, the conventional oxidized material has a 3-point-curve a-destructive boring property of 〇.8 to 11 MPa "left and right: 140~ poorness. Because & ' applied to semiconductor When manufacturing a component for a device, it may be damaged when it is used or used, and the phase absorption during white* processing causes problems in yield, operability, etc. and 2 0 81-94 7 8 -PF/Ahddub 5 200902475 The present invention is The object of the present invention is to provide a cerium oxide material having excellent mechanical properties. [Means for Solving the Problem] - The inventors of the present invention have learned from the results of repeated research. The addition of niobium carbide (Sic) and niobium (4) to niobium oxide (γ2〇3) is sufficient to make the oxidized material stronger, and the productivity, operability, and reliability of the semiconductor manufacturing equipment can be improved.
而且在本發明中，較佳碳化石夕的粒徑為3"以下。-般而σ奴化矽與氧化釔相較之下’顯示了對於鹵素系電 聚的耐姓性顯著低的特性。因此，如將添加了礙化石夕的氧 化紀材料暴露^素系電㈣話，碳化㈣會優先於氧化 I乙材料產生腐蝕 產生孔洞’從而形成了依竣化石夕的粒子 '而大體決定尺寸的段差。另—方面，即使是氧化纪單體 的燒結體，暴露在齒素系電漿的話，會形成起因於結晶方 位的腐蝕容易性不同所導致@ 左右尺寸的段差。因 此’較佳碳化石夕的粒徑為3 # m以下，以使得即使添加碳化 石夕亦不會使氧化纪材料表面的平滑性惡化。而且藉由使碳 化矽的粒徑為3# ID以下，能夠抑制氧化釔材料的強度降 低。 而且在本發明中，氧化釔材料較佳是以1300°C以上、 1850 C以下的燒結溫度，燒結氧化釔、碳化矽、希土類氟 化物的混合粉末以製造。由於氧化釔與氟化釔的共晶溫度 為1 300°C，1 3001以上的燒結溫度會生成液相，因而促進 燃結（sinter)，從而能夠期待氧化釔材料的緻密化。而且 2081-9478-PF；Ahddub 6 200902475 燒結溫度為1850 C以上的話，會產生碳化;5夕或y〇f等的粒 成長而導致氧化纪材料的強度降低。 【實施方式】 以下’藉由比較實施例以及比較例的氧化釔材料的強 度、破壞韌性以及姓刻率，以詳細說明本發明的實施型熊 的氧化纪材料針。 〔實施例1〕 實施例1是將氧化紀（γζ〇3、信越化學製、Uugp等級）、 碳化矽（SiC、IBIDEN(股）製Ultrafine)以及氟化釔（γρ3、 (股）高純度化學研究所）個別以96、3、lv〇1%的比例調配 之後’利用IPA(異丙醇）為溶劑24小時濕式混合（利用Zj~〇2 球石的球磨機）以調製漿料。使漿料通過篩子後，於丨丨〇。〇 的氮氣體環境乾燥1 6小時以得到粉體。其次，將粉體通過 篩子後，以200kg/cm2的施壓將80g的粉末成形為0 5〇mm。 然後’最後在160(TC的氬氣體環境中以200kg/cm2的施壓 進行4小時的熱壓燒結，藉此得到實施例1的氧化釔材料。 〔實施例2〕 實施例 2 除了 γ2〇3、SiC、YFHSl 別以 92、3、5V〇l%的 比例調配之外，進行與實施例丨相同的處理以得到實施例 2的氧化紀材料。 〔實施例3〕 實施例 3 除了 γ2〇3、SiC、YF3個別以 94、5、lv(3l%的 比例調配之外，進行與實施例1.相同的處理以得到實施例 2081-9478-PF;Ahddub 7 200902475 3的乳化紀材料。 〔實施例4〕 實施例4除了 γ2〇3、SiC、YF^別以Q/1 。 ..,^ s ⑴以 94、3、3v〇l%的 比例調配之外，進行與實施例丨相 J.處理以得到實施例 4的氧化紀材料β 〔實施例5] 實施例5除了 γ2〇3、siC、 比例調配之外，進行與實施例 5的氧化釔材料。 〔實施例6〕 實施例6除了 γ2〇3、siC、 比例調配之外，進行與實施例 6的氧化釔材料。 YF3個別以90、5、^〇1%的 1相同的處理以得到實施例 YF3個別以 92、7、1¥〇1%的 1相同的處理以得到實施例 〔實施例7〕 個別以 89、1〇、1ν〇α 相同的處理以得到實施 實施例 7 除了 Y2〇3、SiC、YF ί 的比例調配之外，進行與實施例i 例7的氧化釔材料。 〔實施例8〕 、10、 5vol% 以得到實施 貫施例8除了 Yz〇3、SiC、YF3個別以85 的比例凋配之外’進行與實施例1相同的處理 例8的氧化釔材料。 〔實施例9〕 實施例9除了 的比例調配之外， Υ2〇3、SiC、YF3 個別以 86 進行與實施例1相同的處理 13' 1vo 1 % 以得到實施 2081-9478-PF;Ahddub 8 200902475 例9的氧化紀材料。 〔實施例1 〇〕 實施例 10 除了 Y2〇3、SiC、YF3個別以 82、13、5ν〇ι% 的比例調配之夕卜’進行與實施W Η目Θ的處理以得到實施 例1 〇的氧化釔材料。 〔比較例1〕 匕車乂例1僅藉由氧化纪（Υ2〇3、仏越化學製、UUHP等級） 形成燒結體。 ' 〔比較例2〕 比較例2除了 γ2〇3、YF3個別以95、5ν〇1%的比例調配 之外，進行與實施例1相同的處理以得到比較例2的氧化 崔乙材料。 〔比較例3〕 比較例 3 除了 γ2〇3、siC、YFHil 別以 85、5、1〇ν〇1% 的比例調配之外，進行與實施例1相同的處理以得到比較 例3的氧化釔材料。 〔比較例4〕 比較例 4 除了 γ2〇3、siC、YFs個別以 8〇、5、15ν〇1% 的比例調配之外，進行與實施例1相同的處理以得到比較 例4的氧化紀材料。 〔比較例5〕 比較例5除了 γ2〇3、siC個別以80、20vol%的比例調 配之外，進打與實施例1相同的處理以得到比較例5的氧 化記材料。 2081-9478-PP;Ahddub 9 200902475 〔構成相的評價〕 利用X線繞射裝置（回轉對陰極（Wary ant i⑽ode) 型x線繞射裝置（理學電機製RINT)、CuKa線源、5〇kv、 300mA、2Θ =10〜70。）’對於由實施例卜1〇以及比較例 1〜5的各氧化㈣料所得的χ線繞射圖案而得到的結晶相 進行同定的結果，如以下表1所示，能瞭解實施例1、3、 6、7、9以及比較例5的氧化釔材料是由氧化釔(γζ〇。、碳 化矽（SiC)以及YzSi〇5所構成，實施例2、5、8、10以及比 較例3、4的氧化記材料是由[Ο3、Sic以及γ〇ρ所構成。 亦瞭解貫施例4的氧化釔材料是由Υζ〇3、s丨c構成的。 【表1】Further, in the present invention, it is preferred that the particle diameter of the carbonized carbide is 3 " - σ 奴 矽 矽 矽 矽 钇 钇 钇 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ Therefore, if the oxidized material that has been added to the fossilized ceramsite is exposed to the genus (4), the carbonization (4) will take precedence over the oxidized I-B material to cause corrosion to form pores, thereby forming a particle based on the fossils of the fossils. The difference is the segment. On the other hand, even if the sintered body of the oxidized element is exposed to the dentate-based plasma, a step difference of the size of the left and right sides due to the difference in the easiness of the crystallization is caused. Therefore, the particle diameter of the preferred carbonized carbide is 3 # m or less so that the smoothness of the surface of the oxidized material is not deteriorated even if carbonized carbon is added. Further, by making the particle size of the ruthenium carbide 3 or less, the strength of the ruthenium oxide material can be suppressed from being lowered. Further, in the present invention, the cerium oxide material is preferably produced by sintering a mixed powder of cerium oxide, cerium carbide, and cerium fluoride at a sintering temperature of 1300 ° C or higher and 1850 ° C or lower. Since the eutectic temperature of cerium oxide and lanthanum fluoride is 1,300 ° C, a sintering temperature of 1,3001 or more forms a liquid phase, thereby promoting sinter, and densification of the cerium oxide material can be expected. Further, 2081-9478-PF; Ahddub 6 200902475 When the sintering temperature is 1850 C or more, carbonization occurs; and grain growth such as 5 or y〇f causes the strength of the oxidized material to decrease. [Embodiment] Hereinafter, the oxidized rubber material needle of the embodiment of the present invention will be described in detail by comparing the strength, fracture toughness, and surname of the cerium oxide material of the comparative examples and the comparative examples. [Example 1] Example 1 is an oxidation period (γζ〇3, manufactured by Shin-Etsu Chemical Co., Ltd., Uugp grade), niobium carbide (Ultrafine made of SiC, IBIDEN), and yttrium fluoride (γρ3, (high) purity chemistry) The institutes were individually formulated in a ratio of 96, 3, and lv〇1%, and then the mixture was prepared by using IPA (isopropyl alcohol) as a solvent for 24 hours wet mixing (using a ball mill of Zj~〇2 ball stone) to prepare a slurry. After passing the slurry through the sieve, it is placed in a crucible. The atmosphere of nitrogen gas was dried for 16 hours to obtain a powder. Next, after the powder was passed through a sieve, 80 g of the powder was molded into a thickness of 50 mm at a pressure of 200 kg/cm2. Then, finally, the hot-pressed sintering was carried out for 4 hours at a pressure of 200 kg/cm 2 in an argon atmosphere of 160 (TC), whereby the cerium oxide material of Example 1 was obtained. [Example 2] Example 2 Except γ2〇3 The same treatment as in Example 以 was carried out to obtain the oxidized material of Example 2 except that SiC and YFHS1 were blended at a ratio of 92, 3, and 5 V 〇 1%. [Example 3] Example 3 Except γ 2 〇 3 The SiC and YF3 were individually blended in the ratio of 94, 5, and lv (3l%, and the same treatment as in Example 1. was carried out to obtain the emulsified material of Example 2081-9478-PF; Ahddub 7 200902475 3. Example 4: Example 4 was carried out in the same manner as in Example except that γ2〇3, SiC, and YF were mixed with Q/1, .., and s (1) at a ratio of 94, 3, and 3 v〇l%. Treatment to obtain the oxidized material β of Example 4 [Example 5] Example 5 was carried out in addition to γ2〇3, siC, and proportioning, and the cerium oxide material of Example 5. [Example 6] Example 6 except In addition to γ2〇3, siC, and ratiometric formulation, the cerium oxide material of Example 6 was carried out. YF3 was individually the same as 90, 5, and 1% of 1 The treatment of Example YF3 was carried out in the same manner as in the case of 92, 7, and 1% 以1% to obtain the same example (Example 7). The same treatment was carried out by 89, 1 〇, 1 〇 〇 α to obtain an Example. 7 In addition to the ratio formulation of Y2〇3, SiC, and YF ί, the yttrium oxide material of Example 7 was carried out. [Example 8], 10, 5 vol% to obtain the implementation Example 8 except Yz〇3, The ruthenium oxide material of the same treatment example 8 as that of Example 1 was carried out except that SiC and YF3 were each mixed at a ratio of 85. [Example 9] In addition to the ratio formulation of Example 9, Υ2〇3, SiC, YF3 The same treatment as in Example 1 was carried out separately at 86 13 ' 1 vo 1 % to obtain an oxidized material of Example 2081-9478-PF; Ahddub 8 200902475 Example 9. [Example 1 〇] Example 10 In addition to Y2〇3, SiC And YF3 was individually prepared at a ratio of 82, 13, and 5 〇 %%, and the treatment of the W Η 进行 was performed to obtain the yttrium oxide material of Example 1. [Comparative Example 1] The sintered body was formed by the Oxide (Υ2〇3, 仏越化学, UUHP grade). ' [Comparative Example 2] Comparative Example 2 The same treatment as in Example 1 was carried out except that γ2〇3 and YF3 were each blended at a ratio of 95 and 5 〇 〇 1% to obtain a oxidized cerium material of Comparative Example 2. [Comparative Example 3] Comparison Example 3 The same treatment as in Example 1 was carried out except that γ2〇3, siC, and YFHil were blended at a ratio of 85, 5, and 1 〇 〇 % 1% to obtain a cerium oxide material of Comparative Example 3. [Comparative Example 4] Comparative Example 4 The same treatment as in Example 1 was carried out except that γ2〇3, siC, and YFs were blended at a ratio of 8〇, 5, 15ν〇1%, respectively, to obtain the oxidized material of Comparative Example 4. . [Comparative Example 5] Comparative Example 5 was treated in the same manner as in Example 1 except that γ2〇3 and siC were individually mixed at a ratio of 80% to 20% by volume to obtain an oxidation recording material of Comparative Example 5. 2081-9478-PP; Ahddub 9 200902475 [Evaluation of constituent phase] Using X-ray diffraction device (Wary ant i (10) ode) type x-ray diffraction device (Rining mechanism RINT), CuKa line source, 5〇kv 300 mA, 2 Θ = 10 to 70.) 'The crystal phase obtained by the enthalpy diffraction pattern obtained from each of the oxidized (four) materials of the examples 1 to 5 and the comparative examples 1 to 5 was subjected to the same results, as shown in Table 1 below. As shown, it can be understood that the yttria materials of Examples 1, 3, 6, 7, 9 and Comparative Example 5 are composed of yttrium oxide (γζ〇, yttrium carbide (SiC) and YzSi〇5, Examples 2, 5 The oxidation materials of 8, 10, and 3 and 4 are composed of [Ο3, Sic, and γ〇ρ. It is also understood that the cerium oxide material of Example 4 is composed of Υζ〇3, s丨c. Table 1】
而且，實施例1〜1G的氧化記材料的結構藉由化學分 析評價的結果’能瞭解在YFa的添加量少（於實施例為 lvol%)，Si〇2量比相關於反應的γρ3量多的拄、α 里夕的情況下，進行下 述化學式1、2所示的反應’藉此如圖i(a)、圖1(匕）所一 構成為在YzSiOs材料3中被包接的碳化石夕缸子2 2081-9478-PF;Ahddub 10 200902475 基體1中成為點狀存在。 【化1】 3Si〇2+4YF3—3SiF4 个 +2Υ2〇3 【化2】Further, the structure of the oxidation mark materials of Examples 1 to 1G was evaluated by the results of chemical analysis 'to know that the amount of addition to YFa is small (in the embodiment, 1 vol%), and the amount of Si 〇 2 is larger than the amount of γ ρ 3 related to the reaction. In the case of 拄 and α 里 夕, the reactions shown in the following chemical formulas 1 and 2 are carried out, whereby the carbon which is encapsulated in the YzSiOs material 3 as shown in Fig. i(a) and Fig. 1 (匕) Fossil urn cylinder 2 2081-9478-PF; Ahddub 10 200902475 The base 1 is in the form of dots. [Chemical 1] 3Si〇2+4YF3—3SiF4 +2Υ2〇3 【化2】
Si〇2+ Υ2〇3-> Y2Si〇5 另一方面’能瞭解在YF3的添加量多（於實施例為 5vol%)，Si〇2量比相關於反應的YF3量少的情況下，進行前 述化子式1與下述化學式3所示的反應，藉此如圖2(a)、 圖2(b)所示，構成為在氧化釔基體1中碳化矽粒子2為點 狀存在’並且在碳化矽粒子2之間形成Y0F區域4。 【化3】Si〇2+ Υ2〇3-> Y2Si〇5 On the other hand, it can be understood that the amount of addition of YF3 is large (5 vol% in the example), and the amount of Si〇2 is smaller than the amount of YF3 related to the reaction. The reaction of the above-described chemical formula 1 and the following chemical formula 3 is carried out, whereby as shown in Fig. 2 (a) and Fig. 2 (b), the niobium carbide particles 2 are in the form of dots in the yttrium oxide matrix 1 And a Y0F region 4 is formed between the niobium carbide particles 2. [化3]
Y2O3+ YF3-> 3Y0F 而且，實施例1〜10以及比較例3〜5的氧化釔材料中 的sic的平均粒徑由SEM(掃描式電子顯微鏡）照相評價的 結果’可明瞭任-個的Sic的平均粒徑皆在3“以下的範 圍内。而且’實施例2、5、8、1〇以及比較例2〜4的氧化 ^料中的Y0F的平均粒徑由SEM照相評價的結果，可明 、幻2 5、8、10的氧化釔材料的任一個的Y〇F的平 均粒徑皆在1 〇以m以下的範圍内。 〔SiC的平均粒子徑的測量〕 :施例W。以及比較例3〜5的氧化紀材料以挪的 射電子像進行觀察，測量各氧化紀材料^ Μ的平均 但是’由於粒徑未滿〇.一的训粒子無法被明確 的相，因此僅測量粒徑0·5…上的粒子的短徑尺寸， 2081-9478-pF；Ahddub 11 200902475 並求其平均值以做為平均粒徑。其結果，瞭解到無論何者 的W平均粒徑皆為_以下。而且，粒徑0.5口以上 的較大的SiC粒子，主要是在+ β 要疋存在於粒界。尚且，0.5“程 度以下的細微SiC粒子雖然無法正確的測量，但可觀察到 有無添加肌會造成SlC的存在頻度不同。亦即是添加有 YF3的情況下，可觀察到多數的細嫌粒子存在於氧化紀 的粒内。相對於此，在未添加YF3的情況下，幾乎未財 到細微的SiC粒子。其原因現階段尚未被瞭解，作經考量 其原因可能為藉由添加爪’能夠低溫燒結而細微W粒： 能夠安定的存在，以及Sic粒子能舜容易的進入氧化紀的 粒内。 〔強度的評價〕 對實施例卜10以及比較例卜5的各氧化紀材料進行 3點彎曲測試以評價3點彎曲強度。評價結果如表！所示。 其結果’可明瞭實施例的任一個氧化纪材料的3點 彎曲強度皆在250MPa以上。 ’ 〔破壞韌性的評價〕 對實施例卜10以及比較例卜5的各氧化紀材料，藉 由依循JIS R 1607 # IF法（加重9·8Ν)以評價破壞動性。 評價結果如表i所示。其結果’可明瞭實施例卜1〇的任 一個氧化釔材料的破壞韌性皆在1. 3ΜΡ3/·ηι以上。而且在 添加有YF4材料方面’具有藉由少量的Sic添加量：強 度以及破壞韌性變高的傾向。此理由現階段尚未被瞭解， 但經考量其原因可能為藉由添加YF”比較大的粒徑Ο』以爪 2081-9478-PF；Ahddub 12 200902475 以上的sic粒子存在於氧化釔的粒界，且細微的〇_ 5 # m以 下的SiC粒子存在於氧化釔的粒内，因此粒界以及粒内的 機械特性有效的向上提昇。 〔敍刻率的評價〕 對實施例1〜1 〇以及比較例1〜5的各氧化釔材料，以 耐姓測試裴置進行電漿耐蝕測試。具體而言，氣體使用 NF3、〇2、Ar ’使用ICP(感應耦合電漿）以8〇〇w產生電漿， 所產生的電漿以偏壓30〇W照射被測試片。然後，使用段差 計測量遮蔽面與暴露面的段差並除以測試時間，藉此計算 出各氧化釔材料的蝕刻率。計算出的結果表示於表1。其 結果’可瞭解即使將耐蝕性差的碳化矽添加入耐钱性良好 的氧化釔中，當其量、形狀、分散狀態滿足某些條件時， 耐蝕性並不會大幅地降低。 根據上述，如依實施例的氧化釔材料，可得知藉由添 加了碳化矽而高破壞韌性化，並藉由添加了 YFa而提昇燃 結性，並藉由可在低溫燒結而能夠實現高強度化。尚且， 汀3的添加量多的話則Y0F的粒徑大而強度降低，如依實施 例的氧化釔材料，Y0F的粒徑能夠最適化。 〔至溫體積電阻率與比介電率的評價〕 對實施例1、3、6、7、9以及比較例1的各氧化記材 料’於室溫測量體積電阻率（室溫體積電阻率）與比介電 率。尚且體積電阻率是依據JIS-C2141為基準的方法，在 大氣中進行測量。而且比介電率的測量，是在對□ 21minx21mni、厚〇.1_的平板形狀的試樣表面進行研磨以使 2〇8l-9478-PF;Ahddub 13 200902475 表面粗糙度為Ra=0. 1 ;/ m以下之後 (impedance analyzer)4291A 進行測量 下面的表2。 使用阻抗分析儀 。測量結果表示於 【表2】 ~~~SiC添加量^ (vol%) 室; 實施例1 3 實施例3 貫施例6 7 實施例7 --------- 10 實施例9 13 比較例1 r 0 18.5 --一 X 4/ 如同表2所示，SlC的添加量為〇〜10VOU的範圍内的 !室溫體積電阻率成為㈣.…，氧化紀材料維持 焉電阻，但是當SlC的添加量為13v〇1%時，室溫體積電阻 率成為3x10% . cm ’氧化釔材料低電阻化。另一方面，Y2O3 + YF3-> 3Y0F Further, the average particle diameter of sic in the cerium oxide materials of Examples 1 to 10 and Comparative Examples 3 to 5 was evaluated by SEM (Scanning Electron Microscope) photography, and it was confirmed that Sic was any one. The average particle diameter is in the range of 3" or less. Moreover, the average particle diameter of Y0F in the oxides of Examples 2, 5, 8, and 1 and Comparative Examples 2 to 4 is evaluated by SEM photography. The average particle diameter of Y〇F of any of the cerium oxide materials of Ming, Magic 2, 5, 8, and 10 is in the range of 1 〇 or less. [Measurement of average particle diameter of SiC]: Example W. The oxidized material of Comparative Examples 3 to 5 was observed by the electron image of the eclipse, and the average of the oxidized material ^ was measured, but the particle of the oxidized particle was not sufficient. The short diameter of the particles on the diameter of 0·5..., 2081-9478-pF; Ahddub 11 200902475 and the average value thereof is taken as the average particle diameter. As a result, it is understood that the W average particle diameter is _ or less. Moreover, larger SiC particles having a particle diameter of 0.5 or more are mainly present at the grain boundary at +β. Further, although the fine SiC particles below 0.5" cannot be measured correctly, it can be observed that the presence or absence of the added muscle causes the frequency of occurrence of the SlC to be different. That is, in the case where YF3 was added, it was observed that most of the fine particles were present in the oxidized particles. On the other hand, in the case where YF3 was not added, fine SiC particles were hardly obtained. The reason for this is not known at this stage. The reason for this may be that it can be sintered at a low temperature by adding claws, and the fine W grains can be stabilized, and the Sic particles can easily enter the oxidized particles. [Evaluation of Strength] Each of the oxidized materials of Example 10 and Comparative Example 5 was subjected to a 3-point bending test to evaluate the 3-point bending strength. The evaluation results are as shown! Shown. As a result, it was confirmed that the three-point bending strength of any of the oxidized materials of the examples was 250 MPa or more. 'Evaluation of Destructive Toughness> For each of the oxidized materials of Example 10 and Comparative Example 5, the destructive kinetics were evaluated by following the JIS R 1607 # IF method (emphasis 9.8 Ν). The evaluation results are shown in Table i. As a result, it is understood that the fracture toughness of any of the cerium oxide materials of the embodiment is 1. 3 ΜΡ 3 / · ηι or more. Further, in terms of the addition of the YF4 material, there is a tendency to increase the amount of Sic by a small amount: the strength and the fracture toughness become high. This reason has not been understood at this stage, but the reason may be that by adding YF "larger particle size Ο" to the claw 2081-9478-PF; Ahddub 12 200902475 or more sic particles are present in the grain boundary of yttrium oxide, The fine SiC particles below # 5 5 m are present in the cerium oxide particles, so the grain boundary and the mechanical properties in the granules are effectively lifted upwards. [Evaluation of the etch rate] For Examples 1 to 1 and comparison Each of the cerium oxide materials of Examples 1 to 5 was subjected to a plasma corrosion resistance test using a resistance tester. Specifically, the gas was generated using NF (inductively coupled plasma) using NF 3 , 〇 2 , and Ar ' at 8 〇〇 w The slurry, the generated plasma is irradiated with the test piece at a bias voltage of 30 〇 W. Then, the step difference between the shielding surface and the exposed surface is measured by a step difference meter and divided by the test time, thereby calculating the etching rate of each cerium oxide material. The results are shown in Table 1. As a result, it can be understood that even if the niobium carbide having poor corrosion resistance is added to the niobium oxide having good niobium resistance, the corrosion resistance does not occur when the amount, shape, and dispersion state satisfy certain conditions. Drastically reduced. As described above, according to the cerium oxide material of the embodiment, it is known that high destructive toughness is obtained by adding cerium carbide, and the burning property is improved by adding YFa, and high strength can be achieved by sintering at a low temperature. Further, when the amount of addition of the ternary 3 is large, the particle diameter of the Y0F is large and the strength is lowered, and the particle size of the Y0F can be optimized according to the yttrium oxide material of the example. [To the temperature volume resistivity and the specific dielectric ratio Evaluation] For each of the oxidized materials of Examples 1, 3, 6, 7, and 9 and Comparative Example 1, the volume resistivity (room temperature volume resistivity) and the specific dielectric ratio were measured at room temperature. JIS-C2141 is a reference method for measurement in the atmosphere, and the specific dielectric ratio is measured by grinding the surface of a flat-shaped sample of □ 21 min x 21 mni, thick 〇.1_ to make 2〇8l-9478- PF; Ahddub 13 200902475 Surface roughness Ra = 0.1 1 / m or less (impedance analyzer) 4291A Measurements are shown in Table 2. The impedance analyzer is used. The measurement results are shown in [Table 2] ~~~ SiC addition ^ (vol%) room; Example 1 3 Example 3 Example 6 7 Example 7 --------- 10 Example 9 13 Comparative Example 1 r 0 18.5 --- X 4 / As shown in Table 2, the amount of SlC added is in the range of 〇 10 10 VOU The room temperature volume resistivity becomes (4)...., the oxidized material maintains the 焉 resistance, but when the addition amount of SlC is 13v 〇 1%, the room temperature volume resistivity becomes 3x10%. cm 'The yttria material has low resistance. on the one hand,
當完全未添加训時，氧化纪材料的比介電率412，而SlC 的添加量在3〜1〇的範圍内的話，氧化纪材料的比介電率 f1二〜18.5,顯示了比較高的值。由上述可知，藉由添加 !：10vg1%的範圍内的加，能夠維持高體積電阻率，並提 咼氧化釔材料的比介電率。 、°在特開2006-69843號公報中，記載有以2〜 〇= 的範圍在氧化妃材❹添加⑽，藉此賦予氧 =性的發明。相對於此，本申請發明是以一％ 巳“化紀材料中添加Sic，藉此維持高體積電阻率， 向氧化紀材料的比介電率。一般而言，庫余式的靜電 固持頭為了吸附晶圓，必須要有1〇、犀靜電 > /貝晋百i υ Ω · cin以上的體積電 2〇81-9478-pp;Ahddub 14 200902475 阻率而且靜電固持頭的吸附力以下述的數學式（1)表示， J:到比介電率越高的話，相同的介電體厚度以及施加電 裊可侍到較尚的吸附力。或者是，為了以相同的施加電壓 侍到相同的吸附力’可將介電體的厚度加厚。因此如依本 申明發明，在將機械特性差的氧化釔材料應用於半導體製 、置用構件時，可將構件的厚度增厚，而能夠提昇機械 特性的可靠度。 (1) (1/2)χ ε 2χ ε 〇x(v/d) F為吸附力、£為比介電率、^。為真空的介電率、〗 為施加電壓、d為介電體的厚度（氧化纪材料）。 雖然本申請發明與特開2006-69843號公報添加了相 ::Si、C但導電性不同的理由尚未被瞭解，但經考量其原 因可能為SiC：以及氧化紀的粒子徑與粒成長的容易度:同 所致。亦即是一般而言，在絕緣體中添加導電性粒子而發 見導電I·生的情形作為母體（matrix)的絕緣體的粒徑越大， 相：的導電性粒子的粒徑越小的話，”的添加量即可發 用奴電11 111此，特開2°06—69843號公報記載的發明是使When the training rate is 412, and the addition amount of SlC is in the range of 3 to 1 ,, the specific dielectric constant f1 of the oxidized material f1 is less than 18.5, which shows a relatively high level. value. From the above, it can be seen that the addition of the range of !:10vg1% can maintain the high volume resistivity and improve the specific dielectric constant of the yttrium oxide material. In the Japanese Patent Publication No. 2006-69843, an invention in which oxygen (oxygen) is imparted to the cerium oxide crucible in the range of 2 to 〇 = is described. In contrast, the present invention is based on the addition of Sic to a chemical composition of one percent, thereby maintaining a high volume resistivity and a specific dielectric constant to the oxidized material. In general, the electrostatic retention head of the reservoir is in order to To adsorb the wafer, it must have 1 〇, rhinoceros > / Beijin Bai i υ Ω · cin above the volume of electricity 2 〇 81-9478-pp; Ahddub 14 200902475 resistivity and electrostatic adsorption head adsorption force as follows Mathematical formula (1) indicates that, J: the higher the specific dielectric constant, the same dielectric thickness and the application of electricity can serve a higher adsorption force. Or, in order to serve the same with the same applied voltage The adsorption force can increase the thickness of the dielectric body. Therefore, according to the invention, when the yttria material having poor mechanical properties is applied to a semiconductor device or a member for use, the thickness of the member can be increased, and the thickness can be increased. Reliability of mechanical properties (1) (1/2) χ ε 2χ ε 〇 x (v/d) F is the adsorption force, £ is the specific dielectric ratio, ^ is the dielectric constant of vacuum, 〗 is the applied voltage d is the thickness of the dielectric body (oxidation material). Although the invention of the present application and the special opening 2006-69843 The reason why the phase::Si, C is added but the conductivity is different has not been understood, but the reason may be SiC: and the particle diameter of the oxidized period and the easiness of grain growth: the same. In the case where conductive particles are added to the insulator and the conductive material is formed, the larger the particle diameter of the insulator as the matrix, the smaller the particle diameter of the conductive particles is, the smaller the amount of the conductive particles can be. The invention described in Japanese Laid-Open Patent Publication No. Hei 2 No. 06-69843 is
Siu子以及粒徑大的氧化㈣末。相對於 申清發明為了使機械特性變大，使用包含有粒徑較 粒子與粒徑小的氧化-粒子。而且，-般而言在 其社果乙S1C會阻礙燒結性，變得需要高燒結溫度， =果促進了粒成長。W在燒結中，料S1C與氧化纪 :胜特別是氧化紀的粒成長較容卜基於此理由，被認 為在特開2_-69843 E公報所記載的發明較容易發現導 2081-9478-pp;Ahddub 15 200902475 電性。相對於此，本申請發明添加了 YFs而能夠低溫燒結， 因此被認為能夠抑制氧化釔的粒成長，進一步粒徑 左右以下的細微SiC粒子會進入氧化紀的粒内，因此無導 電性。 以上為對應用於本發明者們所作成㈣明的實施型態 進行說明，但是依此實施型態而成為本發明揭示一部份的 論述以及内纟，並不能用來限定本發日月。例如是本實施型 f態雖然是揭示在氧化記中含有氟化紀，俘是亦可以是氣化 釔以外的希土類氟化物。例如是可舉出以敗化鋼或氣化鏡 來取代敦化纪。依此，基於上述實施型態而為本領域具有 通常知識的技術人員能夠完成的其他實施型態、實施例以 及運用技術’當然全部包含在本發明的範嘴内。 【圖式簡單說明】 圖丄⑷至® i⑻所示為Si〇2量比相關於反應的爪量 U多的情況下’氧化紀的結構的模式圖以及照月圖。 圖2(a)至圖2(b)所為Si〇2量比相關於反應的YF3量 少的情況下，氧化1乙的結構的模式圖以及SEM照片圖。 【主要元件符號說明】 卜氧化釔基體； 2〜碳化矽粒子； 3〜Y2Si〇5材料； 4~Y0F區域。 2〇81-9478-PF;AhddubSiu sub- and the oxidation (4) of the large particle size. In order to increase the mechanical properties of the invention, the oxidized particles having a particle diameter smaller than that of the particles are used. Moreover, in general, in its fruit, S1C hinders sinterability and becomes a high sintering temperature, which promotes grain growth. In the sintering, the material S1C and the Oxide: win, especially the oxidized particle growth is more suitable for this reason, it is considered that the invention described in the Japanese Patent Publication No. 2_-69843 E is relatively easy to find the guide 2081-9478-pp; Ahddub 15 200902475 Electrical. On the other hand, since the YFs of the present invention can be sintered at a low temperature by adding YFs, it is considered that the grain growth of cerium oxide can be suppressed, and fine SiC particles having a particle diameter of about or less become into the oxidized particles, and thus have no conductivity. The above description has been made for the embodiment of the present invention, but the present invention is not limited to the present invention. For example, in the present embodiment, the f-state is disclosed as containing a fluorinated group in the oxidation record, and the capture may be a sulphate-like fluoride other than vaporized ruthenium. For example, it is possible to replace the Dunhua period with a defeated steel or a gasification mirror. Accordingly, other embodiments, embodiments, and application techniques that can be performed by those skilled in the art based on the above-described embodiments are of course all included in the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 4(4) to ® i(8) show a pattern diagram and a illuminating diagram of the structure of the oxidized period when the amount of Si 〇 2 is larger than the amount of claw U of the reaction. Fig. 2 (a) to Fig. 2 (b) show a schematic view and a SEM photograph of the structure of oxidized 1 B when the amount of Si 〇 2 is smaller than the amount of YF 3 associated with the reaction. [Description of main component symbols] Bu ruthenium oxide matrix; 2~ ruthenium carbide particles; 3~Y2Si〇5 material; 4~Y0F region. 2〇81-9478-PF; Ahddub