574377 A7 ___B7__ 五、發明說明（/ ) [技術領域] 本發明係關於以濺鍍法來形成1C、LSI等之閘極或配 線材料等之際所使用之鎢靶及其製造方法。.574377 A7 ___B7__ 5. Description of the Invention (/) [Technical Field] The present invention relates to a tungsten target used for forming gates, wiring materials, etc. of 1C, LSI, etc. by a sputtering method, and a method for manufacturing the same. .
[背景技術] 近年來，伴隨著超LSI高集積化，乃檢討將電氣電阻 値更低之材料當作電極材料與配線材料來使用，其中，電 氣電阻値低、具熱安定性與化學安定性之高純度鎢在做爲 電極材料與配線材料上被賦予厚望。 此超LSI用之電極材料與配線材料一般係以濺鍍法或 CVD法所製造，其中濺鍍法因在裝置之構造以及操作上較 爲單純，容易形成薄膜，且成本低廉，所以較CVD法更廣 爲被使用。 惟，將超LSI用之電極材料與配線材料以電鍍法形成 薄膜之際，若於薄膜形成面存有稱爲粒子之缺陷，則會發 生配線不良等之故障造成產率下降。爲了減少此種薄膜形 成面之粒子的發生，乃需要高密度之結晶粒微細的鎢靶。 以往，在鎢靶之製造方法上，已知有使用電子束熔解 法來製作錠塊，然後熱壓延該錠塊之方法（日本專利特開昭 6M07728);將鎢粉末加壓燒結之後進一步壓延(熱壓延)之 方法(特開平3-150356);以及利用CVD法在鎢之底板的一 面積層鎢層之所謂的CVD-W法(特開平6-158300)。 惟，以前述電子束熔解法或是將鎢粉末加壓燒結後壓 延之方法所製造之鎢靶，由於其結晶粒容易變得巨大所以 機械性脆弱，尙有於濺鍍膜上容易發生粒子缺陷之問題。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公t ) ------------裝--- (請先閱讀背面之注意事項再填寫本頁) -[Background Art] In recent years, with the increase of ultra-LSI, the use of materials with lower electric resistance 値 as electrode materials and wiring materials has been reviewed. Among them, electric resistance 値 is low, with thermal and chemical stability. High-purity tungsten is given high expectations as an electrode material and a wiring material. The electrode materials and wiring materials for this super LSI are generally manufactured by sputtering or CVD. The sputtering method is simpler in structure and operation of the device, is easy to form a thin film, and has a lower cost, so it is more expensive than the CVD method. More widely used. However, when a thin film is formed by using electrode materials and wiring materials for super LSIs by electroplating, if defects called particles are present on the film formation surface, failures such as poor wiring may result in a decrease in yield. In order to reduce the occurrence of particles on the surface of such a thin film, a tungsten target with high density and fine crystal grains is required. In the past, a method for manufacturing a tungsten target has been known by using an electron beam melting method to produce an ingot, and then hot-rolling the ingot (Japanese Patent Laid-Open No. 6M07728); pressing and sintering the tungsten powder and further rolling (Hot rolling) method (Japanese Patent Application Laid-Open No. 3-150356); and the so-called CVD-W method (Japanese Patent Application Laid-Open No. 6-158300) which uses a CVD method to deposit a tungsten layer on an area of a tungsten substrate. However, tungsten targets manufactured by the aforementioned electron beam melting method or the method of pressing and sintering tungsten powders are mechanically fragile because their crystal grains tend to become huge, which is likely to cause particle defects on sputtered films. problem. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 metric t) ------------ Loading --- (Please read the precautions on the back before filling this page)-
574377 A7 _ B7___ 五、發明說明（V) ----------- --- (請先閱讀背面之注意事項再填寫本頁) 例如將鎢粉末燒結後進行熱壓延之靶的抗撓強度爲 400MPa以下，此被認爲係由於鎢燒結材之壓延結構特有 之脆化所導致者。 再者，鎢壓延品所特別存在的問題，係由於需要將以 塊狀之燒結素材爲起始材料之物做強壓延加工之製程，所 以欲獲得較厚或尺寸較大之靶時需要有對應之大型燒結素 材。而此種大型燒結體容易發生結構或密度之不均一。最 近愈來愈需要厚度超過l〇mm之靶或尺寸在400φ以上之大 型靶，而壓延品則無法滿足此需求，是問題所在。 另一方面，CVD-W法雖展現良好之濺鍍特性，惟在靶 之製作上需耗費相當之時間與費用，有經濟效益不佳之問 題，且由於呈柱狀結構，尙有機械性強度不佳之問題。 [發明之揭示] 本發明者著眼於製程較爲簡單之粉末燒結法，其目的 在於獲致一種方法，藉由改善所使用之鎢粉末的燒結特性 與製造條件，可製作出僅利用以往之加壓燒結法所無法達 成之具有高密度、微細結晶結構，且抗撓強度大幅提升之 濺鍍用鎢靶，藉此抑制濺鍍所導致之薄膜形成上之粒子缺 陷的發生，而能以低廉價格來安定地製造該鎢靶。 本發明係提供： 1·一種濺鍍用鎢燒結體靶，其特徵在於，相對密度爲 99%以上、平均粒徑爲ΙΟΟμχη以下、含氧量爲20ppm以下 、且抗撓強度爲500MPa以上。 2·如上述1記載之濺鍍用鎢燒結體靶，其中，Na、κ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 574377 A7 B7 中 法 五、發明說明（ 等之驗金顯量在ippm以下、U、Th处放射 量在lOppb以下、碳含量在l〇ppm以下、 · 一 e、Ni、Cr、574377 A7 _ B7___ V. Description of the invention (V) ----------- --- (Please read the precautions on the back before filling this page) For example, the target of hot rolling after sintering tungsten powder The flexural strength is less than 400 MPa, which is considered to be caused by the brittleness peculiar to the rolled structure of the tungsten sintered material. In addition, the special problems of tungsten rolled products are due to the need to perform a strong rolling process using a block-like sintered material as the starting material, so corresponding measures are required to obtain thicker or larger targets. Large sintered material. Such large sintered bodies are prone to non-uniformity in structure or density. Recently, a target with a thickness exceeding 10 mm or a large target with a size of 400 φ or more is increasingly required, and the rolled product cannot meet this demand, which is a problem. On the other hand, although the CVD-W method exhibits good sputtering characteristics, it takes a considerable amount of time and cost to produce the target, which has the problem of poor economic efficiency, and because of its columnar structure, there is no mechanical strength. The best question. [Disclosure of the invention] The present inventor focused on a powder sintering method with a relatively simple process, and the purpose was to obtain a method by improving the sintering characteristics and manufacturing conditions of the tungsten powder used, which can be produced using only the conventional pressure A tungsten target for sputtering that has high density, fine crystalline structure, and greatly improved flexural strength, which cannot be achieved by the sintering method, thereby suppressing the occurrence of particle defects in film formation caused by sputtering, and can be obtained at a low price. This tungsten target was manufactured stably. The present invention provides: 1. A tungsten sintered body target for sputtering, which has a relative density of 99% or more, an average particle size of 100 μχη or less, an oxygen content of 20 ppm or less, and a flexural strength of 500 MPa or more. 2. The tungsten sintered body target for sputtering as described in 1 above, wherein, Na, κ This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 574377 A7 B7 Chinese method V. Description of invention (etc. The gold test amount is below ippm, the radiation at U and Th is below 10 ppb, the carbon content is below 10 ppm, · e, Ni, Cr,
Mo等之過渡金屬或重金屬之總和爲l〇ppm以下。 3·如上述1或2記載之濺鍍用鎢燒結體鞭，其中密 度爲99.5%以上、平均粒徑爲以下、且結晶^二 爲等向形狀，配向爲不規則。 4·一種濺鍍用鎢燒結體靶之製造方法，其特徵在於^， 係使用粉體比表面積在〇.4m2/g(BET法）以上、含氧量爲 lOOOppm以下之鎢粉末進行燒結。 5·如上述4記載之濺鍍用鎢燒結體靶之製造方法，係 使用粉體比表面積爲〇.6m2/g〜〇.8m2/g (BET法）、含氧量爲 800ppm以下之鎢粉末進行燒結。 6 —種濺鍍用鎢燒結體靶之製造方法，其特徵在於， 係使用粉體比表面積在〇.4m2/g(BET法)以上之鎢粉末，在 真空或還原環境氣氛中，以加壓開始溫度1200°C以下進行 熱壓燒結之後，進一步進行熱均壓燒結(HIP)。 7·如上述6記載之濺鍍用鎢燒結體靶之製造方法，其 粉體比表面積爲〇.6m2/g〜0.8m2/g (BET法）。 8. 如上述4〜7任一記載之濺鍍用鎢燒結體靶之製造方 係利用熱壓燒結調整成爲相對密度93%以上。 9. 如上述4〜8任一記載之濺鍍用鎢燒結體靶之製造方 法，係以溫度1600°C以上、施加壓力150kg/cm2以上來熱 10.如上述4〜9任一記載之濺鍍用鎢燒結體靶之製造方 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------I---裝i丨 (請先閱讀背面之注意事項再填寫本頁) . 574377 A7 ^-----一 —___B7__ 五、發明說明（^ ) 法’係不進行膠囊化即進行熱均壓燒結(HIP)。 11·如上述4〜10任一記載之濺鍍用鎢燒結體靶之製造 方法，係以溫度1700°C以上、施加壓力1000kg/cm2以上來 進行熱均壓燒結。 12·如上述4〜10任一記載之濺鍍用鎢燒結體靶之製造 方法，係以溫度1850°C以上、施加壓力1800kg/cm2以上來 進行熱均壓燒結。 [發明之實施形態] 通常，市售之純度5N以上之高純度鎢粉末，其粉體 比表面積爲〇.3m2/g以下，若嘗試使用該粉末以加壓燒結 法來製作相對密度99%以上之鎢靶時，需要2000°C以上之 燒成溫度。惟，在2000°C以上之燒成溫度下結晶粒會超過 ΙΟΟμηι而巨大化。 又，在此種高溫下之加壓燒結，例如熱壓法會引發模 具與鎢之反應，HIP則會引發與膠囊材之反應，此等重大 之問題，會導致製造成本之增加。 通常，採用粉末冶金法的情況，已知所使用之粉體的 粒度愈微細、亦即比表面積愈大，則燒結性愈爲提升。 惟，前述市售之高純度鎢粉末，其再微細比表面積也 不過0.2m2/g左右。 是以，本發明者乃以甲基鎢酸銨做爲起始原料使用’ 進行高純度化精製，將所得之純度5N以上之鎢酸結晶以 氫還原，此時若提升氫氣供給量與反應生成氣體之去除速 度，則可製作出比表面積〇.4m2/g〜0.8m2/g、粒徑 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)The total of transition metals or heavy metals such as Mo is 10 ppm or less. 3. The tungsten sintered body whip for sputtering as described in 1 or 2 above, wherein the density is 99.5% or more, the average particle size is less than, and the crystals are isotropic and the orientation is irregular. 4. A method for manufacturing a tungsten sintered body target for sputtering, characterized in that sintering is performed using a tungsten powder having a powder specific surface area of 0.4 m2 / g or more (BET method) and an oxygen content of 1,000 ppm or less. 5. The method for manufacturing a tungsten sintered body target for sputtering according to the above 4, using a tungsten powder having a specific surface area of 0.6 m2 / g to 0.8 m2 / g (BET method) and an oxygen content of 800 ppm or less Sintering is performed. 6—A method for manufacturing a tungsten sintered body target for sputtering, characterized in that a tungsten powder having a specific surface area of 0.4 m2 / g or more (BET method) is used, and the pressure is applied in a vacuum or reducing atmosphere After hot-pressing sintering at a starting temperature of 1200 ° C or lower, further hot-pressing sintering (HIP) is performed. 7. The method for producing a tungsten sintered body target for sputtering according to the above 6, wherein the powder has a specific surface area of 0.6 m2 / g to 0.8 m2 / g (BET method). 8. The manufacturing method of the tungsten sintered body target for sputtering as described in any one of 4 to 7 above is adjusted to a relative density of 93% or more by hot press sintering. 9. The method for manufacturing a tungsten sintered body target for sputtering as described in any of 4 to 8 above, which is heated at a temperature of 1600 ° C or higher and a pressure of 150 kg / cm2 or higher. 10. The sputtering according to any of 4 to 9 above Manufacture of tungsten sintered body target for plating The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) --------- I --- install i 丨 (Please read the back Please fill in this page again for the matters needing attention). 574377 A7 ^ ----- 一 —___ B7__ 5. Description of the invention (^) The method is to perform hot pressure sintering (HIP) without encapsulation. 11. The method for manufacturing a tungsten sintered body target for sputtering according to any one of 4 to 10 above, wherein the hot-pressing sintering is performed at a temperature of 1700 ° C or higher and a pressure of 1000 kg / cm2 or higher. 12. The method for producing a tungsten sintered body target for sputtering according to any one of 4 to 10 above, which is performed by hot equalizing sintering at a temperature of 1850 ° C or higher and a pressure of 1800 kg / cm2 or higher. [Embodiments of the Invention] Generally, commercially available high-purity tungsten powder with a purity of 5N or more has a powder specific surface area of 0.3 m2 / g or less. If this powder is attempted to be produced by a pressure sintering method, the relative density is 99% or more For tungsten targets, firing temperatures above 2000 ° C are required. However, at a firing temperature of 2000 ° C or more, the crystal grains will become larger than 100 μηι. In addition, pressure sintering at such a high temperature, for example, the hot pressing method will cause a reaction between the mold and tungsten, and HIP will cause a reaction with the capsule material. These major problems will increase the manufacturing cost. Generally, in the case of the powder metallurgy method, it is known that the finer the particle size of the powder used, that is, the larger the specific surface area, the more improved the sinterability. However, the aforementioned commercially available high-purity tungsten powder has a finer specific surface area of only about 0.2 m2 / g. Therefore, the present inventors used ammonium methyltungstate as a starting material to perform high-purity purification, and reduced the obtained tungstic acid crystals with a purity of 5N or more with hydrogen. At this time, if the amount of hydrogen supply is increased and the reaction is generated The removal speed of the gas can produce a specific surface area of 0.4m2 / g ~ 0.8m2 / g, and the particle size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back first) (Fill in this page again)
574377 A7 _ B7____ 五、發明說明（f ) ο·4〜ο.δμιη、且氧含量爲lOOOppm以下(更佳爲8〇〇ppm以 下)之鎢粉末，進而使用此鎢粉末。若氧含量超過lOOOppm 由於燒結性會降低，所以使用之鎢粉末之氧含量以低者爲 宜。 再者，做爲本發明之鎢靶材料，係使用會影響半導體 特性之Na、K等之驗金屬總量在lppm以下、U、Th等之 放射性元素總量在lOppb以下、碳含量在lOppm以下、Fe 、Ni、Cr、Mo等之過渡金屬或重金屬之總和爲10ppm以 下之鎢粉末。 將此種具有大比表面積之鎢粉末以1600°C以上（更佳 爲1800°C以上）、施加壓力150kg/cm2以上、且加壓開始溫 度1200°C以下之條件進行熱壓，則相對密度成爲93%以上 ，氣孔形態成爲閉氣孔，所以即使不行膠囊化亦能進行 HIP處理。 若加壓開始溫度超過1200°C，則結晶粒成長會造成燒 結性下降，又爲了得到可在無膠囊化下進行HIP之閉氣孔 的密度(93%以上）需要2000°C以上之熱壓溫度，會出現後 述之問題，所以加壓開始溫度以1200°C以下爲佳。 如上所述，將熱壓溫度控制在2000°C以上雖可有效地 緻密化但會出現結晶粒之巨大化並有會與模具發生反應等 之問題，所以在1900°C以下進行熱壓乃爲所希望者。又， 在進行熱壓之際，藉由在上面以及下面使用碳片，可促進 氧自材料解離。 再者，若以1700°C以上(更佳爲1850°C以上)之溫度、 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)574377 A7 _ B7____ V. Description of the invention (f) ο · 4 ~ ο.δμιη and a tungsten powder with an oxygen content of 1000 ppm or less (more preferably 800 ppm or less), and further use of this tungsten powder. If the oxygen content exceeds 100 ppm, the sinterability will be reduced, so the lower oxygen content of the tungsten powder used is preferred. In addition, as the tungsten target material of the present invention, the total amount of test metals such as Na, K and the like that affect semiconductor characteristics is less than 1 ppm, the total amount of radioactive elements such as U and Th is less than 10 ppb and the carbon content is less than 10 ppm Tungsten powder whose total of transition metals or heavy metals such as Fe, Ni, Cr, Mo, etc. is 10 ppm or less. The relative density of such a tungsten powder having a large specific surface area is hot-pressed under conditions of 1600 ° C or higher (more preferably 1800 ° C or higher), a pressure of 150kg / cm2 or higher, and a pressure starting temperature of 1200 ° C or lower. At 93% or more, the stomata form closed stomata, so HIP treatment can be performed even without encapsulation. If the pressing start temperature exceeds 1200 ° C, the growth of crystal grains will reduce the sinterability, and in order to obtain the density of closed pores (93% or more) that can be HIP without encapsulation, a hot pressing temperature of 2000 ° C or more is required. Since there will be problems described later, the starting temperature for pressurization is preferably below 1200 ° C. As mentioned above, although the hot-pressing temperature can be effectively densified above 2000 ° C, it can effectively densify, but the crystal grains will increase and there will be problems such as reaction with the mold. Therefore, hot-pressing below 1900 ° C is necessary. Hope. When hot pressing is performed, the use of carbon chips on the top and bottom can promote the dissociation of oxygen from the material. In addition, if the temperature of the paper is above 1700 ° C (more preferably 1850 ° C), the Chinese standard (CNS) A4 specification (210 X 297 mm) applies to this paper size (please read the precautions on the back before filling (This page)
574377 A7 ___JB7 五、發明說明（L) (請先閱讀背面之注意事項再填寫本頁) 施加壓力l〇〇〇kg/cm2以上(較佳爲1800kg/cm2以上)來進行 HIP處理，則可得到平均結晶粒徑ΙΟΟμηι以下、甚至是平 均結晶粒徑80μπι以下之鎢靶。此時之結晶粒形狀並非壓 延品之異形粒，而是等向形狀、且不規則配向。 又，此時之HIP處理能以無膠囊化來實施。 鎢粉之比表面積愈大則熱壓後之鎢燒結體之密度愈高 ，且結晶結構愈爲微細，HIP處理所造成之密度增加也變 得容易，HIP處理後之密度也變高。 使用以此方式所得之鎢靶所製作之膜上之粒子缺陷的 發生很顯著地減少了。 實施例與比較例 以下依據實施例與比較例做說明。又，本實施例充其 量不過爲一例，本發明並不受限於此。亦即，包含有本發 明所舉之其他態樣或變形。 (實施例1、實施例2、實施例3) 使用粉體比表面積分別爲0.42 m2/g、0.62 m2/g、0.78 m2/g之含氧量分別爲360ppm、540ppm、840ppm之鎢粉末 ，自800°C以壓力300kg/cm2來加壓，然後進行在1600°C 以及1800°C保持2小時之熱壓燒成(分別爲實施例1、實施 例2、實施例3)。所得之鎢燒結體之相對密度係示於表1 〇 將此鎢燒結體進一步以1800°C、1500kg/cm2、2’小時 的條件進行HIP處理，所得之燒結體之相對密度、平均粒 徑、氧含量、3點抗撓強度以及使用該鎢燒結體進行濺鍍 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 574377 300kg/cm2 A7 B7 五、發明說明（1 ) 時之形成薄膜上的粒子數係示於表2。 如表1所示般，熱壓後之燒結體的相對密度爲 93.7%〜98.2%。又如表2所示般，Hlp處理後之鎢燒結體的 相如度爲"％〜99·8%。上述所得之燒結體的平均結晶粒 徑爲55_〜88阿，皆在1〇〇μιη以下。再者，氧含量均在 2〇ΡΡ1Ώ以下，抗撓強度爲520MPa〜630MPa，均在500MPa 以上。 $用此鎢燒結體進行濺鍍之膜上的粒子數爲0.03〜〇 〇7 個/cm，皆在0·1個/cm2以下，得到品質極佳之膜。 表2 本紙張尺度適用 1準(cns)A4 (請先閱讀背面之泫意事項再填寫本頁)574377 A7 ___JB7 V. Description of the invention (L) (Please read the precautions on the back before filling in this page) Apply HIP treatment at a pressure of 100 kg / cm2 or more (preferably 1800 kg / cm2 or more) to obtain Tungsten targets with an average crystal grain size of 100 μm or less, or even an average crystal grain size of 80 μm or less. The crystal grain shape at this time is not an irregular grain of a rolled product, but an isotropic shape and an irregular orientation. The HIP treatment at this time can be performed without encapsulation. The larger the specific surface area of the tungsten powder, the higher the density of the tungsten sintered body after hot pressing, and the finer the crystal structure, the easier the increase in density caused by HIP treatment, and the higher the density after HIP treatment. The occurrence of particle defects on a film made using the tungsten target obtained in this way is significantly reduced. Examples and Comparative Examples The following description is based on the examples and comparative examples. The present embodiment is merely an example at best, and the present invention is not limited thereto. That is, it includes other aspects or modifications as described in the present invention. (Example 1, Example 2, Example 3) Tungsten powders having a specific surface area of powders of 0.42 m2 / g, 0.62 m2 / g, and 0.78 m2 / g, respectively, having an oxygen content of 360 ppm, 540 ppm, and 840 ppm, were used. 800 ° C was pressurized at a pressure of 300 kg / cm2, and then hot-pressed firing was performed at 1600 ° C and 1800 ° C for 2 hours (respectively, Example 1, Example 2, and Example 3). The relative density of the obtained tungsten sintered body is shown in Table 10. The HIP treatment was performed on this tungsten sintered body under the conditions of 1800 ° C, 1500 kg / cm2, and 2 'hours. The relative density, average particle size, Oxygen content, 3-point flexural strength, and sputtering using this tungsten sintered body. This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) 574377 300kg / cm2 A7 B7 V. Description of the invention (1) The number of particles on the formed thin film is shown in Table 2. As shown in Table 1, the relative density of the sintered body after hot pressing was 93.7% to 98.2%. As shown in Table 2, the degree of homogeneity of the tungsten sintered body after the Hlp treatment is "% to 99.8%. The average crystal grain diameter of the sintered bodies obtained above was 55-88 A, all of which were 100 μm or less. Moreover, the oxygen content is all below 20 PP1Ώ, and the flexural strength is 520 MPa to 630 MPa, all of which are above 500 MPa. The number of particles on the film sputtered with this tungsten sintered body is 0.03 to 0.07 particles / cm, all of which are less than 0.1 particles / cm2, and a film of excellent quality is obtained. Table 2 Standards for this paper 1 cns (A4) (Please read the notice on the back before filling this page)
----- 卜^__ 表1 ^— 粉體之比表面積 ^ (m2/g) 粉體中之氧量 熱壓溫度 ΓΟ 熱壓後之相對密度 實施例1 0.42 360 1600 93.7% 1800 96.8% 實施例2 0.62 540 1600 95.2% 1800 97.8% 實施例3 0.78 840 1600 95.9% --- 1800 98.2% 實施例4 1.1 790 1600 96.4% 1800 98.8% 實施例5 1.4 890 1600 96.2% 1800 98.5% 比較1夕U1 比較例Y 0.23 1600 91.1% 比較例Γ 210 1800 93.6% 比較例4 ^ ------- 2200 95.4% 一 U 1310 1800 91.8% 熱鹰 $時，加壓開始溫度 ：800 °C ，施加壓力： 574377 . A7 B7 五、發明說明) HDP處理後 相對密度 平均粒徑 氧量 抗撓強度 私丁獻 (個細2) (%) (μπα) (PPm) (MPa) 99 74 <20 540 0.07 實施例1 99.5 88 <20 520 0.07 99.2 69 <20 550 0.05 實施例2 99.7 80 <20 540 0.06 99.4 55 1 <20 630 0.03 實施例3 99.8 70 <20 580 0.04 99.5 42 <20 680 0.04 實施例4 99.7 56 <20 620 0.01 99.5 40 <20 660 0.03 實施例5 99.7 52 <20 680 0.05 比較例1 93.2 94 <20 220 1.7 比較例2 98.7 130 <20 440 0.6 比較例3 99 177 一 <20 380 0.3 比較例4 97.5 38 90 380 0.7 •--------I----· I I (請先閱讀背面之注意事項再填寫本頁) HIP 條件·· 180(TCxl500kg/cm2x2 小時 (實施例4、實施例5)----- Bu ^ __ Table 1 ^ — Specific surface area of powder ^ (m2 / g) Oxygen amount in powder Hot pressing temperature ΓΟ Relative density after hot pressing Example 1 0.42 360 1600 93.7% 1800 96.8% Example 2 0.62 540 1600 95.2% 1800 97.8% Example 3 0.78 840 1600 95.9% --- 1800 98.2% Example 4 1.1 790 1600 96.4% 1800 98.8% Example 5 1.4 890 1600 96.2% 1800 98.5% Comparison U1 Comparative example Y 0.23 1600 91.1% Comparative example Γ 210 1800 93.6% Comparative example 4 ^ ------- 2200 95.4% One U 1310 1800 91.8% When the thermal eagle is $, the pressure start temperature: 800 ° C, apply Pressure: 574377. A7 B7 V. Description of the invention) Relative density, average particle diameter, oxygen content, flexural strength after HDP treatment (small 2) (%) (μπα) (PPm) (MPa) 99 74 < 20 540 0.07 Example 1 99.5 88 < 20 520 0.07 99.2 69 < 20 550 0.05 Example 2 99.7 80 < 20 540 0.06 99.4 55 1 < 20 630 0.03 Example 3 99.8 70 < 20 580 0.04 99.5 42 < 20 680 0.04 Example 4 99.7 56 < 20 620 0.01 99.5 40 < 20 660 0.03 Example 5 99.7 52 < 20 680 0.05 Comparative Example 1 93.2 94 < 20 220 1.7 Comparative Example 2 98.7 130 < 20 440 0.6 Comparative Example 3 99 177-&20; 380 0.3 Comparative Example 4 97.5 38 90 380 0.7 • -------- I- --- · II (Please read the precautions on the back before filling this page) HIP conditions 180 (TCxl500kg / cm2x2 hours (Example 4 and Example 5)
除了使用讓氧化鎢粉末做氫還原所得之鎢粉末不曝露 於大氣而保存之粉體比表面積分別爲Llm2/g以及Mm2/g 、且氧含量分別爲790ppm、890ppm之鎢粉末(分別爲實施 例4、實施例5)以外，其餘與實施例1同樣條件所製作之 熱壓燒結體以及HIP處理後之燒結體的諸特性係同樣地示 於表1與表2。 由結果可知，任一燒結體均具有99.5%以上的相對密 度，氧含量在20ppm以下，平均結晶粒徑爲6〇μηι以下， 抗撓強度爲600MPa。使用此鎢燒結體所形成之膜上的粒 子數爲0.01個/cm2〜0.05個/cm2，得到品質極佳之膜。 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 574377 A7 B7 五、發明說明（1 ) (實施例6、實施例7、實施例8) 除了使用比表面積〇·78 m2/g、含氧量爲840ppm之鎢 粉末，熱壓時之施加壓力分別爲150、200、..300kg/cm2(分 別爲實施例6、實施例7、實施例8)以外，其餘與實施例3 同樣條件所製作之熱壓燒結體以及HIP處理後之燒結體的 諸特性係示於表3。 所得燒結體之相對密度爲99.7%〜99.8%，平均粒徑爲 67μιη〜72μπι，可得到滿足相對密度在99%以上、平均粒徑 爲ΙΟΟμιη以下之燒結體。 表3In addition to using tungsten powder obtained by reducing tungsten oxide powder for hydrogen reduction, the powder has a specific surface area of Llm2 / g and Mm2 / g, and the oxygen content is 790ppm and 890ppm (respectively, examples). 4. Except for Example 5), the characteristics of the hot-pressed sintered body and HIP-treated sintered body produced under the same conditions as in Example 1 are shown in Tables 1 and 2. From the results, it can be seen that each of the sintered bodies has a relative density of 99.5% or more, an oxygen content of 20 ppm or less, an average crystal grain size of 60 μm or less, and a flexural strength of 600 MPa. The number of particles on the film formed using this tungsten sintered body was 0.01 particles / cm2 to 0.05 particles / cm2, and a film of excellent quality was obtained. 10 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 574377 A7 B7 V. Description of the invention (1) (Example 6, Example 7, Example 8) In addition to using a specific surface area of 0.88 m2 / g, tungsten powder with an oxygen content of 840ppm, the applied pressure during hot pressing is 150, 200, .. 300kg / cm2 (except for Example 6, Example 7, and Example 8), the rest are implemented Example 3 Table 3 shows the characteristics of the hot-pressed sintered body produced under the same conditions and the sintered body after HIP treatment. The obtained sintered body has a relative density of 99.7% to 99.8%, an average particle diameter of 67 μm to 72 μm, and a sintered body that satisfies a relative density of 99% or more and an average particle size of 100 μm or less can be obtained. table 3
熱壓壓力 (kg/cm2) 力口壓開始溫 度(t) 熱壓後之 相對密度 (%) HIP後 相對密度 (%) 平均粒徑 (μιη) 判定 比較例5 120 800 91.9 94.7 55 X 實施例6 150 800 94.3 99.8 67 〇 實施例7 200 800 97.4 99.7 72 〇 實施例8 300 800 98.2 99.8 70 〇 實施例9 300 1000 95.2 99.5 79 〇 實施例10 300 1200 93.8 99.3 82 〇 比較例6 300 1400 92.1 98.4 98 X 使用粉體比表面積：〇.78m2/g 熱壓溫度·保持時間：1800°Cx2小時 HIP 條件：1800°Cxl500kg/cm2x2 小時 (實施例9、實施例10) 除了使用比表面積爲0.78 m2/g、含氧量爲840ppm之 鎢粉末，自1000°C、1200°C(分別爲實施例9、實施例10) 施加300kg/cm2之壓力，然後進行在1800°C之2小時之熱 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝Hot pressing pressure (kg / cm2) Orifice pressure starting temperature (t) Relative density after hot pressing (%) Relative density after HIP (%) Average particle size (μιη) Judgment Comparative Example 5 120 800 91.9 94.7 55 X Example 6 150 800 94.3 99.8 67 〇 Example 7 200 800 97.4 99.7 72 〇 Example 8 300 800 98.2 99.8 70 〇 Example 9 300 1000 95.2 99.5 79 〇 Example 10 300 1200 93.8 99.3 82 〇 Comparative Example 6 300 1400 92.1 98.4 98 X Specific powder surface area: 0.88m2 / g Hot pressing temperature and holding time: 1800 ° Cx2 hours HIP conditions: 1800 ° Cx500kg / cm2x2 hours (Examples 9 and 10) Except that the specific surface area is 0.78 m2 / g. Tungsten powder with an oxygen content of 840ppm. Apply pressure of 300kg / cm2 from 1000 ° C and 1200 ° C (respectively to Example 9 and Example 10), and then heat 11 copies at 1800 ° C for 2 hours. Paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)
574377 A7 _____B7___ 五、發明說明) 壓燒成，其餘與實施例3同樣條件所製作之熱壓燒結體的 相對密度、平均結晶粒徑係示於表3。 ----------LIIW裝—— (請先閱讀背面之注意事項再填寫本頁) 兩者之HIP處理後之相對密度均在99%以上，平均結 晶粒徑亦在1〇〇μηι以下。 (比較例1、比較例2、比較例3) 使用比表面積爲0.23 m2/g、含氧量爲210ppm之鎢粉 末，以施加壓力 300kg/cm2、溫度 1600°C、1800°C、2200 °C分別熱壓燒成，將所得之燒結體以與實施例1同樣條件 進行HIP處理(分別爲比較例1、比較例2、比較例3)。所 得之燒結體之諸特性同樣地示於表1。 比較例1之以溫度1600°C所熱壓之燒結體、比較例2 之以溫度1800°C所熱壓之燒結體，於HIP處理後之相對密 度爲99%以下，於濺鍍所形成之膜上的粒子數也分別多達 0.6個/cm2以及1.7個/cm2，實用性不佳。 又，比較例3之以溫度2200°C所熱壓之燒結體，於 HIP處理後之相對密度雖達99%，惟平均結晶粒徑過於巨 大（高達177μπι)，又於濺鍍所形成之膜上的粒子數也多達 0.3 個/cm2。 (比較例4) 使用比表面積爲1.1 m2/g、含氧量爲1310ppm之鎢粉 末，以1800°C以及300kg/cm2進行熱壓燒成。 之後，以與實施例1同樣的條件進行HIP處理。所得 之燒結體之諸特性同樣地示於表1。 於HIP處理後之燒結體之相對密度爲97.5%，低於 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 574377 ___B7__ 五、發明說明（t l ) 99% 0 (比較例5) 除了將熱壓壓力調整爲120kg/cm2以外，其餘以與實 施例3同樣的條件製作鎢燒結體。所得之鎢燒結體之相對 密度以及平均粒徑同樣地示於表2。平均結晶粒徑雖55μιη 屬微細之物，但相對密度低至94.7%。 (比較例6) 除了將熱壓時之加壓開始溫度調整爲140(TC以外，g 餘以與實施例4同樣的條件製作鎢燒結體。所得之鶴燒，結 體之相對密度以及平均粒徑係示於表2。 平均結晶粒徑雖爲98μτη在ΙΟΟμηι以下，但相較於其 他實施例所得之平均結晶粒徑來得大，又相對密度在99% 以下，不適於做爲進行高品質之薄膜形成時的靶。 [發明之效果] 以本發明之方法所製造之濺鍍用鎢靶，相較於以習知 之加壓燒纟ΡΙ法所得之鶴祀具有密度局、結晶粒徑小之特徵 ，且可大幅地提升抗撓強度，相較於以往之CVD-W法可 顯著地降低製造成本，此爲本發明所具效果。 再者’若使用此鎢靶來進行濺鍍，則可顯著減少膜上 之粒子缺陷，製品良率可大幅提升，此爲本發明所具備之 優異特徵。 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 訂· ·574377 A7 _____B7___ 5. Description of the invention) The relative densities and average crystal grain sizes of the hot-pressed sintered bodies produced under the same conditions as in Example 3 under pressure firing are shown in Table 3. ---------- LIIW pack—— (Please read the precautions on the back before filling this page) The relative density of both after HIP treatment is above 99%, and the average crystal grain size is also 1〇 〇μηι or less. (Comparative Example 1, Comparative Example 2, Comparative Example 3) Tungsten powder having a specific surface area of 0.23 m2 / g and an oxygen content of 210 ppm was used at a pressure of 300 kg / cm2, a temperature of 1600 ° C, 1800 ° C, and 2200 ° C They were respectively hot-pressed and fired, and the obtained sintered bodies were subjected to HIP treatment under the same conditions as in Example 1 (Comparative Example 1, Comparative Example 2, and Comparative Example 3). The characteristics of the obtained sintered body are also shown in Table 1. The relative density of the sintered body that was hot-pressed at a temperature of 1600 ° C in Comparative Example 1 and the sintered body that was hot-pressed at a temperature of 1800 ° C of Comparative Example 2 was 99% or less after HIP treatment. The number of particles on the film is also as high as 0.6 particles / cm2 and 1.7 particles / cm2, which is not practical. In addition, although the relative density of the sintered body hot-pressed at 2200 ° C in Comparative Example 3 after HIP treatment was 99%, the average crystal grain size was too large (up to 177 μm), and the film formed by sputtering The number of particles on it is also as high as 0.3 particles / cm2. (Comparative Example 4) Tungsten powder having a specific surface area of 1.1 m2 / g and an oxygen content of 1310 ppm was subjected to hot-press firing at 1800 ° C and 300 kg / cm2. Thereafter, HIP processing was performed under the same conditions as in Example 1. The characteristics of the obtained sintered body are also shown in Table 1. The relative density of the sintered body after HIP treatment is 97.5%, which is lower than 12. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 574377 ___B7__ V. Description of the invention (tl) 99% 0 ( Comparative Example 5) A tungsten sintered body was produced under the same conditions as in Example 3 except that the hot pressing pressure was adjusted to 120 kg / cm 2. The relative density and average particle diameter of the obtained tungsten sintered body are also shown in Table 2. Although the average crystal grain size is 55 μm, it is a fine substance, but the relative density is as low as 94.7%. (Comparative Example 6) A tungsten sintered body was produced under the same conditions as in Example 4 except that the starting temperature of the pressurization at the time of hot pressing was adjusted to 140 ° C. The obtained crane fired, the relative density of the structure, and the average grain size. The diameters are shown in Table 2. Although the average crystal grain size is 98 μτη or less than 100 μηι, it is larger than the average crystal grain size obtained in other examples, and the relative density is less than 99%, which is not suitable for high-quality products. Target at the time of film formation [Effect of the invention] The tungsten target for sputtering produced by the method of the present invention has a density density and a smaller crystal grain size than a crane target obtained by the conventional pressure firing method. Characteristics, and can greatly improve the flexural strength, which can significantly reduce the manufacturing cost compared with the conventional CVD-W method, which is the effect of the present invention. Furthermore, if this tungsten target is used for sputtering, it can be used. The particle defect on the film is significantly reduced, and the product yield can be greatly improved, which is an excellent feature of the present invention. 13 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back first) Note for refilling This page) stapling · ·