TW202302890A - Ta-B sputtering target - Google Patents
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 94
- 239000002245 particle Substances 0.000 claims abstract description 70
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims description 38
- 150000004767 nitrides Chemical class 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 230000003746 surface roughness Effects 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229910004483 Ta3B4 Inorganic materials 0.000 abstract description 2
- 229910004533 TaB2 Inorganic materials 0.000 abstract description 2
- -1 Ta5B6 Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 79
- 238000004544 sputter deposition Methods 0.000 description 47
- 230000015572 biosynthetic process Effects 0.000 description 39
- 239000000843 powder Substances 0.000 description 32
- 230000002159 abnormal effect Effects 0.000 description 31
- 239000000428 dust Substances 0.000 description 26
- 238000005259 measurement Methods 0.000 description 17
- 238000005245 sintering Methods 0.000 description 13
- 239000010409 thin film Substances 0.000 description 13
- 239000000523 sample Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
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Abstract
Description
本發明係有關成膜含有Ta與B之薄膜(以下稱Ta-B薄膜)時所使用之Ta-B濺鍍靶。 本發明係根據於2021年2月2日,日本申請之日本特願2021-015279號主張優先權,將此內容援用於此。 The present invention relates to a Ta-B sputtering target used when forming a thin film containing Ta and B (hereinafter referred to as a Ta-B thin film). The present invention claims priority based on Japanese Patent Application No. 2021-015279 filed in Japan on February 2, 2021, and the contents thereof are incorporated herein.
以往,例如做為於形成10nm程度之微細配線圖案時所使用之EUV(極紫外線)空白光罩之EUV吸收膜,使用上述Ta-B薄膜(含Ta與B之氮化物薄膜,或含Ta與B之氧化物薄膜)。
在此,於專利文獻1、2中,提案有使用含Ta與B之濺鍍靶(以下,稱Ta-B濺鍍靶),進行氮反應性成膜或氧反應性成膜,成膜上述之EUV吸收膜之方法。
[先前技術文獻]
[專利文獻]
In the past, for example, the above-mentioned Ta-B film (a nitride film containing Ta and B, or a film containing Ta and B oxide film).
Here, in
[專利文獻1] 日本再公表WO2016/204051號公報 [專利文獻2] 日本特許第5760990號公報 [Patent Document 1] Japanese Publication No. WO2016/204051 [Patent Document 2] Japanese Patent No. 5760990
[發明欲解決之課題][Problem to be solved by the invention]
然而,記載於專利文獻1、2之Ta-B濺鍍靶係混合Ta粉與B粉加以燒結製造。為此,於Ta-B濺鍍靶中,成為導電體Ta與絕緣體之B之共存組織。使用如此Ta-B濺鍍靶濺鍍成膜之時,以絕緣體B為起點,產生異常放電,而成為塵埃之原因。
然而,如上所述,EUV空白光罩係使用於形成微細配線圖案時之故,於濺鍍成膜時,產生塵埃時,有無法將成膜Ta-B薄膜(含Ta與B之氮化物薄膜,或含Ta與B之氧化物薄膜),做為EUV吸收膜加以利用之疑慮。
However, the Ta-B sputtering targets described in
此發明係有鑑於上述情事而成,提供可抑制異常放電所造成塵埃之產生,可安定成膜Ta-B薄膜(含Ta與B之氮化物薄膜,或含Ta與B之氧化物薄膜)之Ta-B濺鍍靶為目的。 [為解決課題之手段] This invention is made in view of the above-mentioned circumstances, and provides a method that can suppress the generation of dust caused by abnormal discharge, and can stably form a Ta-B film (a nitride film containing Ta and B, or an oxide film containing Ta and B). Ta-B sputtering target for the purpose. [As a means to solve the problem]
為解決上述課題,本發明之Ta-B濺鍍靶係含有Ta與B之Ta-B濺鍍靶中,含有選自Ta 2B、Ta 3B 2、Ta 3B 4、Ta 5B 6、TaB、TaB 2一種或二種以上所成Ta-B化合物粒子,含有之B中之單體B之存在比為50%以下為特徵。 In order to solve the above-mentioned problems, the Ta-B sputtering target of the present invention is a Ta-B sputtering target containing Ta and B, which contains Ta2B , Ta3B2 , Ta3B4 , Ta5B6 , The Ta-B compound particles formed by one or two or more kinds of TaB and TaB are characterized in that the presence ratio of the monomer B in the contained B is 50% or less.
根據本發明之Ta-B濺鍍靶時,經由具有導電體之Ta-B化合物粒子,以確保B成分,可抑制含有之B中絕緣體之單體B之存在比在50%以下之故,於濺鍍成膜時,可抑制起因單體B之異常放電,而抑制塵埃之產生。According to the Ta-B sputtering target of the present invention, through the Ta-B compound particles having a conductor, to ensure the B component, the existence ratio of the monomer B of the insulator in the contained B can be suppressed below 50%. When forming a film by sputtering, it can suppress the abnormal discharge caused by the monomer B, and suppress the generation of dust.
在此,本發明之Ta-B濺鍍靶中,前述Ta-B化合物粒子之真圓度為0.3以上為佳。 此時,前述Ta-B化合物粒子之真圓度為0.3以上之時,可抑制Ta-B化合物粒子成為針狀或梯形狀,可抑制濺鍍成膜時之Ta-B化合物粒子之端部為起點之異常放電之產生,更可抑制塵埃之產生。 Here, in the Ta-B sputtering target of the present invention, the roundness of the aforementioned Ta-B compound particles is preferably 0.3 or more. At this time, when the roundness of the above-mentioned Ta-B compound particles is more than 0.3, the Ta-B compound particles can be suppressed from becoming acicular or trapezoidal, and the ends of the Ta-B compound particles during film formation by sputtering can be suppressed. The generation of abnormal discharge at the starting point can also suppress the generation of dust.
又,本發明之Ta-B濺鍍靶中,B之含有量為0.3mass%以上且10mass%以下之範圍內為佳。 此時,B之含有量為上述範圍內之故,成膜之Ta-B薄膜中,可得適於EUV之防止反射特性或吸收特性之光學特性,可成膜特別適於EUV吸收膜之Ta-B薄膜。 Moreover, in the Ta-B sputtering target of this invention, it is preferable that content of B exists in the range of 0.3 mass% or more and 10 mass% or less. At this time, because the content of B is within the above range, in the formed Ta-B thin film, optical properties suitable for EUV anti-reflection characteristics or absorption characteristics can be obtained, and Ta can be formed into a film that is especially suitable for EUV absorption films. -B film.
又,本發明之Ta-B濺鍍靶中,更含有選自Ta氮化物、B氮化物、Ta氧化物、B氧化物之一種或二種以上,N及O之合計含有量為20mass%以下者為佳。 此時,含有選自Ta氮化物、B氮化物、Ta氧化物、B氧化物之一種或二種以上之故,無需實施氮反應性成膜或氧反應性成膜,可成膜含Ta與B之氮化物薄膜,或含Ta與B之氧化物薄膜。又,於成膜時無需導入氧或氮等反應性氣體可加以成膜之故,可適用塵埃之產生較少之離子束濺鍍。 更且,N及O之合計含有量限制於20mass%以下之故,成膜之Ta-B薄膜中,可得適於EUV之防止反射特性或吸收特性之光學特性,成膜尤其適於EUV吸收膜之Ta-B薄膜。 In addition, the Ta-B sputtering target of the present invention further contains one or more selected from Ta nitride, B nitride, Ta oxide, and B oxide, and the total content of N and O is 20 mass% or less Whichever is better. At this time, because it contains one or two or more selected from Ta nitride, B nitride, Ta oxide, and B oxide, it is not necessary to perform nitrogen-reactive film formation or oxygen-reactive film formation, and a film containing Ta and A nitride film of B, or an oxide film containing Ta and B. In addition, since the film can be formed without introducing reactive gas such as oxygen or nitrogen, it can be applied to ion beam sputtering which generates less dust. Moreover, since the total content of N and O is limited to less than 20mass%, in the formed Ta-B thin film, optical properties suitable for EUV anti-reflection characteristics or absorption characteristics can be obtained, and the film formation is especially suitable for EUV absorption Film Ta-B thin film.
又,本發明之Ta-B濺鍍靶中,金屬不純物之Fe、Ni、Cr、Cu、Na、K之合計含有量為10000massppm以下為佳。 此時,金屬不純物之Fe、Ni、Cr、Cu、Na、K之合計含有量限制於10000massppm以下之故,可抑制濺鍍成膜時之金屬不純物為起點之異常放電之產生,更可抑制塵埃之產生。 In addition, in the Ta-B sputtering target of the present invention, the total content of Fe, Ni, Cr, Cu, Na, and K as metal impurities is preferably 10000 massppm or less. At this time, the total content of Fe, Ni, Cr, Cu, Na, and K of metal impurities is limited to less than 10,000 massppm, which can suppress the occurrence of abnormal discharge starting from metal impurities during sputtering film formation, and can also suppress dust. of the generation.
又,本發明之Ta-B濺鍍靶中,平均結晶粒子徑為50μm以下為佳。 此時,平均結晶粒子徑限制於50μm以下之故,即使進行濺鍍,於濺鍍面難以產生的凹凸,可更抑制濺鍍成膜時之異常放電之產生,更可抑制塵埃之產生。 Moreover, in the Ta-B sputtering target of this invention, it is preferable that the average crystal particle diameter is 50 micrometers or less. At this time, since the average crystal particle size is limited to 50 μm or less, even if sputtering is performed, unevenness that is difficult to occur on the sputtered surface can be further suppressed from generating abnormal discharge during sputtering film formation, and can further suppress the generation of dust.
又,本發明之Ta-B濺鍍靶中,表面粗糙度Ra(算術平均粗糙度)為1.6μm以下為佳。 此時,表面粗糙度Ra為1.6μm以下之故,可更抑制濺鍍成膜時之異常放電之產生,更可抑制塵埃之產生。 Moreover, in the Ta-B sputtering target of this invention, it is preferable that surface roughness Ra (arithmetic mean roughness) is 1.6 micrometers or less. In this case, since the surface roughness Ra is 1.6 μm or less, the occurrence of abnormal discharge during film formation by sputtering can be further suppressed, and the generation of dust can be further suppressed.
又,本發明之Ta-B濺鍍靶中,密度比為90%以上為佳。 此時,密度比為90%以上,空洞少之故,可更抑制濺鍍成膜時之異常放電之產生,更可抑制塵埃之產生。 Also, in the Ta-B sputtering target of the present invention, the density ratio is preferably 90% or more. At this time, the density ratio is more than 90% and the voids are less, so that the occurrence of abnormal discharge during sputtering film formation can be further suppressed, and the generation of dust can be further suppressed.
又,本發明之Ta-B濺鍍靶中,電阻率為1Ωcm以下為佳。 此時,電阻率為1Ωcm以下之故,充分確保導電性之故,可更抑制濺鍍成膜時之異常放電之產生,更可抑制塵埃之產生。 [發明效果] Moreover, in the Ta-B sputtering target of this invention, it is preferable that resistivity is 1 Ωcm or less. In this case, since the resistivity is 1 Ωcm or less, sufficient electrical conductivity can be ensured, the occurrence of abnormal discharge during film formation by sputtering can be further suppressed, and the generation of dust can be further suppressed. [Invention effect]
根據本發明時,可提供抑制異常放電所造成塵埃之產生,可安定成膜Ta-B薄膜(含Ta與B之氮化物薄膜,或含Ta與B之氧化物薄膜)之Ta-B濺鍍靶。According to the present invention, it is possible to provide Ta-B sputtering that suppresses the generation of dust caused by abnormal discharge and can stably form a Ta-B film (a nitride film containing Ta and B, or an oxide film containing Ta and B). target.
以下,參照對於本發明之實施形態之Ta-B濺鍍靶所附加之圖面加以說明。 關於本實施形態之Ta-B濺鍍靶係例如使用於成膜做為EUV(極紫外線)空白光罩之EUV吸收膜使用之Ta-B薄膜(含Ta與B之氮化物薄膜,或含Ta與B之氧化物薄膜)之時。 Hereinafter, it demonstrates referring drawings attached to the Ta-B sputtering target which concerns on embodiment of this invention. The Ta-B sputtering target of this embodiment is used, for example, to form a Ta-B film (a nitride film containing Ta and B, or a film containing Ta and the oxide film of B).
然而,本實施形態之Ta-B濺鍍靶中,對於該形狀沒有限定,可為濺鍍面成為矩形狀之矩形平板型濺鍍靶,亦可為濺鍍面成為圓形之圓板型濺鍍靶。或,濺鍍面成為圓筒面之圓筒型濺鍍靶亦可。However, in the Ta-B sputtering target of the present embodiment, the shape is not limited, and it may be a rectangular plate-shaped sputtering target whose sputtering surface is rectangular, or a disc-shaped sputtering target whose sputtering surface is circular. Plated target. Alternatively, a cylindrical sputtering target whose sputtering surface becomes a cylindrical surface may also be used.
關於本實施形態之Ta-B濺鍍靶中,具有選自Ta 2B、Ta 3B 2、Ta 3B 4、Ta 5B 6、TaB、TaB 2一種或二種以上所成Ta-B化合物粒子。 Ta係仗為主成分含於Ta-B濺鍍靶,對於Ta-B濺鍍靶整體而言,含有80mass%以上99.9mass%以下之範圍為佳。 然後,關於本實施形態之Ta-B濺鍍靶中,含有B之中,不與Ta化合之單體B之存在比為50%以下。即,關於本實施形態之Ta-B濺鍍靶中,所含有B之50%以上以化合物之形態存在。 Regarding the Ta-B sputtering target of this embodiment, there is a Ta-B compound formed by one or more kinds selected from Ta 2 B, Ta 3 B 2 , Ta 3 B 4 , Ta 5 B 6 , TaB, and TaB 2 particle. Ta is contained in the Ta-B sputtering target as a main component. For the Ta-B sputtering target as a whole, it is preferable to contain 80 mass% or more and 99.9 mass% or less. And, in the Ta—B sputtering target of this embodiment, the abundance ratio of the monomer B which does not combine with Ta among B contained is 50% or less. That is, in the Ta—B sputtering target of this embodiment, 50% or more of contained B exists in the form of a compound.
然而,含有之B中之單體B之存在比係如圖1及圖2所示,經由XRD測定所成尖峰強度比加以算出。即,進行XRD測定,如下述(1)式所示,將歸屬於單體B之尖峰強度,以歸屬於Ta-B化合物之尖峰強度與歸屬於單體B之尖峰強度之和除之,乘上100之比例,做為單體B之存在比(%)。然而,測定單體B及Ta-B化合物之尖峰強度之面係示於以下。 (1)式:單體B之存在比(%)={(B單體)/(Ta-B化合物+B單體)} 單體B:(104)面 Ta 2B:(211)面 Ta 3B 2:(201)面 Ta 3B 4:(031)面 Ta 5B 6:(510)面 TaB:(021)面 TaB 2:(101)面 However, the abundance ratio of the monomer B in the contained B was calculated from the peak intensity ratio of the XRD measurement as shown in FIG. 1 and FIG. 2 . That is, XRD measurement is carried out, as shown in the following formula (1), the peak intensity attributable to monomer B is divided by the sum of the peak intensity attributable to the Ta-B compound and the peak intensity attributable to monomer B, and multiplied by The ratio above 100 is taken as the presence ratio (%) of monomer B. However, the areas for measuring the peak intensities of the monomer B and the Ta-B compound are shown below. (1) Formula: Existence ratio of monomer B (%)={(B monomer)/(Ta-B compound+B monomer)} Monomer B: (104) face Ta 2 B: (211) face Ta 3 B 2 : (201) plane Ta 3 B 4 : (031) plane Ta 5 B 6 : (510) plane TaB: (021) plane TaB 2 : (101) plane
又,於本實施形態之Ta-B濺鍍靶中,Ta-B化合物粒子之真圓度為0.3以上為佳。然而,Ta-B化合物粒子之真圓度係從觀察Ta-B濺鍍靶時之Ta-B化合物粒子之面積與周長,以如下之式加以定義者。 真圓度=4π×(面積)/(周長) 2例如,Ta-B化合物粒子之真圓度係根據觀察Ta-B濺鍍靶所得畫像,經由上述式加以算出。此畫像係Ta-B濺鍍靶之表面中,在10,000μm 2以上100,000μm 2以下之面積範圍所得者為佳。 真圓度之算出係可根據複數之Ta-B化合物粒子之畫像進行。此時,可將複數之真圓度之平均做為Ta-B化合物粒子之真圓度。 Moreover, in the Ta-B sputtering target of this embodiment, it is preferable that the roundness of a Ta-B compound particle is 0.3 or more. However, the roundness of the Ta-B compound particles is defined by the following formula from the area and perimeter of the Ta-B compound particles when observing the Ta-B sputtering target. Circularity=4π×(area)/(circumference) 2 For example, the circularity of Ta-B compound particles is calculated from the image obtained by observing the Ta-B sputtering target through the above formula. This image is preferably obtained from the surface of the Ta-B sputtering target in an area ranging from 10,000 μm 2 to 100,000 μm 2 . The calculation of the true circularity can be performed based on the images of a plurality of Ta-B compound particles. At this time, the average of the roundness of the plural numbers can be taken as the roundness of the Ta-B compound particles.
在此,將本實施形態之Ta-B濺鍍靶之組織觀察照片之一例,示於圖3。於此圖3中,白色部分為單體Ta,白色部分以外之濃色部分為Ta-B化合物粒子(圖3中為TaB 2)、黑色部分為空隙。 Here, an example of the microstructure observation photograph of the Ta-B sputtering target of this embodiment is shown in FIG. 3 . In this Fig. 3, the white part is the monomer Ta, the dark part other than the white part is the Ta-B compound particle ( TaB2 in Fig. 3), and the black part is the void.
又,本實施形態之Ta-B濺鍍靶中,B之含有量為0.3mass%以上且10mass%以下之範圍內為佳。 更且,本實施形態之Ta-B濺鍍靶中,金屬不純物之Fe、Ni、Cr、Cu、Na、K之合計含有量為10000massppm以下為佳。 Moreover, in the Ta-B sputtering target of this embodiment, it is preferable that content of B exists in the range of 0.3 mass% or more and 10 mass% or less. Furthermore, in the Ta-B sputtering target of this embodiment, it is preferable that the total content of Fe, Ni, Cr, Cu, Na, and K of metal impurities is 10000 massppm or less.
又,本實施形態之Ta-B濺鍍靶中,更含有選自Ta氮化物(TaN)、B氮化物(BN)、Ta氧化物(Ta 2O 5)、B氧化物(B 2O 3)之一種或二種以上,N及O之合計含有量為20mass%以下者為佳。 In addition, in the Ta - B sputtering target of the present embodiment , further containing ) of one or more, preferably with a total content of N and O below 20mass%.
更且,本實施形態之Ta-B濺鍍靶中,平均結晶粒子徑為50μm以下為佳。 又,實施形態之Ta-B濺鍍靶中,表面粗糙度Ra為1.6μm以下為佳。 Furthermore, in the Ta-B sputtering target of this embodiment, it is preferable that the average crystal particle diameter is 50 micrometers or less. Moreover, in the Ta-B sputtering target of embodiment, it is preferable that surface roughness Ra is 1.6 micrometers or less.
更且,本實施形態之Ta-B濺鍍靶中,密度比為90%以上為佳。 又,實施形態之Ta-B濺鍍靶中,電阻率為1Ωcm以下為佳。 Furthermore, in the Ta-B sputtering target of this embodiment, it is preferable that the density ratio is 90% or more. Moreover, in the Ta-B sputtering target of embodiment, it is preferable that resistivity is 1 Ωcm or less.
以下,於本實施形態之Ta-B濺鍍靶中,對於Ta-B化合物粒子、相構成、含有B中之單體B之存在比、Ta-B化合物粒子之真圓度、B之含有量、Ta或B之氮化物及氧化物、金屬不純物之含有量、平均結晶粒子徑、表面粗糙度Ra、密度比、電阻率,顯示如上述規定之理由。In the following, in the Ta-B sputtering target of this embodiment, the Ta-B compound particles, the phase composition, the abundance ratio of monomer B in B, the roundness of the Ta-B compound particles, and the B content , Ta or B nitrides and oxides, content of metal impurities, average crystal particle size, surface roughness Ra, density ratio, and resistivity, showing the reasons specified above.
(Ta-B化合物粒子) 本實施形態之Ta-B濺鍍靶中,如上所述,含有選自Ta 2B、Ta 3B 2、Ta 3B 4、Ta 5B 6、TaB、TaB 2一種或二種以上所成Ta-B化合物粒子。此等之Ta-B化合物粒子係導電體之故,經由做為Ta-B化合物粒子含有B,可抑制濺鍍成膜時異常放電之產生。濺鍍面中Ta-B化合物粒子所佔面積比例係50%~99%、較佳為60%~97%、更佳為70%~95%。 (Ta-B Compound Particles) The Ta-B sputtering target according to the present embodiment contains one species selected from Ta 2 B, Ta 3 B 2 , Ta 3 B 4 , Ta 5 B 6 , TaB, and TaB 2 as described above. Or two or more kinds of Ta-B compound particles formed. Since these Ta-B compound particles are electrical conductors, by containing B as the Ta-B compound particles, it is possible to suppress the occurrence of abnormal discharge during sputtering film formation. The area ratio of the Ta-B compound particles on the sputtering surface is 50%-99%, preferably 60%-97%, more preferably 70%-95%.
(單體B之存在比) 如上所述,經由做為導電體之Ta-B化合物粒子含有B,可減低絕緣體之單體B之存在比,可抑制濺鍍成膜時之異常放電之產生。 為此,本實施形態中,將含於Ta-B濺鍍靶之B中之單體B之存在比規定在50%以下。 然而,為了更抑制濺鍍成膜時之異常放電之產生,含有之B中之單體B之存在比係20%以下為佳,較佳為10%以下,更佳為5%以下。雖未特別加以限定,對於B之存在比之下限值成為0.1%亦可。 (Existence ratio of monomer B) As described above, by containing B in the Ta—B compound particles as a conductor, the abundance ratio of the monomer B in the insulator can be reduced, and the occurrence of abnormal discharge during sputtering film formation can be suppressed. Therefore, in this embodiment, the abundance ratio of the monomer B contained in B of a Ta-B sputtering target is made into 50 % or less. However, in order to further suppress the occurrence of abnormal discharge during film formation by sputtering, the ratio of monomer B contained in B is preferably 20% or less, more preferably 10% or less, more preferably 5% or less. Although not particularly limited, the lower limit of the abundance ratio of B may be 0.1%.
(Ta-B化合物粒子之真圓度) 上述Ta-B化合物粒子中,由於生成時之條件,有成為針狀或梯形狀之情形。Ta-B化合物粒子為針狀或梯形狀之時,有在於濺鍍成膜時,將此等組織之端部做為起點產生異常放電之疑慮。 因此,為了更可抑制濺鍍成膜時之異常放電,令Ta-B化合物粒子之真圓度(4π×(面積)/(周長) 2)成為0.3以上為佳。 然而,Ta-B化合物粒子之真圓度係0.4以上為佳,更佳為0.5以上。雖未特別加以限定,對於Ta-B化合物粒子之真圓度之上限值成為1.0亦可。 (Circularity of Ta-B Compound Particles) The above-mentioned Ta-B compound particles may be acicular or trapezoidal depending on the conditions at the time of production. When the Ta-B compound particles are in the shape of needles or trapezoids, there is a possibility that an abnormal discharge may occur at the end of these structures as a starting point during film formation by sputtering. Therefore, in order to further suppress abnormal discharge during film formation by sputtering, it is preferable to set the roundness (4π×(area)/(circumference) 2 ) of Ta—B compound particles to 0.3 or more. However, the roundness of the Ta-B compound particles is preferably at least 0.4, more preferably at least 0.5. Although not particularly limited, the upper limit of the roundness of the Ta-B compound particles may be 1.0.
(B之含有量) 本實施形態之Ta-B濺鍍靶中,B之含有量為0.3mass%以上且10mass%以下之範圍內時,可充分確保成膜之Ta-B薄膜中EUV之反射・吸收特性。 為此,於本實施形態中,B之含有量為0.3mass%以上且10mass%以下之範圍內為佳。 然而,B之含有量係0.5mass%以上為佳,較佳為1.0mass%以上,更佳為1.3mass%以上。又,B之含有量係5.0mass%以下為佳,較佳為3.0mass%以下,更佳為2.0mass%以下。 (Content of B) In the Ta-B sputtering target of this embodiment, when the content of B is within the range of 0.3 mass% or more and 10 mass% or less, the reflection and absorption characteristics of EUV in the formed Ta-B thin film can be sufficiently ensured. Therefore, in this embodiment, the content of B is preferably in the range of 0.3 mass% or more and 10 mass% or less. However, the content of B is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, more preferably 1.3 mass% or more. Also, the content of B is preferably 5.0 mass% or less, more preferably 3.0 mass% or less, more preferably 2.0 mass% or less.
(Ta或B之氮化物及氧化物) 本實施形態之Ta-B濺鍍靶中,含有選自Ta氮化物、B氮化物、Ta氧化物、B氧化物之一種或二種以上之時,無需實施氮反應性成膜或氧反應性成膜,可成膜含Ta與B之氮化物薄膜,或含Ta與B之氧化物薄膜。 然後,N及O之合計含有量經由限制於20mass%以下,成膜之Ta-B薄膜中,可充分確保EUV之反射特性・吸收特性。 然而,N及O之合計含有量係15mass%以下為佳,更佳為12mass%以下。N及O之合計含有量之下限雖無特別限制,0.5mass%以上為佳,1.0mass%以上為更佳。 (Nitrides and oxides of Ta or B) When the Ta-B sputtering target of this embodiment contains one or more kinds selected from Ta nitrides, B nitrides, Ta oxides, and B oxides, it is not necessary to perform nitrogen-reactive film formation or oxygen-reactive film formation. For film formation, it can form a nitride film containing Ta and B, or an oxide film containing Ta and B. Then, by limiting the total content of N and O to less than 20mass%, the formed Ta-B thin film can sufficiently ensure EUV reflection and absorption characteristics. However, the total content of N and O is preferably at most 15 mass%, more preferably at most 12 mass%. The lower limit of the total content of N and O is not particularly limited, but it is preferably 0.5 mass% or more, more preferably 1.0 mass% or more.
(金屬不純物之含有量) 本實施形態之Ta-B濺鍍靶中,金屬不純物之Fe、Ni、Cr、Cu、Na、K之合計含有量經由限制於低水準,可抑制濺鍍成膜時之金屬不純物為起點之異常放電之產生。 為此,本實施形態中,金屬不純物之Fe、Ni、Cr、Cu、Na、K之合計含有量限制在10000massppm以下為佳。 然而,金屬不純物之Fe、Ni、Cr、Cu、Na、K之合計含有量係成為1000massppm以下為佳。更佳為500massppm以下。雖未特別加以限定,對於金屬不純物之合計含有量之下限值成為10massppm亦可。 (Content of metal impurities) In the Ta-B sputtering target of this embodiment, the total content of Fe, Ni, Cr, Cu, Na, and K as metal impurities is limited to a low level, which can suppress the abnormality starting from the metal impurities during sputtering film formation. generation of discharge. Therefore, in this embodiment, it is preferable to limit the total content of Fe, Ni, Cr, Cu, Na, and K as metal impurities to 10000 massppm or less. However, the total content of Fe, Ni, Cr, Cu, Na, and K of metal impurities is preferably 1000 massppm or less. More preferably, it is 500 massppm or less. Although not particularly limited, the lower limit of the total content of metal impurities may be 10 massppm.
(平均結晶粒子徑) 本實施形態之Ta-B濺鍍靶中,經由平均結晶粒子徑變小,即使進行濺鍍,於濺鍍面難以產生的凹凸,可更抑制濺鍍成膜時之異常放電之產生。 為此,本實施形態中,平均結晶粒子徑限制在50μm以下為佳。 又,平均結晶粒子徑係成為30μm以下為佳,更佳為20μm以下。 雖未特別加以限定,對於平均結晶粒子徑之下限值成為0.1μm亦可。 (average crystal particle diameter) In the Ta-B sputtering target of this embodiment, since the average crystal grain size is reduced, even if sputtering is performed, unevenness hardly occurs on the sputtering surface, and the occurrence of abnormal discharge during sputtering film formation can be further suppressed. Therefore, in this embodiment, it is preferable to limit the average crystal particle size to 50 μm or less. Also, the average crystal particle diameter is preferably 30 μm or less, more preferably 20 μm or less. Although not particularly limited, the lower limit of the average crystal particle size may be 0.1 μm.
(表面粗糙度Ra) 本實施形態之Ta-B濺鍍靶中,經由使表面粗糙度(算術平均粗糙度)Ra變小,可更抑制濺鍍成膜時之異常放電之產生。 為此,本實施形態中,表面粗糙度Ra限制在1.6μm以下為佳。 又,表面粗糙度Ra係成為1.2μm以下為佳,更佳為0.6μm以下。 雖未特別加以限定,對於表面粗糙度Ra之下限值成為0.01μm亦可。 (surface roughness Ra) In the Ta-B sputtering target of the present embodiment, by reducing the surface roughness (arithmetic mean roughness) Ra, the occurrence of abnormal discharge during sputtering film formation can be further suppressed. Therefore, in this embodiment, it is preferable that the surface roughness Ra is limited to 1.6 μm or less. In addition, the surface roughness Ra is preferably 1.2 μm or less, more preferably 0.6 μm or less. Although not particularly limited, the lower limit of the surface roughness Ra may be 0.01 μm.
(密度比) 本實施形態之Ta-B濺鍍靶中,經由使密度比變高,內部之空洞則變少,可更抑制濺鍍成膜時之異常放電之產生。 為此,本實施形態中,密度比係90%以上為佳。 然而,密度比係95%以上為佳,更佳為97%以上。 雖未特別加以限定,對於密度比之上限值成為100%亦可。 (density ratio) In the Ta-B sputtering target of this embodiment, by increasing the density ratio, the internal voids are reduced, and the occurrence of abnormal discharge during sputtering film formation can be further suppressed. Therefore, in this embodiment, the density ratio is preferably 90% or more. However, the density ratio is preferably at least 95%, more preferably at least 97%. Although not particularly limited, the upper limit of the density ratio may be 100%.
(電阻率) 本實施形態之Ta-B濺鍍靶中,伴隨含有上述Ta-B化合物粒子,經由將絕緣體之單體B之存在比率抑制在50%以下,使電阻率變低,可充分確保導電性,可更抑制濺鍍成膜時之異常放電之產生。 為此,本實施形態中,電阻率限制在1Ωcm以下為佳。然而,電阻率係成為0.1Ωcm以下為佳,更佳為0.01Ωcm以下。雖未特別加以限定,對於電阻率之下限值成為0.001Ωcm亦可。 (resistivity) In the Ta-B sputtering target of this embodiment, by containing the above-mentioned Ta-B compound particles, by suppressing the abundance ratio of the monomer B of the insulator to 50% or less, the resistivity becomes low, and the electrical conductivity can be sufficiently ensured. It also suppresses the occurrence of abnormal discharge during sputtering film formation. Therefore, in this embodiment, it is preferable to limit the resistivity to 1 Ωcm or less. However, the resistivity is preferably 0.1 Ωcm or less, more preferably 0.01 Ωcm or less. Although not particularly limited, the lower limit of the resistivity may be 0.001 Ωcm.
接著,對於上述本實施形態之Ta-B濺鍍靶之製造方法之一例,參照圖4加以說明。Next, an example of the manufacturing method of the Ta-B sputtering target of this Embodiment mentioned above is demonstrated with reference to FIG. 4. FIG.
(原料粉準備工程S01) 準備純度99.9mass%以上之Ta粉、和純度99mass%以上之Ta-B化合物粉。又,依需要,準備純度為99mass%以上之Ta氮化物粉、Ta氧化物粉、B氮化物粉、B氧化物粉。然而,此等之各原料粉之平均粒子徑係成為0.1μm以上且50μm以下之範圍內為佳。 在此,對於Ta-B化合物粉,為除去金屬不純物,以王水進行酸洗淨,以純水洗濯後,經由真空乾燥,充分加以乾燥為佳。 又,對於Ta-B化合物粉而言,為了提升燒結性,可以球磨機或噴射碾磨機進行粉碎。噴射碾磨機之粉碎係令噴射碾磨機之風量為0.3m 3/min以上、令壓力為0.6MPa以上為佳。 (Raw material powder preparation process S01) Prepare Ta powder with a purity of 99.9 mass% or higher and Ta-B compound powder with a purity of 99 mass% or higher. Also, Ta nitride powder, Ta oxide powder, B nitride powder, and B oxide powder with a purity of 99 mass% or more are prepared as needed. However, the average particle diameter of each of these raw material powders is preferably within a range of 0.1 μm or more and 50 μm or less. Here, the Ta-B compound powder should be acid-washed with aqua regia to remove metal impurities, washed with pure water, and then vacuum-dried to fully dry. In addition, the Ta-B compound powder may be pulverized by a ball mill or a jet mill in order to improve sinterability. The pulverization of the jet mill is to make the air volume of the jet mill more than 0.3m 3 /min and the pressure to be more than 0.6MPa.
(原料粉混合工程S02) 將上述各原料粉(Ta粉、Ta-B化合物粉、Ta氮化物粉、Ta氧化物粉、B氮化物粉、B氧化物粉)秤量成特定的比率,以球磨機加以混合。球磨機係可為濕式或乾式,為了更為均勻混合,以濕式進行為佳。 (Raw material powder mixing project S02) The above raw material powders (Ta powder, Ta-B compound powder, Ta nitride powder, Ta oxide powder, B nitride powder, B oxide powder) were weighed to a specific ratio and mixed with a ball mill. The ball mill system can be wet or dry, for more uniform mixing, it is better to use wet.
(燒結工程S03) 接著,將如上述混合之混合粉,填充於成形容器內,將此加熱及加壓進行燒結,得到燒結體。然而,本實施形態中,經由熱等靜壓法(HIP)進行燒結。 此燒結工程S03之燒結溫度係在400℃以上2000℃以下之範圍內,燒結溫度之保持時間在60分以上300分以下之範圍內。又,燒結工程S03之加壓壓力係25MPa以上。 在此,本實施形態中,燒結溫度係成為1000℃以上為佳,更佳為1500℃以上。又,燒結溫度係以1900℃以下為佳,更佳為1800℃以下。 更且,加壓壓力係35MPa以上為佳,更佳為100MPa以上。 (Sintering Engineering S03) Next, the mixed powder mixed as above is filled in a molding container, and the mixture is sintered by heating and pressing to obtain a sintered body. However, in this embodiment, sintering is performed by hot isostatic pressing (HIP). The sintering temperature of this sintering process S03 is in the range of 400°C to 2000°C, and the holding time of the sintering temperature is in the range of 60 minutes to 300 minutes. In addition, the pressurized pressure of the sintering process S03 is 25MPa or more. Here, in this embodiment, the sintering temperature is preferably 1000°C or higher, more preferably 1500°C or higher. Also, the sintering temperature is preferably lower than 1900°C, more preferably lower than 1800°C. Furthermore, the pressurized pressure is preferably 35 MPa or higher, more preferably 100 MPa or higher.
(加工工程S04) 接著,對於所得之燒結體而言,進行機械加工,得特定尺寸之Ta-B濺鍍靶。然而,Ta-B濺鍍靶係經由進行研磨粒之鏡面加工,將表面粗糙度Ra變小為佳。 (Processing Engineering S04) Then, the obtained sintered body is mechanically processed to obtain a Ta-B sputtering target with a specific size. However, the Ta-B sputtering target is better to reduce the surface roughness Ra by mirror-finishing the abrasive grains.
經由以上之工程,製造本實施形態之Ta-B濺鍍靶。Through the above process, the Ta-B sputtering target of this embodiment is manufactured.
根據如以上之構成之本實施形態之Ta-B濺鍍靶時,具有導電體之選自Ta 2B、Ta 3B 2、Ta 3B 4、Ta 5B 6、TaB、TaB 2一種或二種以上所成Ta-B化合物粒子的同時,可抑制絕緣體之單體B之存在比在50%以下之故,於濺鍍成膜時,可抑制起因單體B之異常放電,而抑制塵埃之產生。因此,可成膜可做為形成微細之配線圖案之EUV空白光罩之EUV吸收膜使用之Ta-B薄膜。 According to the Ta-B sputtering target according to the present embodiment with the above structure, one or both of the conductors are selected from Ta 2 B, Ta 3 B 2 , Ta 3 B 4 , Ta 5 B 6 , TaB, and TaB 2 . At the same time, it can suppress the existence ratio of the monomer B of the insulator to less than 50% at the same time as the above-mentioned Ta-B compound particles. Therefore, during sputtering film formation, it can suppress the abnormal discharge caused by the monomer B and suppress the formation of dust. produce. Therefore, it is possible to form a Ta-B thin film that can be used as an EUV absorbing film for an EUV blank mask for forming fine wiring patterns.
本實施形態之Ta-B濺鍍靶中,Ta-B化合物粒子之真圓度為0.3以上之時,可抑制所含有Ta-B化合物粒子成為針狀或梯形狀,可抑制濺鍍成膜時之Ta-B化合物粒子之端部為起點之異常放電之產生,更可抑制塵埃之產生。In the Ta-B sputtering target of this embodiment, when the roundness of the Ta-B compound particles is 0.3 or more, the contained Ta-B compound particles can be suppressed from becoming acicular or trapezoidal, and the sputtering film formation can be suppressed. The end of the Ta-B compound particle is the starting point for the generation of abnormal discharge, and it can also suppress the generation of dust.
本實施形態之Ta-B濺鍍靶中,B之含有量為0.3mass%以上且10mass%以下之範圍內時,成膜之Ta-B薄膜中,可抑制EUV反射機能之下降,可成膜特別適於EUV吸收膜之Ta-B薄膜。In the Ta-B sputtering target of this embodiment, when the content of B is in the range of 0.3 mass% or more and 10 mass% or less, in the formed Ta-B thin film, the decrease of the EUV reflective function can be suppressed, and the film can be formed. Especially suitable for Ta-B thin film of EUV absorbing film.
本實施形態之Ta-B濺鍍靶中,含有選自Ta氮化物、B氮化物、Ta氧化物、B氧化物之一種或二種以上之時,無需實施氮反應性成膜或氧反應性成膜,可成膜含Ta與B之氮化物薄膜,或含Ta與B之氧化物薄膜。然後,可適用塵埃之產生較少之離子束濺鍍。 又,本實施形態之Ta-B濺鍍靶中,N及O之合計含有量限制於20mass%以下之故,成膜之Ta-B薄膜中,可抑制EUV反射機能下降,成膜尤其適於EUV吸收膜之Ta-B薄膜。 When the Ta-B sputtering target of this embodiment contains one or more kinds selected from Ta nitrides, B nitrides, Ta oxides, and B oxides, it is not necessary to perform nitrogen-reactive film formation or oxygen-reactive film formation. For film formation, it can form a nitride film containing Ta and B, or an oxide film containing Ta and B. Then, ion beam sputtering with less generation of dust can be applied. In addition, in the Ta-B sputtering target of this embodiment, the total content of N and O is limited to 20 mass% or less. In the Ta-B film formed into the film, the decrease of the EUV reflection function can be suppressed, and it is especially suitable for film formation. Ta-B film for EUV absorbing film.
本實施形態之Ta-B濺鍍靶中,金屬不純物之Fe、Ni、Cr、Cu、Na、K之合計含有量為10000massppm以下之時,可抑制濺鍍成膜時之金屬不純物為起點之異常放電之產生,可抑制塵埃之產生。In the Ta-B sputtering target of this embodiment, when the total content of Fe, Ni, Cr, Cu, Na, and K of metal impurities is 10000 massppm or less, it is possible to suppress the abnormality starting from the metal impurities during sputtering film formation. The generation of discharge can suppress the generation of dust.
本實施形態之Ta-B濺鍍靶中,平均結晶粒子徑為50μm以下之時,即使進行濺鍍,於濺鍍面難以產生的凹凸,可更抑制濺鍍成膜時之異常放電之產生,更可抑制塵埃之產生。In the Ta-B sputtering target of this embodiment, when the average crystal grain size is 50 μm or less, even if sputtering is performed, unevenness is hardly produced on the sputtering surface, and the occurrence of abnormal discharge during sputtering film formation can be further suppressed. It can also suppress the generation of dust.
本實施形態之Ta-B濺鍍靶中,表面粗糙度Ra為1.6μm以下之時,可更抑制濺鍍成膜時之異常放電之產生,更可抑制塵埃之產生。In the Ta-B sputtering target of the present embodiment, when the surface roughness Ra is 1.6 μm or less, the occurrence of abnormal discharge during sputtering film formation can be further suppressed, and the generation of dust can be further suppressed.
本實施形態之Ta-B濺鍍靶中,密度比為90%以上之時,於內部空洞為少之故,可更抑制濺鍍成膜時之異常放電之產生,更可抑制塵埃之產生。In the Ta-B sputtering target of this embodiment, when the density ratio is 90% or more, there are few internal voids, and the occurrence of abnormal discharge during sputtering film formation can be further suppressed, and the generation of dust can be further suppressed.
本實施形態之Ta-B濺鍍靶中,電阻率為1Ωcm以下之時,可充分確保導電性之故,可更抑制濺鍍成膜時之異常放電之產生,更可抑制塵埃之產生。In the Ta-B sputtering target of this embodiment, when the resistivity is 1Ωcm or less, the electrical conductivity can be ensured sufficiently, and the occurrence of abnormal discharge during sputtering film formation can be further suppressed, and the generation of dust can be further suppressed.
以上,雖對於本發明的實施形態做了說明,但本發明非限定於此,在不脫離該發明之技術思想之範圍下,可適切加以變更。 例如,本實施形態中,雖就經由熱等靜壓法(HIP)得燒結體做了說明,但非限定於此,亦可經由加熱加壓法(HP),得燒結體。 [實施例] As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably without departing from the range of the technical idea of this invention. For example, in this embodiment, although the sintered body obtained by the hot isostatic pressing method (HIP) was demonstrated, it is not limited to this, The sintered body can also be obtained by the heat press method (HP). [Example]
以下,對於確認本發明之有效性所進行之確認實驗之結果,加以說明。Hereinafter, the results of confirmation experiments carried out to confirm the effectiveness of the present invention will be described.
準備純度99.9mass%平均粒子徑5μm之Ta粉、和純度99mass%平均粒子徑15.5μm之B粉、和純度99mass%平均粒子徑8μm之Ta-B化合物粉(TaB 2粉)、和純度99mass%平均粒子徑3.7μm之TaN粉、和純度99.9mass%平均粒子徑3.6μm之Ta 2O 5粉、和純度99.9mass%平均粒子徑0.8μm之BN粉、和純度99mass%平均粒子徑1.2μm之B 2O 3粉。 然而,Ta-B化合物粉(TaB 2粉)係,為除去金屬不純物,於混合前以壬水進行酸洗淨,以純水洗濯後,經由真空乾燥,充分加以乾燥。 Prepare Ta powder with a purity of 99.9mass% average particle diameter of 5 μm, B powder with a purity of 99mass% of an average particle diameter of 15.5 μm, and Ta-B compound powder with a purity of 99mass% of an average particle diameter of 8 μm (TaB 2 powder), and a purity of 99mass% TaN powder with an average particle diameter of 3.7 μm, and Ta 2 O 5 powder with a purity of 99.9mass% and an average particle diameter of 3.6 μm, and BN powder with a purity of 99.9mass% and an average particle diameter of 0.8 μm, and a powder with a purity of 99mass% and an average particle diameter of 1.2 μm B2O3 powder . However, the Ta-B compound powder (TaB 2 powder) was acid-washed with nonyl water before mixing in order to remove metal impurities, and after washing with pure water, it was sufficiently dried by vacuum drying.
將上述原料粉,成為表1斤示配合比加以秤量,經由濕式球磨機加以混合。The above-mentioned raw material powders were weighed into the compounding ratio shown in Table 1, and mixed by a wet ball mill.
將球以篩子除去之後,於內徑ϕ135mm之碳製之成形模具,置入混合粉,使用真空環境之加熱加壓裝置(HP),在表1所示燒結溫度及加壓荷重之條件下,進行3小時之加壓燒結。 企將上述混合粉,填充於ϕ160mm之SPCC模具,使用(HIP),在表1所示燒結溫度及加壓荷重之條件下,進行3小時之加壓燒結。 After removing the balls with a sieve, put the mixed powder in a carbon forming mold with an inner diameter of ϕ135mm, and use a heating and pressing device (HP) in a vacuum environment. Under the conditions of sintering temperature and pressure load shown in Table 1, Pressure sintering was carried out for 3 hours. Fill the above mixed powder into the SPCC mold of ϕ160mm, use (HIP), and carry out pressure sintering for 3 hours under the conditions of sintering temperature and pressure load shown in Table 1.
將所得燒結體之表面,以鑽石磨石#100粗加工之後,以#400進行精加工。又,依需要,對於該燒結體之表面,實施研磨粒所進行之鏡面加工。由此,得本發明例及比較例之Ta-B濺鍍靶。The surface of the obtained sintered body was rough-cut with diamond grindstone #100, and then finished with #400. Also, if necessary, the surface of the sintered body is subjected to mirror-finishing by abrasive grains. Thereby, the Ta-B sputtering target of the example of this invention and a comparative example was obtained.
對於所得Ta-B濺鍍靶,對於以下之項目,實施評估。將評估結果示於表2~4。The following items were evaluated about the obtained Ta-B sputtering target. The evaluation results are shown in Tables 2 to 4.
(XRD測定) 對於所得Ta-B濺鍍靶之濺鍍面,進行XRD測定,將有歸屬於Ta 2B、Ta 3B 2、Ta 3B 4、Ta 5B 6、TaB、TaB 2之尖峰時,評估為「有」Ta-B化合物粒子。 又,將歸屬於單體B之尖峰強度,以歸屬於Ta-B化合物之尖峰強度與歸屬於單體B之尖峰強度之和除之,乘上100之比例,做為「單體B之存在比(%)」。此時,使用於Ta-B化合物之尖峰係使用強度最強的。然而,無法得Ta-B化合物之尖峰強度時,令單體B之存在比(%)為100%。 (XRD measurement) For the sputtering surface of the obtained Ta-B sputtering target, perform XRD measurement, and there will be sharp peaks belonging to Ta 2 B, Ta 3 B 2 , Ta 3 B 4 , Ta 5 B 6 , TaB, and TaB 2 , it was evaluated as "presence" of Ta-B compound particles. Also, divide the peak intensity attributable to monomer B by the sum of the peak intensity attributable to Ta-B compound and the peak intensity attributable to monomer B, and multiply the ratio by 100, as "existence of monomer B Compare(%)". At this time, the peak used for the Ta-B compound is the strongest. However, when the peak intensity of the Ta-B compound cannot be obtained, the abundance ratio (%) of the monomer B is 100%.
然而,將單體B及Ta-B化合物之DB卡片號碼和主尖峰之結晶面,示於以下。 單體B:DB卡片號碼01-074-5416、結晶面(104) Ta 2B:DB卡片號碼01-089-7191、結晶面(211) Ta 3B 2:DB卡片號碼01-072-9378、結晶面(201) Ta 3B 4:DB卡片號碼01-089-3916、結晶面(031) Ta 5B 6:DB卡片號碼01-080-0733、結晶面(510) TaB:DB卡片號碼01-089-2310、結晶面(021) TaB 2:DB卡片號碼00-038-1462、結晶面(101) However, the DB card numbers of the monomer B and the Ta-B compound and the crystal plane of the main peak are shown below. Monomer B: DB card number 01-074-5416, crystal face (104) Ta 2 B: DB card number 01-089-7191, crystal face (211) Ta 3 B 2 : DB card number 01-072-9378, Crystal face (201) Ta 3 B 4 : DB card number 01-089-3916, crystal face (031) Ta 5 B 6 : DB card number 01-080-0733, crystal face (510) TaB: DB card number 01- 089-2310, crystal face (021) TaB 2 : DB card number 00-038-1462, crystal face (101)
(B之含有量) 從所得Ta-B濺鍍靶採取測定試料,將採取之測定試料以氟化銨水溶液溶解,進行ICP-AES分析,測定含於Ta-B濺鍍靶中之B之含有量(mass%)。 (Content of B) A measurement sample was taken from the obtained Ta-B sputtering target, and the collected measurement sample was dissolved in ammonium fluoride aqueous solution, and ICP-AES analysis was performed to measure the B content (mass%) contained in the Ta-B sputtering target.
(N,O之含有量) 從所得Ta-B濺鍍靶採取測定試料1g,經由LECO公司之氮・氧分析裝置,測定N,O之含有量(mass%)。 (N, O content) 1 g of a measurement sample was collected from the obtained Ta-B sputtering target, and the N,O content (mass%) was measured by a nitrogen and oxygen analyzer of LECO Company.
(金屬不純物之含有量) 從所得Ta-B濺鍍靶採取測定試料,將採取之測定試料以氟化銨水溶液溶解,進行ICP-AES分析,測定Fe、Ni、Cr、Cu之含有量(massppm)。更且,使用火焰光度法,測定Na,K之含有量(massppm)。然後,算出此等之金屬不純物之合計含有量。 (Content of metal impurities) A measurement sample was collected from the obtained Ta-B sputtering target, and the collected measurement sample was dissolved in an ammonium fluoride aqueous solution, and analyzed by ICP-AES to measure the content (massppm) of Fe, Ni, Cr, and Cu. Furthermore, Na and K content (massppm) were measured using flame photometry. Then, the total content of these metal impurities was calculated.
(Ta-B化合物粒子之真圓度) 從所得Ta-B濺鍍靶採取觀察試料,將濺鍍面進行CP加工,將10,800μm 2(90μm×120μm)之領域,經由EPMA以1000倍之倍率,攝影COMPO像。 將所得畫像,使用畫像解析軟體imageJ,進行二值化,僅就含有B之領域著色。畫像中最為白色之領域為Ta,除此之外之成分視為B含有成分。含有B之領域係存在Ta-B化合物粒子之時,為含於Ta-B化合物粒子之B之領域或含於Ta-B化合物粒子與單體B之B之領域,不存在Ta-B化合物粒子之時,為含於單體B之B之領域。 對於著色領域而言,使用Shape Descriptors機能,對於選擇之Ta-B化合物粒子,計算真圓度(4π×(面積)/(周長) 2)。求得所得結果中,對於粒子面積為1μm 2以上之Ta-B化合物粒子而言之真圓度之平均值。將此作業,對於觀察試料之任意位置之5處所,進行同樣計算,求得該平均值。 (Roundness of Ta-B compound particles) Observation samples were collected from the obtained Ta-B sputtering target, and the sputtered surface was subjected to CP processing, and the area of 10,800 μm 2 (90 μm×120 μm) was magnified by 1000 times through EPMA , photography compo like. The obtained image was binarized using the image analysis software imageJ, and only the area containing B was colored. The whitest area in the image is Ta, and the other components are considered to contain B components. The domain containing B means that when Ta-B compound particles exist, it is the domain of B contained in Ta-B compound particles or the domain of B contained in Ta-B compound particles and monomer B, and Ta-B compound particles do not exist In this case, it is the domain of B contained in the monomer B. For the coloring field, use the Shape Descriptors function to calculate the roundness (4π×(area)/(circumference) 2 ) of the selected Ta-B compound particles. Among the obtained results, the average value of the roundness of Ta-B compound particles having a particle area of 1 μm 2 or more was obtained. Carry out the same calculation for 5 arbitrary positions of the observed sample by using this operation, and obtain the average value.
(平均粒子徑) 從所得Ta-B濺鍍靶採取觀察試料,將濺鍍面進行CP加工,將10,800μm 2(90μm×120μm)之領域,經由EPMA以1000倍之倍率,攝影COMPO像。 將所得畫像,使用畫像解析軟體imageJ之Find maxima機能,從觀察試料之組織之粒子之領域內之極大點,分割粒子,將所得畫像,使用Analyze particle機能,進行粒子徑測定,計算該平均值。將此作業,對於觀察試料之任意位置之5處所,進行同樣計算,求得該平均值。 (Average Particle Size) Observation samples were taken from the obtained Ta-B sputtering target, the sputtered surface was subjected to CP processing, and a COMPO image was taken at a magnification of 1000 times by EPMA in an area of 10,800 μm 2 (90 μm×120 μm). Use the Find maxima function of the image analysis software imageJ to divide the particles from the maximum point in the particle range of the observed tissue of the sample, and use the Analyze particle function to measure the particle diameter of the obtained image, and calculate the average value. Carry out the same calculation for 5 arbitrary positions of the observed sample by using this operation, and obtain the average value.
(密度比) 從所得Ta-B濺鍍靶(ϕ135mm、厚度5mm)之尺寸與重量,計算燒結體之密度。將尺寸密度除以計算密度之比例,做為「密度比」記載於表。然而,計算密度係根據下述之式加以算出。 計算密度(g/cm 3)=100/{Ta準備量(mass%)/Ta密度(g/cm 3)+B準備量(mass%)/B密度(g/cm 3)+TaB化合物準備量(mass%)/TaB化合物密度(g/cm 3)+添加物準備量(mass%)/添加物密度(g/cm 3)} 然而,添加物係TaN,BN,Ta 2O 5,B 2O 3。 (Density ratio) Calculate the density of the sintered body from the size and weight of the obtained Ta-B sputtering target (ϕ135mm, thickness 5mm). Divide the ratio of the dimensional density by the calculated density, and record it in the table as "Density Ratio". However, the calculated density is calculated according to the following formula. Calculated density (g/cm 3 )=100/{Ta preparation amount (mass%)/Ta density (g/cm 3 )+B preparation amount (mass%)/B density (g/cm 3 )+TaB compound preparation amount (mass%)/TaB compound density (g/cm 3 )+Additive preparation amount (mass%)/Additive density (g/cm 3 )} However, the additive system is TaN, BN, Ta 2 O 5 , B 2 O 3 .
(電阻率) 對於所得Ta-B濺鍍靶(ϕ135mm、厚度5mm)之濺鍍面之任意之位置之5處所,使用三菱化學股份有限公司製之低電阻率計(Loresta-GP),將以四探針法測定之值之平均值,記載於表。測定時之溫度係23±5℃,濕度係50±20%。然而,測定時之探針係使用ASP探針。 (resistivity) For 5 places at any position on the sputtering surface of the obtained Ta-B sputtering target (ϕ135mm, thickness 5mm), use a low resistivity meter (Loresta-GP) manufactured by Mitsubishi Chemical Co., Ltd., and use the four-probe method The average value of the measured values is recorded in the table. The temperature at the time of measurement is 23±5°C, and the humidity is 50±20%. However, as a probe for measurement, an ASP probe was used.
(濺鍍特性) 將所得Ta-B濺鍍靶(ϕ135mm、厚度5mm),使用In焊錫,接合於Cu製之支撐板。 然後,裝備於裝設粒子監視器裝置(Wexx公司製ISPM)之濺鍍裝置,真空吸引至5×10 -4Pa以下後,在Ar流量30sccm、壓力0.67Pa、DC615W之條件下,實施12小時濺鍍。12小時濺鍍後,將更以1小時、同樣條件進行濺鍍之異常放電之產生次數,以DC電源(mks公司製RPG-50)之電弧計數機能加以計數。 又,與異常放電之計測的同時,將濺鍍中之塵埃數以塵埃監視器裝置加以計測。此時,將塵埃尺寸250nm以上且不足600nm、600nm以上且不足1000nm、1000nm以上且不足3000nm,3000nm以上且不足3600nm、3600nm以上之共計5種類之計測資料之總數,做為濺鍍中之粒子量,記載於實施例之表。 (Sputtering characteristics) The obtained Ta-B sputtering target (ϕ135 mm, thickness 5 mm) was joined to a support plate made of Cu using In solder. Then, equip a sputtering device equipped with a particle monitor device (ISPM manufactured by Wexx Co., Ltd.), vacuum suction to 5 × 10 -4 Pa or less, and implement it under the conditions of Ar flow rate 30 sccm, pressure 0.67 Pa, and DC 615W for 12 hours. Sputtering. After 12 hours of sputtering, the number of abnormal discharges that were sputtered under the same conditions for 1 hour was counted by the arc counting function of the DC power supply (RPG-50 manufactured by mks company). In addition, simultaneously with the measurement of abnormal discharge, the number of dust in sputtering was measured with a dust monitor device. At this time, the total number of 5 types of measurement data with a dust size of 250nm or more and less than 600nm, 600nm or more and less than 1000nm, 1000nm or more and less than 3000nm, 3000nm or more and less than 3600nm, and 3600nm or more is used as the amount of particles in sputtering , Recorded in the table of the embodiment.
(膜之組成分析) 以與異常放電計測同樣之濺鍍條件,於20mm×20mm尺寸之Si基板上,成膜厚度50nm之膜。對於成膜之Si基板而言,進行XPS裝置之定量分析,將所得B,N,O之定量值,記載於表4。 (Membrane Composition Analysis) A film with a thickness of 50 nm was formed on a Si substrate with a size of 20 mm x 20 mm under the same sputtering conditions as the abnormal discharge measurement. For the film-formed Si substrate, the quantitative analysis of the XPS device was carried out, and the quantitative values of B, N, and O obtained were recorded in Table 4.
比較例1中,不含有Ta-B化合物粒子,單體B之存在比為100%。比較例2中,雖經由XRD測定,觀察歸屬於TaB 2之尖峰,但單體B之存在比為58%。 此等比較例1、2中,於濺鍍成膜時,多次產生異常放電,塵埃之產生個數亦多。 In Comparative Example 1, no Ta-B compound particles were contained, and the abundance ratio of the monomer B was 100%. In Comparative Example 2, although a sharp peak attributed to TaB was observed through XRD measurement, the abundance ratio of monomer B was 58%. In these comparative examples 1 and 2, abnormal discharges occurred many times during sputtering film formation, and the number of dust generated was also large.
對此,於本發明例1~7中,含有Ta-B化合物粒子,單體B之存在比為50%以下。又,於本發明例1、2、4~7中,所含有B中之單體B之存在比為0%。於本發明例3中,所含有B中之單體B之存在比為42%,於本發明例8中,所含有B中之單體B之存在比為13%,於本發明例9中,所含有B中之單體B之存在比為5%。 此等本發明例1~9中,於濺鍍成膜時,抑制異常放電之產生,塵埃之產生個數則變少。 On the other hand, in Examples 1 to 7 of the present invention, Ta-B compound particles were contained, and the abundance ratio of the monomer B was 50% or less. In addition, in Examples 1, 2, and 4 to 7 of the present invention, the abundance ratio of the monomer B contained in B was 0%. In Example 3 of the present invention, the presence ratio of monomer B contained in B is 42%, in Example 8 of the present invention, the presence ratio of monomer B contained in B is 13%, and in Example 9 of the present invention , the presence ratio of monomer B contained in B is 5%. In Examples 1 to 9 of the present invention, during sputtering film formation, the generation of abnormal discharge was suppressed, and the number of dust generated was reduced.
由以上得知,根據本發明例時,可確認提供抑制異常放電所造成塵埃之產生,可安定成膜Ta-B薄膜(含Ta與B之氮化物薄膜,或含Ta與B之氧化物薄膜等)之Ta-B濺鍍靶。From the above, according to the examples of the present invention, it can be confirmed that the generation of dust caused by abnormal discharge can be suppressed, and the Ta-B thin film (nitride thin film containing Ta and B, or oxide thin film containing Ta and B) can be stably formed. etc.) Ta-B sputtering target.
[圖1]顯示關於本發明之一實施形態之Ta-B濺鍍靶之XRD測定結果圖。 [圖2]顯示關於本發明之一實施形態之Ta-B濺鍍靶之XRD測定結果圖。 [圖3]關於本發明之一實施形態之Ta-B濺鍍靶之組織觀察照片。 [圖4]顯示關於本發明之一實施形態之Ta-B濺鍍靶之製造方法之流程圖。 [FIG. 1] It is a figure which shows the XRD measurement result of the Ta-B sputtering target concerning one embodiment of this invention. [ Fig. 2] Fig. 2 is a graph showing the XRD measurement results of a Ta-B sputtering target according to one embodiment of the present invention. [ Fig. 3] Fig. 3 is an observation photograph of a structure of a Ta-B sputtering target according to an embodiment of the present invention. [FIG. 4] It is a flow chart which shows the manufacturing method of the Ta-B sputtering target concerning one embodiment of this invention.
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