WO2017051820A1 - スパッタリングターゲット、ターゲット製造方法 - Google Patents
スパッタリングターゲット、ターゲット製造方法 Download PDFInfo
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- WO2017051820A1 WO2017051820A1 PCT/JP2016/077815 JP2016077815W WO2017051820A1 WO 2017051820 A1 WO2017051820 A1 WO 2017051820A1 JP 2016077815 W JP2016077815 W JP 2016077815W WO 2017051820 A1 WO2017051820 A1 WO 2017051820A1
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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
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
Definitions
- FIG. 11A shows a state in which a base 103 serving as the uppermost single-layer substrate 111 2 is stuck on the single-layer substrate 111 1 .
- the base 103 is provided with a connection hole 102, and the surface of the wiring film 110 of the lower single-layer substrate 111 1 is exposed at the bottom of the connection hole 102.
- the exposed adhesion layer 118 is etched while leaving the adhesion layers 108 located below the copper thin films 106 and 107 and the seed layer 105 as shown in FIG.
- the substrate 103 is exposed in the removed portion.
- a Cu—Ni—Al target containing nickel and aluminum in copper was prepared, and the Cu—Ni—Al target was sputtered to expose the resin.
- a copper alloy thin film is formed on the surface of the substrate and a conductive thin film made of pure copper is formed on the surface of the copper alloy thin film to form a wiring film, the adhesion between the copper alloy thin film and the resin, the copper alloy thin film and the conductive thin film As a result, a wiring film that did not peel from the substrate was obtained.
- the Cu—Ni—Al target has a large number of occurrences of arc discharge during sputtering, and thus the formed copper alloy thin film may be defective.
- the present invention was created to solve such problems.
- a melt containing copper, nickel and aluminum in a predetermined ratio is cooled and solidified, the melt contains Zn and Mn. It was discovered that either one or both of these may be contained, and the present invention has been created.
- a wiring film formed by sputtering with fewer holes in the sputtering target and less arc discharge can be patterned by a single etching process.
- FIG. (1) for demonstrating the manufacturing process of the mounting apparatus of this invention
- FIG. (2) for explaining the manufacturing process of the mounting apparatus of the present invention
- FIG. (3) for explaining the manufacturing process of the mounting apparatus of the present invention
- FIG. (4) for demonstrating the manufacturing process of the mounting apparatus of this invention
- Drawing (5) for demonstrating the manufacturing process of the mounting apparatus of this invention
- FIG. (6) for demonstrating the manufacturing process of the mounting apparatus of this invention
- FIG. 7 is a view for explaining a manufacturing process of the mounting apparatus of the present invention (7).
- Arc discharge graph (a)-(d) The figure for demonstrating the manufacturing process of the mounting apparatus of a prior art Diagram for explaining the substrate Figure showing a mounting device of the prior art
- the mounting apparatus 10 includes a support substrate 14 and first and second multilayer substrates 11 and 12 disposed on both surfaces of the support substrate 14, respectively. Each have a plurality of single-layer substrates 11 1 to 11 3 and 12 1 to 12 3 .
- FIG. 9 shows a single-layer substrate 11 3 that is the uppermost layer of the first multilayer substrate 11 and a part of the single-layer substrate 11 2 that is one layer below the single-layer substrate 11 3 .
- the single-layer substrates 11 1 to 11 3 and 12 1 to 12 3 have the same structure, and the single-layer substrates 11 1 to 11 3 and 12 1 to 12 3 are formed on the plate-like substrate 3 and the substrate 3.
- connection holes 2 of the single-layer substrates 11 1 to 11 3 and 12 1 to 12 3 are connected to the wiring film 9 of the lower-layer single-layer substrates 11 1 , 11 2 , 12 1 , and 12 2 or the wiring of the support substrate 14.
- the metal plugs 8 of the single-layer substrates 11 1 to 11 3 and 12 1 to 12 3 are located on the film 14d, and the wiring films 9 of the lower-layer single-layer substrates 11 1 , 11 2 , 12 1 , and 12 2 are provided. Alternatively, it is electrically connected to the wiring film 14 d of the support substrate 14.
- the wiring film 9 of the uppermost single-layer substrate 11 3, 12 3 of the second multi-layer substrates 11 and 12 are connected to the wiring layer 14d on one surface and the other surface of the supporting substrate 14 Since the wiring films 14d on both sides of the support substrate 14 are connected via the connecting body 14c, the wiring films 9 of the uppermost single-layer substrates 11 3 and 12 3 are also electrically connected. Yes.
- the motherboard 20 includes a motherboard body 20a and a wiring film 20b disposed on the motherboard body 20a.
- the terminal 13b of the semiconductor device 13 is electrically connected to an integrated circuit of a semiconductor element disposed inside the semiconductor device main body 13a. Therefore, the integrated circuit is connected via the mounting device 10 and the metal body 24.
- the wiring film 20b of the mother board 20 is electrically connected.
- each monolayer substrate 11 1 to 11 3, 12 1 to 12 3 of the base body 3 is comprised with the board
- FIG. 2 shows a sputtering apparatus 50 for forming the alloy thin films 4 and 5.
- a heating device 56 is disposed inside the carry-in / out chamber 51a, and the in-process substrate 32 disposed in the transfer device 54 is heated by the heating device 56 while being evacuated.
- the gate valve 59a is opened, and the in-process substrate 32 is moved together with the transfer device 54 from the inside of the loading / unloading chamber 51a to the inside of the pretreatment chamber 51b.
- a sputtering target 55 is disposed inside the film forming chamber 51c.
- the sputtering target 55 is configured by attaching a plate-like target alloy containing a base material containing copper, nickel, and aluminum and an additive added to the base material to the cathode electrode.
- the additive content is 0.01 atomic% or more with respect to 100 atomic% of the base material, and the zinc content in the additive is 1.0 atomic% or less.
- the content of manganese in the inside is also 1.0 atomic% or less.
- the copper raw material, the nickel raw material, and the aluminum raw material contain more than 50 atomic percent of copper when the total number of atoms of copper, nickel, and aluminum is 100 atomic percent, and nickel is 5 atomic percent.
- the aluminum is contained at a content of not less than 40% by atom and not more than 40% by atom, and aluminum is contained at a content of not less than 3% by atom and not more than 10% by atom.
- the content of zinc in the additive is 1.0 atomic% or less, and the content of manganese in the additive is 1.0 atomic% or less.
- the melt copper, nickel, aluminum, zinc, and manganese are uniformly dispersed, the melt is cooled, the solidified product is formed into a plate shape, and a sputtering target is formed.
- the composition of the melt and the sputtering target 55 is the same as the ratio of copper, nickel, aluminum, and additives contained in the copper raw material, nickel raw material, aluminum raw material, and composition raw material disposed in the melting vessel.
- a gas releasing device 53 is provided inside the film forming chamber 51c. While the inside of the film forming chamber 51c is evacuated by the vacuum evacuating device 58c, a rare gas such as Ar is supplied from the gas supply device 52 to the gas releasing device 53. A sputtering gas composed of a gas is supplied, the sputtering gas is released from the gas release device 53 into the film formation chamber 51c, a voltage is applied to the sputtering target 55, and plasma of the sputtering gas is generated.
- a rare gas such as Ar
- the surface of the substrate 3 that has been pretreated faces the sputtering target 55, and when the surface of the sputtering target 55 is sputtered by the generated plasma, the sputtered particles adhere to the surface of the substrate 3 that has been pretreated, An alloy thin film having the same content of copper, nickel, aluminum, zinc and manganese as the sputtering target 55 is grown on the surface.
- the alloy thin film 15 is in contact with the surface of the base 3 (excluding the inside of the connection hole 2), the inner peripheral surface of the connection hole 2, and the conductive film 7 on the bottom surface of the connection hole 2.
- the bottom surface in contact with the wiring film 9 of a single-layer substrate 11 and second one lower, are electrically connected.
- One underlying monolayer substrate 11 and second wiring layer 9 is composed of an alloy thin film 5 and the conductive film 7.
- the adhesion strength is higher than that when not irradiated.
- the voltage application to the sputtering target 55 and the introduction of the sputtering gas are stopped, and the sputtering ends.
- the in-process substrate 33 on which the gate valves 59a and 59b are opened and the alloy thin film 15 is formed passes through the pretreatment chamber 51b and is moved to the carry-in / out chamber 51a in which the inside is in a vacuum atmosphere.
- a patterned resist film 28 is disposed on the surface of the alloy thin film 15.
- openings 29 are formed above the connection holes 2 of the uppermost substrate 3 and above a predetermined position of the alloy thin film 15 on the surface of the substrate 3. Below the bottom surface, the alloy thin film 15 disposed on the bottom surface and the inner peripheral side surface of each connection hole 2 or the alloy thin film 15 located on the surface of the substrate 3 is exposed.
- the work substrate 33 in which the alloy thin film 15 is exposed on the bottom surface of the opening 29 of the resist film 28 and on a predetermined position on the surface of the base 3 is plated with copper ions.
- the exposed alloy thin film 15 is immersed in the solution and brought into contact with the plating solution, the copper electrode immersed in the plating solution and the alloy thin film 15 are connected to a power source, the power source is operated, and the alloy thin film is passed through the copper electrode.
- a voltage is applied between 15 and the plating solution to attach positive metal ions in the plating solution to the portion of the alloy thin film 15 that contacts the plating solution, and a conductive film containing more copper than the alloy thin film 15 is grown.
- a work-in-process substrate 34 in which the conductive films 6 and 7 are formed below the bottom surface of the opening 29 on the connection hole 2 and below the bottom surface of the opening 29 on the surface of the base 3 is produced. .
- the electrolytic plating method has a higher growth rate than the sputtering method, and the films of the conductive films 6 and 7 formed by the electrolytic plating method rather than the film thickness of the alloy thin film 15 formed by the sputtering method.
- the conductive film 6 formed on the surface of the alloy thin film 15 in the connection hole 2 fills the inside of the connection hole 2, and its upper portion is on the surface of the base 3. It is located above the surface of the alloy thin film 15.
- the conductive film 6 inside the connection hole 2 is connected to the conductive film 7 on the surface of the base 3, but the conductive film 7 on the surface of the base 3 includes conductive films separated from each other, In a state where the resist film 28 is peeled off, the inner conductive film 6 and the surface conductive film 7 are electrically connected to each other by the alloy thin film 15.
- the exposed alloy thin film 15 is removed by etching, and as shown in FIG. 9, the portion where the alloy thin film 15 is removed is removed.
- the surface of the base 3 located under the alloy thin film 15 is exposed, and the uppermost single-layer substrate 11 3 on which the conductive films 6 and 7 are patterned is formed.
- connection hole 2 In each of the single-layer substrates 11 1 to 11 3 and 12 1 to 12 3 , the inside of the connection hole 2 is a conductive film 6 inside the connection hole 2 and an alloy thin film 4 positioned under the conductive film 6. A metal plug 8 filling the connection hole 2 is formed, and a wiring film 9 is formed on the substrate 3 by a conductive film 7 and an alloy thin film 5 positioned under the conductive film 7.
- the adhesion of the pure copper thin film to the resin 25 exposed on the surface of the substrate 3 is poor.
- the alloy thin films 4 and 5 in contact with the resin 25 were measured for adhesion by containing elements other than copper in a thin film material containing more than 50 atomic% of copper, as shown in the following experiment.
- a thin film material containing 5 atomic% to 30 atomic% of nickel and 3 atomic% to 10 atomic% of aluminum has higher adhesion to the resin 25 than a thin film of pure copper or copper oxide.
- the additive includes 0.01 atomic% or more and 1.0 atomic% or less zinc, and 0.01 atomic% or more and 1.0 atomic% when the total number of atoms of copper, nickel and aluminum is 100%.
- One or both of the following ranges of manganese are contained.
- the additive does not deteriorate the adhesiveness with the resin 25, and the copper content of the base material is larger than 50 atomic%, so the adhesiveness with the pure copper thin film is high, and the base 3 to the metal plug 8 or Since the wiring film 9 does not peel off and the conductive films 6 and 7 have a higher copper content than the alloy thin films 4 and 5, the conductive films 6 and 7 do not peel off from the alloy thin films 4 and 5. Yes.
- a 50 nm alloy film that contacts the surface of the glass substrate was formed by sputtering using each sputtering target, a 1 mm ⁇ 1 mm ⁇ 100 square scratch pattern was formed, and the adhesion was evaluated by a cross-cut test.
- Each sputtering target was cut, the cross section was observed, and the number of holes was measured.
- the measured target was 100 mm ⁇ ⁇ 10 mm thickness
- the cross-sectional area after cutting was 100 mm ⁇ 10 mm
- observation was performed using a dye penetrant flaw detector, and the number of holes having a size of 0.5 mm ⁇ or more was counted.
- the measurement results of the number of holes are shown in Table 2.
- the numerical values in Table 2 are the additive content (atomic%) when the total number of atoms of copper, nickel and aluminum is 100 atomic%, and the number of vacancies was observed to be more than 3 / cm 2 . “ ⁇ ” was described for the sputtering target, “ ⁇ ” was described for the sputtering target observed at 1 to 3 / cm 2, and “ ⁇ ”was described for the sputtering target where no vacancy was observed.
- the horizontal axis of the graph of FIG. 10 is the additive content (atomic%) when the total number of atoms of copper, nickel, and aluminum is 100 atomic%, and the vertical axis is the measured number of vacancies. The relationship between the additive content and the number of vacancies is shown. From Table 2 and the graph of FIG. 10, when the total number of atoms of copper, nickel and aluminum is 100 atomic%, the number of vacancies should be reduced when 1.0% of zinc and manganese are contained. Can be predicted.
- additives for the sputtering target are either manganese or zinc, and have different contents in the range of 0 atomic% to 1.2 atomic%.
- the effect of reducing vacancies is obtained when either one or both of zinc and manganese are contained in an amount of 0.01 atomic% or more, and when either or both are contained in an amount of 0.25 atomic% or more, respectively. This is preferable because there are no voids.
- the additive consisting of one or both of zinc and manganese is included at a content of 1.2 atomic% or more with respect to 100 atomic% of the base material to form a sputtering target.
- Good adhesion cannot be obtained with respect to the conductive films 6 and 7 formed by the Cu plating method performed in the subsequent process of the sputtering film formation of the sputtering target.
- the alloy thin films 4 and 5 can be formed.
- the additive comprising, when the total number of atoms of copper, nickel and aluminum is 100 atomic%, contains copper more than 50 atomic% and contains nickel in the range of 5 atomic% to 40 atomic%
- zinc and manganese are either 0.01 atomic percent or more and one or both of zinc and manganese with respect to 100 atomic percent of the base material, respectively.
- a sputtering target with good workability and few voids can be obtained.
- Alloy thin films 4 and 5 having good adhesion to conductive films 6 and 7 formed by a Cu plating method performed in a subsequent process of ring film formation can be formed, and an alloy thin film having good adhesion to the resin. 4 and 5 can be formed.
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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Abstract
Description
本発明は、前記添加物に含有されたZnの含有率とMnの含有率とは、それぞれ1.0原子%以下にされたスパッタリングターゲットである。
また、本発明は、上記記載のスパッタリングターゲットを製造するターゲット製造方法であって、固体の前記母材と、固体の前記添加物とを同じ容器中に配置し、加熱して前記母材と前記添加物とを含有する溶融物を形成し、前記溶融物を冷却して固化させて前記スパッタリングターゲットを形成するターゲット製造方法である。
空孔数の測定結果を表2に示す。
表2と図10のグラフとから、銅とニッケルとアルミニウムとの合計原子数を100原子%としたときに、亜鉛とマンガンは、それぞれ1.0%含有させると、空孔数を小さくすることができることを予測することができる。
3……基体
4、5……合金薄膜
6、7……導電膜
8……金属プラグ
9……配線膜
10……搭載装置
55……スパッタリングターゲット
Claims (3)
- CuとNiとAlとを含有し、CuとNiとAlとを100原子%としたときに、Cuを50原子%よりも多く含有し、Niを5原子%以上40原子%以下の含有率で含有し、Alを3原子%以上10原子%以下の含有率で含有する母材と、
前記母材に添加された添加物とを含有するスパッタリングターゲットであって、
前記添加物は、ZnとMnのいずれか一方又は両方から成り、前記母材の100原子%に対して、0.01原子%以上の含有率で含有されたスパッタリングターゲット。 - 前記添加物に含有されたZnの含有率とMnの含有率とは、それぞれ1.0原子%以下にされた請求項1記載のスパッタリングターゲット。
- 請求項1又は請求項2のいずれか1項記載のスパッタリングターゲットを製造するターゲット製造方法であって、
固体の前記母材と、固体の前記添加物とを同じ容器中に配置し、
加熱して前記母材と前記添加物とを含有する溶融物を形成し、
前記溶融物を冷却して固化させて前記スパッタリングターゲットを形成するターゲット製造方法。
Priority Applications (3)
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KR1020177016247A KR20170083611A (ko) | 2015-09-25 | 2016-09-21 | 스퍼터링 타겟, 타겟 제조 방법 |
CN201680004797.XA CN107109635B (zh) | 2015-09-25 | 2016-09-21 | 溅射靶、靶制备方法 |
JP2017516967A JP6442603B2 (ja) | 2015-09-25 | 2016-09-21 | スパッタリングターゲット、ターゲット製造方法 |
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JP2015188506 | 2015-09-25 | ||
JP2015-188506 | 2015-09-25 |
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JP (1) | JP6442603B2 (ja) |
KR (1) | KR20170083611A (ja) |
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TW (1) | TWI694162B (ja) |
WO (1) | WO2017051820A1 (ja) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010082638A1 (ja) * | 2009-01-16 | 2010-07-22 | 株式会社神戸製鋼所 | Cu合金膜および表示デバイス |
WO2014185301A1 (ja) * | 2013-05-13 | 2014-11-20 | 株式会社アルバック | 搭載装置、その製造方法、その製造方法に用いるスパッタリングターゲット |
WO2015068527A1 (ja) * | 2013-11-06 | 2015-05-14 | 三菱マテリアル株式会社 | 保護膜形成用スパッタリングターゲットおよび積層配線膜 |
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KR20130094352A (ko) * | 2011-08-29 | 2013-08-23 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Cu-Ga 합금 스퍼터링 타깃 및 그 제조 방법 |
TWI537400B (zh) * | 2011-12-06 | 2016-06-11 | 神戶製鋼所股份有限公司 | 觸控面板感測器用銅合金配線膜及其之製造方法、以及觸控面板感測器、以及濺鍍靶 |
JP6135275B2 (ja) * | 2013-04-22 | 2017-05-31 | 三菱マテリアル株式会社 | 保護膜形成用スパッタリングターゲット |
-
2016
- 2016-09-21 WO PCT/JP2016/077815 patent/WO2017051820A1/ja active Application Filing
- 2016-09-21 KR KR1020177016247A patent/KR20170083611A/ko not_active Application Discontinuation
- 2016-09-21 CN CN201680004797.XA patent/CN107109635B/zh active Active
- 2016-09-21 JP JP2017516967A patent/JP6442603B2/ja active Active
- 2016-09-23 TW TW105130847A patent/TWI694162B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010082638A1 (ja) * | 2009-01-16 | 2010-07-22 | 株式会社神戸製鋼所 | Cu合金膜および表示デバイス |
WO2014185301A1 (ja) * | 2013-05-13 | 2014-11-20 | 株式会社アルバック | 搭載装置、その製造方法、その製造方法に用いるスパッタリングターゲット |
WO2015068527A1 (ja) * | 2013-11-06 | 2015-05-14 | 三菱マテリアル株式会社 | 保護膜形成用スパッタリングターゲットおよび積層配線膜 |
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CN107109635A (zh) | 2017-08-29 |
CN107109635B (zh) | 2019-04-16 |
JPWO2017051820A1 (ja) | 2017-09-21 |
KR20170083611A (ko) | 2017-07-18 |
JP6442603B2 (ja) | 2018-12-19 |
TW201726932A (zh) | 2017-08-01 |
TWI694162B (zh) | 2020-05-21 |
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