JP4985083B2 - Method for producing oxygen-containing copper target - Google Patents
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Description
この発明は、表面平滑性に優れかつガラス基板表面に対する密着性に優れた酸素含有銅膜を形成するための酸素含有銅ターゲットの製造方法に関するものである。 The present invention relates to a method for producing an oxygen-containing copper target for forming an oxygen-containing copper film having excellent surface smoothness and adhesion to a glass substrate surface.
一般に、フラットパネルディスプレイなどの液晶表示装置にはガラス基板表面に格子状に金属薄膜からなる配線が密着して形成されており、さらにこの金属薄膜からなる格子状配線の交差点にＴＦＴトランジスターが設けられていてこのＴＦＴトランジスターのゲート電極も金属薄膜で形成されている。前記配線または電極となる金属薄膜として、純銅膜を使用することが知られているが、近年、ガラス基板に対する密着性を向上させるために、酸素を含んだ銅膜が使用されるようになり、この酸素を含んだ銅膜は純銅ターゲットを用い、酸素を含む不活性ガス雰囲気中でスパッタすることにより形成されている（特許文献１、２参照）。
従来の酸素を含んだ銅膜からなる配線および電極はガラス基板表面に対する密着性は優れているものの、表面粗さが大きく、この表面粗さの大きな酸素を含んだ銅膜をＴＦＴトランジスターのゲート電極として使用するとＴＦＴトランジスターの性能が低下する。したがって、表面粗さの小さい一層滑らかな酸素を含んだ銅膜が求められている。 Wiring and electrodes made of a conventional copper film containing oxygen have excellent adhesion to the glass substrate surface, but the surface roughness is large, and the copper film containing oxygen with a large surface roughness is used as the gate electrode of the TFT transistor. When used as a TFT transistor, the performance of the TFT transistor is degraded. Therefore, there is a need for a smoother copper film containing oxygen with a small surface roughness.
そこで、本発明者等は、表面粗さの小さい表面が一層滑らかな酸素を含んだ銅膜を得るべく研究を行った。その結果、酸素：０．４〜６原子％を含有し、残部がＣｕおよび不可避不純物からなる組成を有する銅ターゲットであって、この銅ターゲットに含まれる酸素はＣｕ２Ｏとして含まれており、このＣｕ２Ｏが素地中に均一分散している銅ターゲットを作製し、この成分組成および組織を有する銅ターゲット用い、不活性ガス雰囲気中でスパッタリングすることにより得られた酸素を含んだ銅膜は、表面平滑性に優れるとともに密着性にも優れており、これをＴＦＴトランジスターのゲート電極として用いるとＴＦＴトランジスターの性能が劣化することはない、という研究結果が得られたのである。 Accordingly, the present inventors have studied to obtain a copper film containing oxygen with a smooth surface having a small surface roughness. As a result, it is a copper target containing oxygen: 0.4 to 6 atom%, the balance being composed of Cu and inevitable impurities, oxygen contained in this copper target is contained as Cu 2 O, The copper film containing oxygen obtained by producing a copper target in which this Cu 2 O is uniformly dispersed in the substrate, and sputtering in an inert gas atmosphere using a copper target having this component composition and structure is: In addition, it has excellent surface smoothness as well as excellent adhesion, and a research result has been obtained that when this is used as a gate electrode of a TFT transistor, the performance of the TFT transistor does not deteriorate.
この発明は、上記の研究結果に基づいてなされたものであって、
無酸素銅を不活性ガス雰囲気中で高周波溶解し、得られた無酸銅溶湯にＣｕＯ粉末を添加し、溶湯を鉄製鋳型に鋳込んでインゴットを作製し、得られたインゴットを熱間圧延したのち機械加工することにより酸素含有銅ターゲットを作製し、該ターゲットが、酸素：０．４〜６原子％を含有し、残部がＣｕおよび不可避不純物からなる組成、並びに素地中にＣｕ２Ｏが均一に分散している組織を有する酸素含有銅ターゲットの製造方法、に特徴を有するものである。
This invention was made based on the above research results,
Oxygen-free copper was melted at high frequency in an inert gas atmosphere, CuO powder was added to the resulting acid-free copper melt, the molten metal was cast into an iron mold, an ingot was produced, and the resulting ingot was hot-rolled After that, an oxygen-containing copper target is prepared by machining, and the target contains oxygen: 0.4 to 6 atomic%, the balance is composed of Cu and inevitable impurities, and Cu 2 O is uniform in the substrate. It has the characteristics in the manufacturing method of the oxygen containing copper target which has the structure | tissue disperse | distributed to.
この発明の表面平滑性に優れかつ密着性に一層優れた液晶表示装置用配線および電極の形成方法において使用する銅ターゲットに含まれる酸素を０．４〜６原子％にした理由は下記の理由によるものである。すなわち、銅ターゲットに含まれる酸素含有量が０．４原子％未満ではスパッタ中に形成されるＣｕ２Ｏ微結晶の量が少なく、Ｃｕ結晶の微細化効果が得られず、さらにスパッタリングして得られた銅膜の密着性の向上が実現できないからであり、一方、銅ターゲットに含まれる酸素含有量が６原子％を越えて含有すると、得られた銅膜の電気抵抗が著しく増加して配線または電極として使用できなくなるからである。 The reason why the oxygen contained in the copper target used in the method for forming a wiring for a liquid crystal display device and an electrode having excellent surface smoothness and excellent adhesion is 0.4 to 6 atomic% is as follows. Is. That is, when the oxygen content contained in the copper target is less than 0.4 atomic%, the amount of Cu 2 O microcrystals formed during sputtering is small, and the effect of refining Cu crystals cannot be obtained. This is because the adhesion of the obtained copper film cannot be improved. On the other hand, when the oxygen content contained in the copper target exceeds 6 atomic%, the electrical resistance of the obtained copper film is remarkably increased. Alternatively, it cannot be used as an electrode.
酸素：０．４〜６原子％含む銅ターゲットを使用してスパッタリングするための雰囲気は、Ａｒガスなどの不活性ガスで十分であるが、酸素を３体積％以下含む不活性ガス雰囲気中でスパッタリングしても良い。 As an atmosphere for sputtering using a copper target containing 0.4 to 6 atomic% of oxygen, an inert gas such as Ar gas is sufficient, but sputtering is performed in an inert gas atmosphere containing 3% by volume or less of oxygen. You may do it.
この発明の表面平滑性に優れかつ密着性に優れた銅膜の形成に使用するターゲットは、まず純度：９９．９％以上（望ましくは９９．９９％以上）の無酸素銅を、不活性ガス雰囲気中、ジルコニア坩堝で高周波溶解し、得られた無酸素銅溶湯にＣｕＯ粉末を添加し、溶湯を鉄製鋳型に鋳込んでインゴットを作製し、得られたインゴットをさらに熱間圧延したのち機械加工することにより作製することができる。
The target used for forming a copper film having excellent surface smoothness and excellent adhesion according to the present invention is first made of oxygen-free copper having a purity of 99.9% or more (preferably 99.99% or more), and an inert gas. atmosphere, high-frequency heating zirconia crucible, was added to CuO powder oxygen-free molten copper obtained, after produced ingots were rolled further heat the resulting ingot by casting the molten iron manufactured by the mold machine It can be produced by processing .
この発明の方法によると、表面平滑性に優れかつガラス基板表面に対する密着性が優れた銅膜を形成することができ、この銅膜をＴＦＴトランジスターのゲート電極として使用するとＴＦＴトランジスターの性能が低下することがなく、さらにＴＦＴトランジスターを用いたフラットパネルディスプレイの配線としても用いることができるなど優れた効果を奏するものである。 According to the method of the present invention, a copper film having excellent surface smoothness and excellent adhesion to the glass substrate surface can be formed. When this copper film is used as a gate electrode of a TFT transistor, the performance of the TFT transistor is lowered. In addition, it has excellent effects such as being usable as wiring for a flat panel display using a TFT transistor.
実施例１
純度：９９．９９原子％の無酸素銅（酸素含有量：０．００１原子％）を用意し、この無酸素銅をＡｒガス雰囲気中、高純度ジルコニア坩堝内で高周波溶解し、得られた溶湯に平均粒径：５μｍ以下のＣｕＯ粉末を添加し、溶湯を温度：１２５０℃で１０分間保持したのち、鉄製鋳型に鋳込み、さらに熱間加工することにより表１に示される成分組成を有し、直径：１５４ｍｍ、厚さ：１０ｍｍの寸法を有する本発明酸素含有銅ターゲット１〜１０、比較ターゲット１〜２を作製した。これら本発明酸素含有銅ターゲット１〜１０、比較酸素含有銅ターゲット１〜２の組織を金属顕微鏡で観察した結果、素地中にＣｕ２Ｏの微細な粒が均一分散しているのが観察された。
Example 1
Purity: 99.99 atomic% oxygen-free copper (oxygen content: 0.001 atomic%) was prepared, and this oxygen-free copper was melted at high frequency in a high-purity zirconia crucible in an Ar gas atmosphere. After adding CuO powder having an average particle size of 5 μm or less and holding the molten metal at a temperature of 1250 ° C. for 10 minutes, it is cast into an iron mold and further hot-worked to have the component composition shown in Table 1, Inventive oxygen-containing copper targets 1 to 10 and comparative targets 1 and 2 having a diameter of 154 mm and a thickness of 10 mm were produced. As a result of observing the structures of these oxygen-containing copper targets 1 to 10 and comparative oxygen-containing copper targets 1 and 2 with a metallographic microscope, it was observed that fine particles of Cu 2 O were uniformly dispersed in the substrate. .
これら本発明酸素含有銅ターゲット１〜１０、比較酸素含有銅ターゲット１〜２を使用し、さらにガラス基板としてコーニング社１７３７＃（縦：５０、横：５０、厚さ：０．７ｍｍ）を使用し、
到達真空度：５×１０−５Ｐａまで真空に引いた後、Ａｒガスを真空チャンバーに導入して圧力：０．３ＰａのＡｒガス雰囲気とし、スパッタパワー：６００Ｗで１分間成膜し、ガラス基板上に厚さ：３００ｎｍの酸素含有銅膜を形成した。
These oxygen-containing copper targets 1 to 10 and comparative oxygen-containing copper targets 1 to 2 are used, and Corning 1737 # (length: 50, width: 50, thickness: 0.7 mm) is used as a glass substrate. ,
Ultimate vacuum: After vacuuming to 5 × 10 −5 Pa, Ar gas is introduced into the vacuum chamber to form an Ar gas atmosphere having a pressure of 0.3 Pa, and a film is formed at a sputtering power of 600 W for 1 minute. An oxygen-containing copper film having a thickness of 300 nm was formed thereon.
得られた厚さ：３００ｎｍの酸素含有銅膜について下記の評価を行った。
（ａ）膜密着強度試験
本発明酸素含有銅ターゲット１〜１０、比較酸素含有銅ターゲット１〜２を使用してガラス基板上に形成した厚さ：３００ｎｍの酸素含有銅膜にＪＩＳ-Ｋ５４００に準じて１ｍｍ間隔で縦横１１本ずつ碁盤目状に切れ目を入れ、住友３Ｍ社製テープを膜に貼り付けたのち引き剥がし、ガラス基板中央部の１０ｍｍ角内でガラス基板に付着していた膜の面積％を測定する碁盤目付着試験を実施し、その結果を表１に示し、ガラス基板に対する銅膜の密着性を評価した。
The following evaluation was performed on the obtained oxygen-containing copper film having a thickness of 300 nm.
(A) Film adhesion strength test Thickness formed on a glass substrate using the oxygen-containing copper targets 1 to 10 and comparative oxygen-containing copper targets 1 to 2 of the present invention: according to JIS-K5400 to a 300 nm oxygen-containing copper film The area of the film adhered to the glass substrate within a 10 mm square in the center of the glass substrate was cut into a grid pattern of 11 pieces vertically and horizontally at 1 mm intervals, and a tape made by Sumitomo 3M was applied to the film. A cross-cut adhesion test for measuring% was carried out. The results are shown in Table 1, and the adhesion of the copper film to the glass substrate was evaluated.
（ｂ）膜表面粗さの測定：
ガラス基板上に形成した厚さ：３００ｎｍの酸素含有銅膜の表面粗さを原子間顕微鏡（ＡＦＭ）で測定し、その結果を表１に示した。
(B) Measurement of film surface roughness:
The surface roughness of the 300 nm thick oxygen-containing copper film formed on the glass substrate was measured with an atomic microscope (AFM), and the results are shown in Table 1.
（ｃ）膜比抵抗値の測定：
本発明酸素含有銅ターゲット１〜１０、比較酸素含有銅ターゲット１〜２を使用してガラス基板上に形成した厚さ：３００ｎｍの酸素含有銅膜をそれぞれ赤外線加熱炉に装入し、到達真空度：２×１０−４Ｐａの真空雰囲気中、最高温度：３５０℃、３０分間保持の熱処理を施し、前記熱処理後の銅膜の５点の比抵抗を、ロレタスＧＰ ＭＣＰ−Ｔ６１０型 三菱化学製の抵抗率計を用いて四探針法により測定し、その平均値を求め、それらの結果を表１に示した。
(C) Measurement of film specific resistance value:
Thickness formed on glass substrate using oxygen-containing copper targets 1-10 of the present invention and comparative oxygen-containing copper targets 1-2: An oxygen-containing copper film having a thickness of 300 nm was charged into an infrared heating furnace, and the ultimate vacuum : Heat treatment of holding at a maximum temperature of 350 ° C. for 30 minutes in a vacuum atmosphere of 2 × 10 −4 Pa, and the specific resistance of five points of the copper film after the heat treatment is the Loletus GP MCP-T610 type manufactured by Mitsubishi Chemical Measurements were made by a four-probe method using a resistivity meter, the average value was determined, and the results are shown in Table 1.
従来例１
純度：９９．９９原子％の無酸素銅（酸素含有量：０．００１原子％）を用意し、この無酸素銅をＡｒガス雰囲気中、高純度ジルコニア坩堝内で高周波溶解し、得られた溶湯を鉄製鋳型に鋳込み、さらに熱間加工することにより表１に示される成分組成を有し、直径：１５４ｍｍ、厚さ：１０ｍｍの寸法を有する従来銅ターゲットを作製した。この従来ターゲットを用い、スパッタ雰囲気を酸素：５％を含むＡｒガス雰囲気とする以外は、実施例１と全く同様にして酸素含有銅膜を成膜し、得られた酸素含有銅膜について実施例１と同様にして膜密着試験、膜表面粗さの測定および膜比抵抗値の測定を実施し、その結果を表１に示した。
Conventional Example 1
Purity: 99.99 atomic% oxygen-free copper (oxygen content: 0.001 atomic%) was prepared, and this oxygen-free copper was melted at high frequency in a high-purity zirconia crucible in an Ar gas atmosphere. Was cast into an iron mold and further hot worked to produce a conventional copper target having the component composition shown in Table 1, having a diameter of 154 mm and a thickness of 10 mm. An oxygen-containing copper film was formed in the same manner as in Example 1 except that this conventional target was used and the sputtering atmosphere was changed to an Ar gas atmosphere containing oxygen: 5%. The film adhesion test, the measurement of the film surface roughness and the measurement of the film specific resistance value were carried out in the same manner as in Example 1, and the results are shown in Table 1.
表１に示される結果から、本発明酸素含有銅ターゲット１〜１０で作製した酸素含有銅膜は、従来銅ターゲットを用いて酸素含有不活性ガス雰囲気中で作製した酸素含有銅膜に比べて比抵抗および密着性はほぼ同じであるが表面粗さが格段に小さく、表面滑らかな酸素含有銅膜が得られることがわかる。さらにこの発明の条件から外れた値を有する比較酸素含有銅ターゲット１〜２を使用して作製した酸素含有銅膜は比抵抗が増加したり密着性が低下するなど好ましくない特性が現れることが分かる。 From the results shown in Table 1, the oxygen-containing copper film produced with the oxygen-containing copper targets 1 to 10 of the present invention is compared with the oxygen-containing copper film produced in an oxygen-containing inert gas atmosphere using a conventional copper target. It can be seen that although the resistance and adhesion are almost the same, the surface roughness is remarkably small, and a smooth surface oxygen-containing copper film can be obtained. Furthermore, it can be seen that oxygen-containing copper films produced using comparative oxygen-containing copper targets 1 and 2 having values outside the conditions of the present invention exhibit undesirable characteristics such as an increase in specific resistance and a decrease in adhesion. .
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| WO2018159753A1 (en) * | 2017-03-01 | 2018-09-07 | 三菱マテリアル株式会社 | Sputtering target and method for manufacturing sputtering target |
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