JP2010265524A - Etchant for copper-containing stacked film - Google Patents

Etchant for copper-containing stacked film Download PDF

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JP2010265524A
JP2010265524A JP2009119170A JP2009119170A JP2010265524A JP 2010265524 A JP2010265524 A JP 2010265524A JP 2009119170 A JP2009119170 A JP 2009119170A JP 2009119170 A JP2009119170 A JP 2009119170A JP 2010265524 A JP2010265524 A JP 2010265524A
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etching
copper
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oxide layer
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JP5604056B2 (en
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Masaru Kato
勝 加藤
Ryo Kono
良 河野
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Kanto Chemical Co Inc
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof

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Abstract

<P>PROBLEM TO BE SOLVED: To provide an etchant for collectively etching a film of Cu metal and an oxide layer of a Cu alloy, which can control a dissolution of the oxide film of the copper alloy, and realizes such conditions that the dissolution of all layers including the oxide layer of the Cu alloy proceeds with a moderate balance, particularly in a stacked film which is an object to be collectively etched, and to provide an etching method therefor. <P>SOLUTION: The etchant is directed for etching a copper-containing stacked film on a substrate containing an oxide layer of copper or the oxide layer of the copper alloy which contacts the substrate, and includes a peroxide and an organic acid. The etching method is directed for etching the copper-containing stacked film on the substrate containing the oxide layer of copper or the oxide layer of the copper alloy which contacts the substrate, and includes a step of etching the stacked film by using the etchant including the peroxide and the organic acid. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、半導体等に用いる積層膜のエッチング液に関する。   The present invention relates to an etching solution for a laminated film used for a semiconductor or the like.

液晶表示装置の表示面積が大型化すると、薄膜トランジスタと接続されるゲート線およびデータ線が長くなり、それらの配線の抵抗も高くなるため、信号遅延などの問題が生じる。従来の液晶表示装置の金属配線にはＡｌが使用されているが、大型基板についてはより抵抗の低いＣｕ配線が使用されている。   When the display area of the liquid crystal display device is increased, gate lines and data lines connected to the thin film transistors become longer, and the resistance of those wirings also increases, which causes problems such as signal delay. Al is used for the metal wiring of the conventional liquid crystal display device, but Cu wiring with lower resistance is used for the large substrate.

Ｃｕ配線の場合のバリアメタルには、Ｃｕが半導体膜へ拡散するのを防止するため、また半導体膜との密着性の向上のため、Ｔｉ、Ｍｏ、Ｃｒなどの金属膜が使用される。すなわち、Ｃｕ／Ｍｏ、Ｃｕ／Ｔｉ、Ｃｕ／Ｃｒなどの積層膜構成となる。このような積層膜構造をエッチング加工する場合、Ｃｕ膜のエッチング加工を行い、続いて下地膜であるＭｏやＴｉのエッチング加工を行う２段階方式と、Ｃｕ／ＭｏまたはＣｕ／Ｔｉ積層膜を一液で一度にエッチング加工を行う一括加工方式との２つの方法がある。後者の一括加工方式が、作業工程としては有利であるが、耐食性の異なる金属積層膜を一液でエッチングすることが難しい上に、電池効果などの影響も考慮すると積層膜を段差のないテーパー形状に一括エッチングすることは容易ではない。さらに、配線の加工精度から横方向に過度のエッチングが起こること（サイドエッチング）は、極力避けなければならないことから、一括エッチング液の開発は極めて困難となる。   For the barrier metal in the case of Cu wiring, a metal film such as Ti, Mo, or Cr is used to prevent Cu from diffusing into the semiconductor film and to improve adhesion to the semiconductor film. That is, a laminated film structure such as Cu / Mo, Cu / Ti, or Cu / Cr is formed. In the case of etching such a laminated film structure, a Cu film is etched into a two-stage method in which a Cu film is etched and subsequently an etching process of Mo or Ti as a base film is performed, and a Cu / Mo or Cu / Ti laminated film is combined. There are two methods: a batch processing method in which etching is performed at once with a liquid. The latter batch processing method is advantageous as a work process, but it is difficult to etch metal laminated films with different corrosion resistance with a single solution, and considering the effect of battery effect etc., the laminated film has a tapered shape with no steps It is not easy to perform batch etching. Furthermore, excessive etching in the lateral direction (side etching) must be avoided as much as possible due to the processing accuracy of the wiring, so that it is very difficult to develop a batch etching solution.

このような背景において、それぞれ層を構成する各金属に有効な酸化剤を選択することでＣｕ／ＭｏやＣｕ／Ｔｉ並びにＣｕ／Ｃｒなどの一括エッチング方法が検討されている。
例えば、特許文献１には、Ｃｕ溶解の酸化剤としてペルオキソ一硫酸一水素カリウムを用いたエッチング技術が記載され、下地積層金属に合わせて各種酸を組み合わせたエッチング液について検討されている。すなわち、ペルオキソ一硫酸一水素カリウムを必須成分とし、Ｃｕ／Ｔｉの場合は、さらにフッ酸またはペルオキソ硫酸塩とフッ化物とを組合わせ、Ｃｕ／Ｍｏの場合は、さらにリン酸と硝酸とを組合わせ、Ｃｕ／Ｃｒの場合は、さらに塩酸を組み合わせたエッチング組成物が示されている。 In such a background, a batch etching method such as Cu / Mo, Cu / Ti, and Cu / Cr has been studied by selecting an oxidizing agent effective for each metal constituting each layer.
For example, Patent Document 1 describes an etching technique using potassium peroxomonosulfate as an oxidizing agent for dissolving Cu, and studies are made on an etching solution in which various acids are combined in accordance with an underlying laminated metal. That is, potassium peroxomonosulfate monobasic is an essential component. In the case of Cu / Ti, a combination of hydrofluoric acid or peroxosulfate and fluoride is further combined. In the case of Cu / Mo, a combination of phosphoric acid and nitric acid is further combined. In addition, in the case of Cu / Cr, an etching composition in which hydrochloric acid is further combined is shown.

また、特許文献２〜４には、Ｃｕ溶解の酸化剤として過酸化水素を用いたエッチング技術が記載され、各種有機酸もしくは中性塩、さらには各種添加物を併用することによって、Ｃｕ／ＭｏまたはＣｕ／Ｔｉ積層膜を同時にエッチングすることが検討されている。
最近、Ｃｕ／Ｍｏ、Ｃｕ／Ｔｉ積層膜に代わる積層膜として、銅合金酸化層を含む積層膜が開発された。これらは、下地膜としての性能に優れるだけではなく、成膜工程においても積層の各層を同一装置で成膜できるというメリットを有する。しかしながら、この新たに開発された銅合金酸化層を含む積層膜に対する効果的なエッチング方法については、全く検討されていない。 Patent Documents 2 to 4 describe an etching technique using hydrogen peroxide as an oxidizing agent for dissolving Cu. By using various organic acids or neutral salts and various additives in combination, Cu / Mo Alternatively, simultaneous etching of the Cu / Ti laminated film has been studied.
Recently, a multilayer film including a copper alloy oxide layer has been developed as a multilayer film that replaces the Cu / Mo and Cu / Ti multilayer films. These have not only excellent performance as a base film, but also have an advantage that each layer of the laminated layer can be formed with the same apparatus in the film forming process. However, an effective etching method for the newly developed laminated film including the copper alloy oxide layer has not been studied at all.

特許第３９７４３０５号公報Japanese Patent No. 3974305 特開２００２−３０２７８０号公報JP 2002-302780 A 米国特許出願公開第２００６／１０５５７９号明細書US Patent Application Publication No. 2006/105579 特開２００４−１９３６２０号公報JP 2004-193620 A

本発明者らは、前記の背景技術を踏まえ、ＣｕＭｇ／ＣｕＭｇＯ、ＣｕＣａ／ＣｕＣａＯ、Ｃｕ／ＣｕＣａＯ、Ｃｕ／ＣｕＡｌＭｇＯなどの銅と銅合金酸化物からなる新たな積層膜を一括エッチングする技術の開発を試みる中で、例えば、Ｃｕ単層膜のエッチングやＣｕ／Ｍｏ、Ｃｕ／Ｔｉ、Ｃｕ／Ｃｒなどの既存の銅積層膜用一括エッチングに使用されてきたＦｅＣｌ３、ＣｕＣｌ２系、混酸系のエッチング液では、ＣｕＭｇＯやＣｕＣａＯ等の下層膜の溶解性が高いため、下地膜のサイドエッチングが大きくなり、テーパー状の形が得られないなどの問題に直面した。 Based on the above-mentioned background art, the present inventors have developed a technique for collectively etching a new laminated film made of copper and a copper alloy oxide such as CuMg / CuMgO, CuCa / CuCaO, Cu / CuCaO, and Cu / CuAlMgO. While trying, for example, etching of Cu single layer film and etching of FeCl 3 , CuCl 2 type, mixed acid type that have been used for batch etching for existing copper laminated films such as Cu / Mo, Cu / Ti, Cu / Cr, etc. In the liquid, since the solubility of the lower layer film such as CuMgO or CuCaO is high, the side etching of the base film is increased, and a problem such as a taper shape cannot be obtained.

すなわち、本発明の課題は、前記のような問題を解決し、Ｃｕ金属層とＣｕ合金酸化物層を一括エッチングするための、溶解性の高い銅合金酸化物層の溶解を制御することができ、さらにまた、一括エッチングの対象となる積層において、Ｃｕ合金酸化物層を含む全ての層の溶解が適度なバランスで進む条件を実現するエッチング液およびエッチング方法を提供することにある。   That is, the object of the present invention is to solve the above-described problems and to control the dissolution of a highly soluble copper alloy oxide layer for collectively etching the Cu metal layer and the Cu alloy oxide layer. Furthermore, another object of the present invention is to provide an etching solution and an etching method that realize a condition in which dissolution of all layers including a Cu alloy oxide layer proceeds with an appropriate balance in a stack to be subjected to batch etching.

本発明者らは、上記の課題を解決すべく鋭意研究を重ねる中で、驚くべきことに、過酸化物と有機酸とを含むエッチング液を用いることによって、上記の積層膜を良好に一括エッチングできることを見出し、さらに検討を進めた結果、本発明を完成するに至った。   The inventors of the present invention have made extensive studies to solve the above problems, and surprisingly, by using an etching solution containing a peroxide and an organic acid, the above laminated film can be satisfactorily etched together. As a result of finding out what can be done and further studying it, the present invention has been completed.

すなわち本発明は、基板と接する銅酸化物層または銅合金酸化物層を含む、基板上の銅含有積層膜をエッチングするためのエッチング液であって、
過酸化物および有機酸を含む、前記エッチング液に関する。
さらに本発明は、銅含有積層膜が、Ｃｕ／ＣｕＸＯまたはＣｕＸ／ＣｕＸＯ（式中、Ｘは、Ｍｇ、ＣａまたはＭｇＡｌである）である、前記のエッチング液に関する。
また本発明は、ｐＨが３〜６である、前記のエッチング液に関する。
さらに本発明は、過酸化物が、過酸化水素である、前記のエッチング液に関する。
また本発明は、さらにキレート剤を含有する、前記のエッチング液に関する。
さらに本発明は、キレート剤が、エチレンジアミン四酢酸およびそのアルカリ塩、またはジエチレントリアミン五酢酸およびそのアルカリ塩である、前記のエッチング液に関する。
また本発明は、有機酸が、クエン酸またはグリシンである、前記のエッチング液に関する。 That is, the present invention is an etching solution for etching a copper-containing laminated film on a substrate including a copper oxide layer or a copper alloy oxide layer in contact with the substrate,
The present invention relates to the etching solution containing a peroxide and an organic acid.
Furthermore, this invention relates to the said etching liquid whose copper containing laminated film is Cu / CuXO or CuX / CuXO (In formula, X is Mg, Ca, or MgAl).
Moreover, this invention relates to the said etching liquid whose pH is 3-6.
Furthermore, this invention relates to the said etching liquid whose peroxide is hydrogen peroxide.
Moreover, this invention relates to the said etching liquid which contains a chelating agent further.
Furthermore, the present invention relates to the etching solution, wherein the chelating agent is ethylenediaminetetraacetic acid and its alkali salt, or diethylenetriaminepentaacetic acid and its alkali salt.
The present invention also relates to the above etching solution, wherein the organic acid is citric acid or glycine.

さらに本発明は、過酸化物が、過硫酸または過硫酸塩を含む、前記のエッチング液に関する。
また本発明は、過硫酸塩が、ＫＨＳＯ５、ＮａＨＳＯ５、Ｋ２Ｓ２Ｏ８、Ｎａ２Ｓ２Ｏ８および（ＮＨ４）２Ｓ２Ｏ８からなる群から選択される、前記のエッチング液に関する。
さらに本発明は、有機酸が、酢酸である、前記のエッチング液に関する。
また本発明は、基板と接する銅酸化物層または銅合金酸化物層を含む、基板上の銅含有積層膜をエッチングする方法であって、
過酸化物および有機酸を含むエッチング液を用いてエッチングする工程を含む、前記方法に関する。 Furthermore, the present invention relates to the etching solution, wherein the peroxide contains persulfuric acid or persulfate.
Further, the present invention provides the above etching, wherein the persulfate is selected from the group consisting of KHSO 5 , NaHSO 5 , K 2 S 2 O 8 , Na 2 S 2 O 8 and (NH 4 ) 2 S 2 O 8. Regarding liquids.
Furthermore, this invention relates to the said etching liquid whose organic acid is an acetic acid.
The present invention is also a method for etching a copper-containing laminated film on a substrate including a copper oxide layer or a copper alloy oxide layer in contact with the substrate,
It is related with the said method including the process of etching using the etching liquid containing a peroxide and an organic acid.

本発明は、上記の構成により、銅含有積層膜の基板と接する層が、銅酸化物層または銅合金酸化物層に対して作用させると、銅合金酸化物層の溶解速度を制御することができ、例えば、Ｃｕ／ＣｕＸＯ（Ｘは任意の金属）積層膜をテーパー形状でサイドエッチングも少ない一括エッチングを達成することができる。
これは、既存の銅積層膜用一括エッチング液はいずれも金属の酸化溶解によるものであり、銅合金酸化物積層膜の溶解は、銅の価数変化を伴わない、すなわち酸化溶解ではなく化学溶解であると考えられるところ、Ｃｕ合金酸化物膜をＣｕＯ、ＣｕＯ２等の酸化物と同様に考えた場合、Ｃｕの電位−ｐＨ線状態図から、ｐＨ４以下では酸化物の安定領域はなくＣｕイオンとなるため、ＣｕＯ、ＣｕＯ２の安定領域とＣｕイオン安定領域の境界条件付近（例えば、ｐＨ３〜６）に制御することで、Ｃｕ合金酸化物膜の溶解速度を制御することができるためであると説明することもできる。 In the present invention, when the layer in contact with the substrate of the copper-containing laminated film acts on the copper oxide layer or the copper alloy oxide layer, the dissolution rate of the copper alloy oxide layer can be controlled. For example, it is possible to achieve batch etching of Cu / CuXO (X is an arbitrary metal) laminated film with a tapered shape and less side etching.
This is because all of the existing batch etching solutions for copper laminated films are due to metal oxidative dissolution, and the dissolution of copper alloy oxide laminated films does not involve a change in the valence of copper, that is, chemical dissolution rather than oxidation dissolution. When the Cu alloy oxide film is considered in the same manner as an oxide such as CuO and CuO 2 , there is no stable region of oxide at pH 4 or lower from the Cu potential-pH line state diagram. Therefore, the dissolution rate of the Cu alloy oxide film can be controlled by controlling the boundary conditions between the stable region of CuO and CuO 2 and the stable region of the Cu ion (for example, pH 3 to 6). It can also be explained.

図１は、Ｎｏ．３溶液によるＣｕＭｇ／ＣｕＭｇＯ基板処理結果１１０ｓｅｃ（ＪＥＴ×１．５）エッチング処理後の断面観察図である（実施例３）。FIG. FIG. 6 is a cross-sectional observation view after a CuMg / CuMgO substrate processing result with 3 solutions 110 sec (JET × 1.5) etching processing (Example 3). 図２は、Ｎｏ．３溶液によるＣｕ／Ｍｏ基板処理結果１７１ｓｅｃ（ＪＥＴ×１．５）エッチング処理後の断面観察図である（比較例３）。FIG. It is a cross-sectional observation figure after Cu / Mo board | substrate process result 171sec (JET * 1.5) etching process by 3 solutions (comparative example 3). 図３は、Ｎｏ．８溶液によるＣｕＭｇ／ＣｕＭｇＯ基板処理結果９６ｓｅｃ（ＪＥＴ×１．５）エッチング処理後の断面観察図である（実施例８）。FIG. FIG. 12 is a cross-sectional observation view after etching processing of CuMg / CuMgO substrate with 8 solutions for 96 sec (JET × 1.5) (Example 8). 図４は、Ｎｏ．９溶液によるＣｕＭｇ／ＣｕＭｇＯ基板処理結果１３２ｓｅｃ（ＪＥＴ×１．５）エッチング処理後の断面観察図である（実施例９）。FIG. FIG. 11 is a cross-sectional observation view after etching processing of a CuMg / CuMgO substrate with 9 solutions 132 sec (JET × 1.5) (Example 9). 図５は、Ｎｏ．８溶液によるＣｕ／Ｍｏ基板処理結果１５８ｓｅｃ（ＪＥＴ×１．２）エッチング処理後の断面観察図である（比較例８）。FIG. It is a cross-sectional observation figure after the Cu / Mo board | substrate process result by 8 solutions 158sec (JET * 1.2) etching process (comparative example 8). 図６は、Ｎｏ．１０溶液によるＣｕ／ＣｕＣａＯ基板処理結果５３ｓｅｃ（ＪＥＴ×１．５）エッチング処理後の断面観察図である（実施例１０）。FIG. It is a cross-sectional observation figure after 53 / sec (JET * 1.5) etching process result of the Cu / CuCaO board | substrate process by 10 solutions (Example 10). 図７は、Ｎｏ．１０溶液によるＣｕ／Ｍｏ基板処理結果３５４ｓｅｃ（ＪＥＴ×１．５）エッチング処理後の断面観察図である（比較例１０）。FIG. It is a cross-sectional observation figure after 354 sec (JET * 1.5) etching process result of Cu / Mo board | substrate process by 10 solutions (comparative example 10).

本発明は、一態様において、基板と接する銅酸化物層または銅合金酸化物層を含む、基板上の銅含有積層膜をエッチングするためのエッチング液であって、過酸化物および有機酸を含む、前記エッチング液を提供する。
ここで基板は、半導体基板等に用いられ得る任意のものでよく、典型的には、ガラス、石英、セラミックなどが挙げられる。 In one aspect, the present invention is an etching solution for etching a copper-containing laminated film on a substrate, which includes a copper oxide layer or a copper alloy oxide layer in contact with the substrate, and includes a peroxide and an organic acid. The etching solution is provided.
Here, the substrate may be any substrate that can be used for a semiconductor substrate, and typically includes glass, quartz, ceramic, and the like.

本発明において、銅含有積層膜は、銅または銅合金（銅と任意の金属の合金）の層と、銅酸化物または銅合金酸化物の層とを含む。積層は、典型的には２層であるが、３層以上であっても一括エッチングすることができる。また、銅合金層における銅以外の金属元素は、銅合金酸化物層における銅以外の金属元素を同一であっても異なっていてもよい。本発明において、好ましい銅含有積層膜は、Ｃｕ／ＣｕＸＯまたはＣｕＸ／ＣｕＸＯ（式中、Ｘは、Ｍｇ、ＣａまたはＭｇＡｌである）である。   In the present invention, the copper-containing laminated film includes a layer of copper or a copper alloy (an alloy of copper and an arbitrary metal) and a layer of copper oxide or a copper alloy oxide. The lamination is typically two layers, but even if there are three or more layers, batch etching can be performed. Further, the metal element other than copper in the copper alloy layer may be the same as or different from the metal element other than copper in the copper alloy oxide layer. In the present invention, a preferable copper-containing laminated film is Cu / CuXO or CuX / CuXO (wherein X is Mg, Ca or MgAl).

本発明において、エッチング液のｐＨは、限定されるものではないが、積層膜種および膜厚、テーパー形状、サイドエッチング量などの観点から、３〜６が好ましく、３．５〜５．５がとくに好ましい。ｐＨの調整は、有機酸および有機酸塩の緩衝系を利用したり、ｐＨ調整剤を加えることで行うことができる。ｐＨが低いと、下層の銅酸化物膜の溶解が早く良好なテーパー形状が得られにくくなり、ｐＨが高いと、Ｃｕ膜のエッチング反応が進行しないかもしくは実用的なエッチング速度ではエッチングが進行しない虞がある。   In the present invention, the pH of the etching solution is not limited, but 3 to 6 is preferable, and 3.5 to 5.5 is preferable from the viewpoint of the type and thickness of the laminated film, the taper shape, the amount of side etching, and the like. Particularly preferred. The pH can be adjusted by using a buffer system of an organic acid and an organic acid salt or adding a pH adjusting agent. When the pH is low, the lower copper oxide film dissolves quickly and it becomes difficult to obtain a good taper shape. When the pH is high, the etching reaction of the Cu film does not proceed or the etching does not proceed at a practical etching rate. There is a fear.

本発明のエッチング液に用いられる酸化剤（過酸化物）は、とくに限定されないが、過酸化水素、過硫酸、過硫酸塩、過酢酸、過酢酸塩、過炭酸、過炭酸塩などが挙げられる。とくに、過酸化物の安定性、入手しやすさ、取り扱いやすさ、コストなどの観点から、過酸化水素、過硫酸、過硫酸塩が好ましい。また、過硫酸塩としては、例えば、ＫＨＳＯ５、ＮａＨＳＯ５、Ｋ２Ｓ２Ｏ８、Ｎａ２Ｓ２Ｏ８、（ＮＨ４）２Ｓ２Ｏ８などが挙げられる。また過酸化物は、適宜、２種類以上を組み合わせて用いてもよい。 The oxidizing agent (peroxide) used in the etching solution of the present invention is not particularly limited, and examples thereof include hydrogen peroxide, persulfuric acid, persulfate, peracetic acid, peracetate, percarbonate, and percarbonate. . In particular, hydrogen peroxide, persulfuric acid, and persulfate are preferable from the viewpoint of stability, availability, ease of handling, and cost of the peroxide. Examples of the persulfate include KHSO 5 , NaHSO 5 , K 2 S 2 O 8 , Na 2 S 2 O 8 , (NH 4 ) 2 S 2 O 8, and the like. Moreover, you may use a peroxide in combination of 2 or more types suitably.

本発明において、過酸化物の濃度はとくに限定されないが、過酸化水素を用いた場合、好ましくは、０．０１〜３．０ｍｏｌ／Ｌであり、より好ましくは、０．０５〜２．０ｍｏｌ／Ｌであり、さらに好ましくは、０．１〜１．０ｍｏｌ／Ｌである。過酸化水素の濃度が低いと、エッチング速度が遅くなり、高いとエッチング速度が早くなりすぎて、得られるパターンのコントロールが困難になる虞がある。   In the present invention, the concentration of the peroxide is not particularly limited, but when hydrogen peroxide is used, it is preferably 0.01 to 3.0 mol / L, more preferably 0.05 to 2.0 mol / L. L, more preferably 0.1 to 1.0 mol / L. If the concentration of hydrogen peroxide is low, the etching rate is slow, and if it is high, the etching rate is too fast, and it may be difficult to control the resulting pattern.

また、過硫酸または過硫酸塩を用いた場合、過硫酸の濃度は、好ましくは、０．０１〜３．０ｍｏｌ／Ｌであり、より好ましくは、０．０５〜２．０ｍｏｌ／Ｌであり、さらに好ましくは、０．１〜１．０ｍｏｌ／Ｌである。過硫酸の濃度が低いと、エッチング速度が遅くなり、高いとエッチング速度が早くなりすぎて、得られるパターンのコントロールが困難になる虞がある。   When persulfuric acid or persulfate is used, the concentration of persulfuric acid is preferably 0.01 to 3.0 mol / L, more preferably 0.05 to 2.0 mol / L. More preferably, it is 0.1-1.0 mol / L. If the concentration of persulfuric acid is low, the etching rate becomes slow, and if it is high, the etching rate becomes too fast, and it may be difficult to control the resulting pattern.

本発明のエッチング液に用いられる有機酸は、とくに限定されないが、クエン酸、グリシン、酢酸、酒石酸、コハク酸、乳酸、フタル酸などが挙げられる。とくに、ｐH緩衝能力と溶解性、入手のしやすさ、コストなどの観点から、クエン酸、グリシン、酢酸が好ましい。また有機酸は、適宜、２種類以上を組み合わせて用いてもよい。   The organic acid used in the etching solution of the present invention is not particularly limited, and examples thereof include citric acid, glycine, acetic acid, tartaric acid, succinic acid, lactic acid, and phthalic acid. In particular, citric acid, glycine, and acetic acid are preferable from the viewpoints of pH buffering capacity and solubility, availability, and cost. Moreover, you may use an organic acid in combination of 2 or more types suitably.

本発明において、有機酸の濃度はとくに限定されないが、０．０５〜５．０ｍｏｌ／Ｌであることが好ましく、より好ましくは０．０５〜３．０ｍｏｌ／Ｌ、とくに好ましくは０．１〜２．０ｍｏｌ／Ｌであり、さらに好ましくは０．１〜１．０ｍｏｌ／Ｌである。有機酸濃度が低いと、ｐＨ緩衝剤としての働きが不十分となり、エッチング液を所定ｐＨ範囲内に維持することが困難になる。また有機酸濃度が高いと、溶解性の問題が生じ、高濃度化による効果が十分には得られない虞がある。   In the present invention, the concentration of the organic acid is not particularly limited, but is preferably 0.05 to 5.0 mol / L, more preferably 0.05 to 3.0 mol / L, and particularly preferably 0.1 to 2. 0.0 mol / L, more preferably 0.1 to 1.0 mol / L. When the organic acid concentration is low, the function as a pH buffering agent becomes insufficient, and it becomes difficult to maintain the etching solution within a predetermined pH range. Further, when the organic acid concentration is high, there is a problem of solubility, and there is a possibility that the effect of increasing the concentration cannot be obtained sufficiently.

本発明のエッチング液に用いられるキレート剤は、とくに限定されないが、エチレンジアミン四酢酸およびそのアルカリ塩、ジエチレントリアミン五酢酸およびそのアルカリ塩、ニトリロ三酢酸およびそのアルカリ塩などが挙げられる。とくに、キレート化能力、キレート剤の溶解性などの観点から、エチレンジアミン四酢酸およびそのアルカリ塩、ジエチレントリアミン五酢酸およびそのアルカリ塩が好ましい。またキレート剤は、適宜、２種類以上を組み合わせて用いてもよい。かかるキレート剤を配合することにより、エッチングによって溶解したＣｕ、Ｃａ、Ｍｇなどの金属イオンをキレート化することで、エッチング反応物の溶液内析出を抑える効果があり、例えば、Ｃｕイオンによる過酸化水素の分解反応を抑制することができる。   The chelating agent used in the etching solution of the present invention is not particularly limited, and examples thereof include ethylenediaminetetraacetic acid and its alkali salt, diethylenetriaminepentaacetic acid and its alkali salt, nitrilotriacetic acid and its alkali salt, and the like. In particular, ethylenediaminetetraacetic acid and its alkali salt, diethylenetriaminepentaacetic acid and its alkali salt are preferable from the viewpoint of chelating ability, solubility of the chelating agent, and the like. Moreover, you may use a chelating agent suitably combining 2 or more types. By compounding such a chelating agent, metal ions such as Cu, Ca, Mg and the like dissolved by etching are chelated, thereby suppressing the precipitation of etching reaction products in the solution. For example, hydrogen peroxide by Cu ions Decomposition reaction can be suppressed.

本発明において、キレート剤の濃度はとくに限定されないが、０．０１〜０．２ｍｏｌ／Ｌであることが好ましく、より好ましくは０．０３〜０．１５ｍｏｌ／Ｌであり、さらに好ましくは０．０５〜０．１ｍｏｌ／Ｌである。キレート剤濃度が低いと、キレート剤としての働きが不十分であり、高いと溶解度不足で均一溶液とならない虞がある。   In the present invention, the concentration of the chelating agent is not particularly limited, but is preferably 0.01 to 0.2 mol / L, more preferably 0.03 to 0.15 mol / L, still more preferably 0.05. -0.1 mol / L. When the chelating agent concentration is low, the function as a chelating agent is insufficient, and when it is high, there is a possibility that a uniform solution cannot be obtained due to insufficient solubility.

本発明において、過酸化物として過酸化水素を用いた場合、有機酸としてクエン酸またはグリシンを用いることが好ましい。またこの場合、さらにキレート剤として、エチレンジアミン四酢酸二ナトリウム、ジエチレントリアミン五酢酸三ナトリウムを含むことが好ましい。このように、過酸化水素、有機酸およびキレート剤を含む場合、それぞれの濃度は、とくに限定されないが、例えば、過酸化水素０．０１〜３．０ｍｏｌ／Ｌに対して、有機酸は、０．０５〜３．０ｍｏｌ／Ｌ、好ましくは、０．１〜２．０ｍｏｌ／Ｌ、さらに好ましくは、０．１〜１．０ｍｏｌ／Ｌであり、キレート剤は、０．０１〜０．２ｍｏｌ／Ｌ、好ましくは、０．０３〜０．１５ｍｏｌ／Ｌ、さらに好ましくは、０．０５〜０．１ｍｏｌ／Ｌとすることができる。   In the present invention, when hydrogen peroxide is used as the peroxide, it is preferable to use citric acid or glycine as the organic acid. In this case, it is preferable to further contain disodium ethylenediaminetetraacetate and trisodium diethylenetriaminepentaacetate as chelating agents. Thus, when hydrogen peroxide, an organic acid, and a chelating agent are included, the concentration of each is not particularly limited. For example, for hydrogen peroxide of 0.01 to 3.0 mol / L, the organic acid is 0 0.05 to 3.0 mol / L, preferably 0.1 to 2.0 mol / L, more preferably 0.1 to 1.0 mol / L, and the chelating agent is 0.01 to 0.2 mol / L. L, preferably 0.03 to 0.15 mol / L, and more preferably 0.05 to 0.1 mol / L.

本発明において、過酸化物として過硫酸または過硫酸塩を用いた場合、有機酸として酢酸を用いることが好ましい。この場合、それぞれの濃度は、とくに限定されないが、例えば、過硫酸または過硫酸塩０．０１〜３．０ｍｏｌ／Ｌに対して、酢酸は、０．０５〜５．０ｍｏｌ／Ｌ、好ましくは、０．１〜３．０ｍｏｌ／Ｌ、さらに好ましくは０．１〜１．０ｍｏｌ／Ｌとすることができる。酢酸濃度が低いと、ｐＨ緩衝剤としての働きが不十分で、エッチング液を所定ｐＨ範囲内に維持することが困難となり、高いと酢酸の臭気の問題もあり、また高濃度化による効果も十分には得られない虞がある。   In the present invention, when persulfuric acid or persulfate is used as the peroxide, acetic acid is preferably used as the organic acid. In this case, the concentration of each is not particularly limited. For example, acetic acid is 0.05 to 5.0 mol / L, preferably 0.01 to 3.0 mol / L persulfuric acid or persulfate, It can be 0.1 to 3.0 mol / L, more preferably 0.1 to 1.0 mol / L. If the acetic acid concentration is low, the pH buffering agent is insufficient and it becomes difficult to maintain the etching solution within the predetermined pH range. If the acetic acid concentration is high, there is a problem of acetic acid odor, and the effect of increasing the concentration is sufficient. May not be obtained.

本発明のエッチング方法は、一態様において、基板と接する銅酸化物層または銅合金酸化物層を含む、基板上の銅含有積層膜をエッチングする方法であって、過酸化物および有機酸を含むエッチング液を用いてエッチングする工程を含む、前記方法である。
したがって、エッチング対象が銅含有積層膜の基板と接する層が、銅酸化物層または銅合金酸化物層であること、エッチング液として過酸化物および有機酸を含むエッチング液を用いること以外は、とくに限定されず、適宜、従来から用いられているエッチングのための工程を用いることができる。 In one aspect, the etching method of the present invention is a method for etching a copper-containing laminated film on a substrate including a copper oxide layer or a copper alloy oxide layer in contact with the substrate, and includes a peroxide and an organic acid. It is the said method including the process of etching using an etching liquid.
Therefore, except that the layer in contact with the substrate of the copper-containing laminated film is a copper oxide layer or a copper alloy oxide layer, and an etching solution containing a peroxide and an organic acid is used as an etching solution. Without being limited, a conventionally used process for etching can be used as appropriate.

１．ＣｕＭｇ／ＣｕＭｇＯ／ｇｌａｓｓ基板処理（実施例１〜６）
ガラス基板上に５００ÅのＣｕＭｇＯ膜をスパッタリングし、さらにその上に３０００ÅのＣｕＭｇ膜をスパッタリングしてＣｕＭｇ／ＣｕＭｇＯ二重積層膜を形成した。さらに、このＣｕＭｇ／ＣｕＭｇＯ二重積層膜上にフォトレジストコーティングした後、選択的に露光および現像して、エッチングマスクを形成した。表１に示すエッチング液（Ｎｏ．１〜６）を調製し、上記基板を液温度３０℃、撹拌条件で浸漬処理を行った。目視によりジャストエッチング時間（ＪＥＴ）を確認し、ＪＥＴの１．５倍を処理時間とした。 1. CuMg / CuMgO / glass substrate processing (Examples 1 to 6)
A 500M CuMgO film was sputtered on a glass substrate, and a 3000M CuMg film was further sputtered thereon to form a CuMg / CuMgO double laminated film. Further, a photoresist coating was formed on this CuMg / CuMgO double laminated film, and then selectively exposed and developed to form an etching mask. Etching solutions (Nos. 1 to 6) shown in Table 1 were prepared, and the substrate was subjected to immersion treatment at a liquid temperature of 30 ° C. under stirring conditions. The just etching time (JET) was confirmed by visual observation, and 1.5 times JET was defined as the processing time.

液Ｎｏ．１〜６を用いてＣｕＭｇ／ＣｕＭｇＯ／ｇｌａｓｓ基板を処理した結果を表２に示す。
Liquid No. Table 2 shows the results of treating the CuMg / CuMgO / glass substrate using 1-6.

実施例１〜６ではいずれも、断面がテーパー形状となり、サイドエッチング量も１．０〜１．６μｍと比較的少なく抑えられている。また、ガラス基板上に、エッチング残渣等も認められなかった。
また、典型的な断面観察図（走査型電子顕微鏡（ＳＥＭ）による写真。倍率：40,000倍）を図１（Ｎｏ．３溶液によるＣｕＭｇ／ＣｕＭｇＯ基板処理結果１１０ｓｅｃ（ＪＥＴ×１．５）エッチング処理後（実施例３））に示す。 In each of Examples 1 to 6, the cross section is tapered, and the amount of side etching is relatively small, 1.0 to 1.6 μm. Further, no etching residue or the like was observed on the glass substrate.
In addition, a typical cross-sectional view (photograph by a scanning electron microscope (SEM). Magnification: 40,000 times) is shown in FIG. 1 (CuMg / CuMgO substrate processing result by No. 3 solution after 110 sec (JET × 1.5) etching process. (Example 3)).

２．Ｃｕ／Ｍｏ／ｇｌａｓｓ基板処理（比較例２〜６）
ガラス基板上に２５０ÅのＭｏ膜をスパッタリングし、さらにその上に４０００ÅのＣｕ膜をスパッタリングしてＣｕ／Ｍｏの二重積層膜を形成した。さらに、このＣｕ／Ｍｏ二重積層膜上にフォトレジストコーティングした後、選択的に露光および現像して、エッチングマスクを形成した。実施例と同様に表１に示すエッチング液（Ｎｏ．２〜６）を調製し、上記基板を液温度３０℃、撹拌条件で浸漬処理を行った。目視によりジャストエッチング時間（ＪＥＴ）を確認し、ＪＥＴの１．５倍を処理時間とした。
液Ｎｏ．２〜６を用いてＣｕ／Ｍｏ／ｇｌａｓｓ基板を処理した結果を表３に示す。
なお、比較例１となるべき液Ｎｏ．１を用いた実験は、該液Ｎｏ．１のｐＨが３．３であり、液Ｎｏ．２〜６の結果から形状が不良となることが明らかなため行わなかった。 2. Cu / Mo / glass substrate processing (Comparative Examples 2 to 6)
A 250 膜 Mo film was sputtered on a glass substrate, and a 4000 Ｃｕ Cu film was further sputtered thereon to form a Cu / Mo double laminated film. Further, a photoresist coating was applied on the Cu / Mo double laminated film, and then selectively exposed and developed to form an etching mask. Etching solutions (Nos. 2 to 6) shown in Table 1 were prepared in the same manner as in Examples, and the substrate was subjected to immersion treatment at a liquid temperature of 30 ° C. under stirring conditions. The just etching time (JET) was confirmed by visual observation, and 1.5 times JET was defined as the processing time.
Liquid No. Table 3 shows the results of processing the Cu / Mo / glass substrate using 2-6.
In addition, liquid No. which should be Comparative Example 1 In the experiment using No. 1, the liquid No. 1 was used. 1 has a pH of 3.3, and liquid No. Since it was clear from the results of 2 to 6 that the shape was defective, it was not carried out.

Ｃｕ／Ｍｏ二重積層膜では、どの処理液においても、下地Ｍｏ膜の溶解が速く進むため断面形状は『くの字型』となり、正常な配線を形成することは困難であった。本態様におけるエッチング液組成物はＣｕＸ／ＣｕＸＯ二重積層膜用に調整したものであり、銅合金酸化物膜が適切な速度で溶解することがポイントである。そのため、単純に既存Ｃｕ／Ｍｏ二重積層膜へ適用することはできない。
また、典型的な断面観察図（走査型電子顕微鏡（ＳＥＭ）による写真。倍率：40,000倍）を図２（Ｎｏ．３溶液によるＣｕ／Ｍｏ基板処理結果１７１ｓｅｃ（ＪＥＴ×１．５）エッチング処理後（比較例３））に示す。 In the Cu / Mo double laminated film, the dissolution of the underlying Mo film progresses quickly in any processing solution, so that the cross-sectional shape becomes a “<shape” and it is difficult to form a normal wiring. The etching solution composition in this embodiment is prepared for a CuX / CuXO double laminated film, and the point is that the copper alloy oxide film dissolves at an appropriate rate. Therefore, it cannot be simply applied to an existing Cu / Mo double laminated film.
In addition, a typical cross-sectional view (photograph by a scanning electron microscope (SEM), magnification: 40,000 times) is shown in FIG. (Comparative Example 3))

３．ＣｕＭｇ／ＣｕＭｇＯ／ｇｌａｓｓ基板処理（実施例７〜９）
実施例１〜６で用いた基板と同様のＣｕＭｇ／ＣｕＭｇＯ二重積層膜を用意し、下記表４に示す液（Ｎｏ．７〜９）によるエッチング処理を実施した。液温度３０℃、撹拌条件で浸漬処理を行い、目視によりジャストエッチング時間（ＪＥＴ）を確認し、ＪＥＴの１．５倍を処理時間とした。 3. CuMg / CuMgO / glass substrate treatment (Examples 7 to 9)
A CuMg / CuMgO double laminated film similar to the substrate used in Examples 1 to 6 was prepared, and an etching process using liquids (Nos. 7 to 9) shown in Table 4 below was performed. The immersion treatment was performed at a liquid temperature of 30 ° C. under stirring conditions, and the just etching time (JET) was confirmed by visual observation. The treatment time was 1.5 times JET.

液Ｎｏ．７〜９を用いてＣｕＭｇ／ＣｕＭｇＯ／ｇｌａｓｓ基板を処理したを表５に示す。
Liquid No. Table 5 shows the results of treating CuMg / CuMgO / glass substrates using 7-9.

実施例７〜９ではいずれも、断面がテーパー形状となり、サイドエッチング量も０．９〜１．３μｍと比較的少なく抑えられている。また、ガラス基板上に、エッチング残渣等も認められなかった。
また、典型的な断面観察図（走査型電子顕微鏡（ＳＥＭ）による写真。倍率：40,000倍）を図３（Ｎｏ．８溶液によるＣｕＭｇ／ＣｕＭｇＯ基板処理結果９６ｓｅｃ（ＪＥＴ×１．５）エッチング処理後（実施例８））および図４（Ｎｏ．９溶液によるＣｕＭｇ／ＣｕＭｇＯ基板処理結果１３２ｓｅｃ（ＪＥＴ×１．５）エッチング処理後（実施例９））に示す。 In each of Examples 7 to 9, the cross section has a tapered shape, and the amount of side etching is relatively small, 0.9 to 1.3 μm. Further, no etching residue or the like was observed on the glass substrate.
Further, a typical cross-sectional observation view (photograph by scanning electron microscope (SEM). Magnification: 40,000 times) is shown in FIG. 3 (CuMg / CuMgO substrate processing result with No. 8 solution after 96 sec (JET × 1.5) etching process. (Example 8)) and FIG. 4 (CuMg / CuMgO substrate processing result with No. 9 solution 132 sec (JET × 1.5) after etching process (Example 9)).

４．Ｃｕ／Ｍｏ／ｇｌａｓｓ基板処理（比較例７〜９）
比較例として、前述の比較例２〜６と同様のＣｕ／Ｍｏの二重積層膜を用い、実施例と同じく表４に示すエッチング液（Ｎｏ．７〜９）により、液温度３０℃、撹拌条件で浸漬処理を行った。目視によりジャストエッチング時間（ＪＥＴ）を確認し、ＪＥＴの１．２倍および１．５倍を処理時間とした。
液Ｎｏ．７〜９を用いてＣｕ／Ｍｏ／ｇｌａｓｓ基板を処理した結果を表６に示す。 4). Cu / Mo / glass substrate processing (Comparative Examples 7 to 9)
As a comparative example, the same Cu / Mo double laminated film as the above-mentioned comparative examples 2 to 6 was used, and the liquid temperature was 30 ° C. and stirring was performed with the etching solution (Nos. 7 to 9) shown in Table 4 as in the examples. Immersion treatment was performed under conditions. The just etching time (JET) was visually confirmed, and 1.2 times and 1.5 times of JET were set as the processing time.
Liquid No. Table 6 shows the results of processing the Cu / Mo / glass substrate using 7-9.

Ｃｕ／Ｍｏ二重積層膜では、どの処理液においても、下地Ｍｏ膜の溶解が速く進むため断面形状は『垂直からわずかな逆くの字型』となり、また、サイドエッチング量も３．０μｍ以上となり正常な配線を形成することは困難であった。本態様におけるエッチング液組成物はＣｕＸ／ＣｕＸＯ二重積層膜用に調整したものであり、銅合金酸化物膜が適切な速度で溶解することがポイントである。既存Ｃｕ／Ｍｏ二重積層膜へ適用することはできない。
また、典型的な断面観察図（走査型電子顕微鏡（ＳＥＭ）による写真。倍率：40,000倍）を図５（Ｎｏ．８溶液によるＣｕ／Ｍｏ基板処理結果１５８ｓｅｃ（ＪＥＴ×１．２）エッチング処理後（比較例８））に示す。 In the Cu / Mo double laminated film, the dissolution of the underlying Mo film progresses quickly in any processing solution, so that the cross-sectional shape becomes “slightly inverted from the vertical” and the side etching amount is 3.0 μm or more. Therefore, it was difficult to form normal wiring. The etching solution composition in this embodiment is prepared for a CuX / CuXO double laminated film, and the point is that the copper alloy oxide film dissolves at an appropriate rate. It cannot be applied to existing Cu / Mo double laminated films.
In addition, a typical cross-sectional view (photograph by a scanning electron microscope (SEM), magnification: 40,000 times) is shown in FIG. 5 (Cu / Mo substrate processing result with No. 8 solution, 158 sec (JET × 1.2) after the etching process. (Comparative Example 8)).

５．各種Ｃｕ積層膜の処理（実施例１０〜１２および比較例１０）
ガラス基板上に５００ÅのＣｕＣａＯ膜をスパッタリングし、さらにその上に３０００ÅのＣｕ膜をまたはＣｕＣａ膜をスパッタリングしてＣｕ／ＣｕＣａＯ二重積層膜およびＣｕＣａ／ＣｕＣａＯ二重積層膜を作製した。また、ガラス基板上に下地層として５００ÅのＣｕＭｇＡｌＯ膜をスパッタリングした後、その上に３０００ÅのＣｕ膜スパッタリングしてＣｕ／ＣｕＭｇＡｌＯ二重積層を作製した。、これらの二重積層膜にフォトレジストコーティングした後、選択的に露光および現像して、エッチングマスクを形成した。次に、表７に示すエッチング液（Ｎｏ．１０）を調製し、上記各二重層基板について、液温度３０℃、撹拌条件で浸漬処理を行った。目視によりジャストエッチング時間（ＪＥＴ）を確認し、ＪＥＴの１．５倍を処理時間とした。 5). Treatment of various Cu laminated films (Examples 10 to 12 and Comparative Example 10)
A Cu / CuCaO double laminated film and a CuCa / CuCaO double laminated film were produced by sputtering a 500 Ｃｕ CuCaO film on a glass substrate and sputtering a 3000 ３ Cu film or CuCa film thereon. Further, after sputtering a 500 Ｃｕ CuMgAlO film as a base layer on a glass substrate, a Cu / CuMgAlO double stack was produced by sputtering a 3000 Ｃｕ Cu film thereon. These double laminated films were coated with a photoresist, and then selectively exposed and developed to form an etching mask. Next, an etching solution (No. 10) shown in Table 7 was prepared, and each of the double layer substrates was subjected to an immersion treatment at a liquid temperature of 30 ° C. under stirring conditions. The just etching time (JET) was confirmed by visual observation, and 1.5 times JET was defined as the processing time.

また、比較例１０として、前述の比較例２〜６と同様のＣｕ／Ｍｏの二重積層膜を用い、実施例と同じく表７に示すエッチング液（Ｎｏ．１０）により、液温度３０℃、撹拌条件で浸漬処理を行った。目視によりジャストエッチング時間（ＪＥＴ）を確認し、ＪＥＴの１．５倍を処理時間とした。
Moreover, as Comparative Example 10, the same Cu / Mo double laminated film as in Comparative Examples 2 to 6 described above was used, and the etching temperature (No. 10) shown in Table 7 was the same as in the example. Immersion treatment was performed under stirring conditions. The just etching time (JET) was confirmed by visual observation, and 1.5 times JET was defined as the processing time.

液Ｎｏ．１０による各種Ｃｕ積層膜を処理した結果を表８に示す。
Liquid No. Table 8 shows the results of treating various Cu laminated films according to No. 10.

Ｃｕ／ＣｕＣａＯ、ＣｕＣａ／ＣｕＣａＯ、Ｃｕ／ＣｕＭｇＡｌＯいずれの二重積層膜でも、断面が純テーパー形状となり、サイドエッチング量も０．６〜１．３μｍと比較的少なく抑えられている。また、ガラス基板上に、エッチング残渣等も認められなかった。
断面観察図（走査型電子顕微鏡（ＳＥＭ）による写真。倍率：40,000倍）を図６（Ｎｏ．１０溶液によるＣｕ／ＣｕＣａＯ基板処理結果５３ｓｅｃ（ＪＥＴ×１．５）エッチング処理後（実施例１０））に示す。 In any of the double laminated films of Cu / CuCaO, CuCa / CuCaO, and Cu / CuMgAlO, the cross section has a pure taper shape, and the side etching amount is suppressed to a relatively small value of 0.6 to 1.3 μm. Further, no etching residue or the like was observed on the glass substrate.
Cross-sectional observation (photograph by scanning electron microscope (SEM). Magnification: 40,000 times) is shown in FIG. 6 (Cu / CuCaO substrate treatment result with No. 10 solution 53 sec (JET × 1.5) after etching treatment (Example 10) ).

一方、Ｃｕ／Ｍｏ二重積層膜では、下地Ｍｏ膜の溶解が速く進むため断面形状は『逆テーパー形状』となり、また、サイドエッチング量も３．０μｍと大きく、ガラス基板上に微細粒子状の残渣も認められ、正常な配線を形成することは困難であった。本態様におけるエッチング液組成物はＣｕＸ／ＣｕＸＯ二重積層膜用に調整したものであり、銅合金酸化物膜が適切な速度で溶解することがポイントである。既存Ｃｕ／Ｍｏ二重積層膜への適用することはできない。
断面観察図（走査型電子顕微鏡（ＳＥＭ）による写真。倍率：40,000倍）を図７（Ｎｏ．１０溶液によるＣｕ／Ｍｏ基板処理結果３５４ｓｅｃ（ＪＥＴ×１．５）エッチング処理後（比較例１１））に示す。 On the other hand, in the Cu / Mo double laminated film, the dissolution of the underlying Mo film proceeds rapidly, so that the cross-sectional shape becomes “reverse tapered shape”, and the side etching amount is as large as 3.0 μm, and the fine particle shape is formed on the glass substrate. Residue was also observed, and it was difficult to form normal wiring. The etching solution composition in this embodiment is prepared for a CuX / CuXO double laminated film, and the point is that the copper alloy oxide film dissolves at an appropriate rate. It cannot be applied to existing Cu / Mo double laminated films.
Cross-sectional observation (photograph by scanning electron microscope (SEM), magnification: 40,000 times) is shown in FIG. 7 (Cu / Mo substrate treatment result with No. 10 solution 354 sec (JET × 1.5) after etching treatment (Comparative Example 11)) ).

６．各種Ｃｕ積層膜の処理（実施例１３〜１５および比較例１１）
実施例１０〜１２で用いたＣｕ／ＣｕＣａＯ、ＣｕＣａ／ＣｕＣａＯ、Ｃｕ／ＣｕＭｇＡｌＯ各二重積層膜について、表４に示すエッチング液（Ｎｏ．７）を調製し、液温度３０℃、撹拌条件で浸漬処理を行った。目視によりジャストエッチング時間（ＪＥＴ）を確認し、ＪＥＴの１．５倍を処理時間とした。 6). Treatment of various Cu laminated films (Examples 13 to 15 and Comparative Example 11)
For each of the Cu / CuCaO, CuCa / CuCaO, and Cu / CuMgAlO double laminated films used in Examples 10 to 12, the etching solution (No. 7) shown in Table 4 was prepared, and immersed under stirring conditions at a liquid temperature of 30 ° C. Processed. The just etching time (JET) was confirmed by visual observation, and 1.5 times JET was defined as the processing time.

比較例１１として、前述の比較例２〜６と同様のＣｕ／Ｍｏの二重積層膜を用い、実施例と同じく表４に示すエッチング液（Ｎｏ．７）により、液温度３０℃、撹拌条件で浸漬処理を行った。目視によりジャストエッチング時間（ＪＥＴ）を確認し、ＪＥＴの１．５倍を処理時間とした。
液Ｎｏ．７による各種Ｃｕ積層膜を処理した結果を表９に示す。
As Comparative Example 11, the same Cu / Mo double laminated film as in Comparative Examples 2 to 6 described above was used, and the etching temperature shown in Table 4 was the same as in the example. The immersion treatment was performed. The just etching time (JET) was confirmed by visual observation, and 1.5 times JET was defined as the processing time.
Liquid No. Table 9 shows the results of treating various Cu laminated films according to No. 7.

Ｃｕ／ＣｕＣａＯ、ＣｕＣａ／ＣｕＣａＯ、Ｃｕ／ＣｕＭｇＡｌＯいずれの二重積層膜も、断面が純テーパー形状となり、サイドエッチング量も０．５〜１．０μｍと比較的少なく抑えられている。また、ガラス基板上に、エッチング残渣等も認められなかった。   In any of the double laminated films of Cu / CuCaO, CuCa / CuCaO, and Cu / CuMgAlO, the cross section is a pure taper shape, and the side etching amount is suppressed to a relatively small value of 0.5 to 1.0 μm. Further, no etching residue or the like was observed on the glass substrate.

一方、Ｃｕ／Ｍｏ二重積層膜では、下地Ｍｏ膜の溶解が速く進むため断面形状は垂直となり、また、サイドエッチング量は８．３μｍとなり、正常な配線を形成することは困難であった。   On the other hand, in the Cu / Mo double laminated film, the dissolution of the underlying Mo film progresses rapidly, so that the cross-sectional shape becomes vertical and the side etching amount becomes 8.3 μm, and it is difficult to form a normal wiring.

本態様におけるエッチング液組成物はＣｕＸ／ＣｕＸＯ二重積層膜用に調整したものであり、銅合金酸化物膜が適切な速度で溶解することがポイントである。既存Ｃｕ／Ｍｏ二重積層膜へ適用することはできない。   The etching solution composition in this embodiment is prepared for a CuX / CuXO double laminated film, and the point is that the copper alloy oxide film dissolves at an appropriate rate. It cannot be applied to existing Cu / Mo double laminated films.

本発明のエッチング液およびエッチング方法は、銅含有積層膜の基板と接する層が、銅酸化物層または銅合金酸化物層である新しい半導体等の積層体基板において、テーパー形状でサイドエッチングも少ない一括エッチングを達成することができる。   The etching solution and etching method of the present invention is a batch substrate having a tapered shape and less side etching in a laminated substrate such as a new semiconductor in which the layer in contact with the substrate of the copper-containing laminated film is a copper oxide layer or a copper alloy oxide layer. Etching can be achieved.

Claims (11)

基板と接する銅酸化物層または銅合金酸化物層を含む、基板上の銅含有積層膜をエッチングするためのエッチング液であって、
過酸化物および有機酸を含む、前記エッチング液。 An etching solution for etching a copper-containing laminated film on a substrate, comprising a copper oxide layer or a copper alloy oxide layer in contact with the substrate,
The etching solution comprising a peroxide and an organic acid. 銅含有積層膜が、Ｃｕ／ＣｕＸＯまたはＣｕＸ／ＣｕＸＯ（式中、Ｘは、Ｍｇ、ＣａまたはＭｇＡｌである）である、請求項１に記載のエッチング液。   The etching solution according to claim 1, wherein the copper-containing laminated film is Cu / CuXO or CuX / CuXO (wherein X is Mg, Ca, or MgAl). ｐＨが３〜６である、請求項１または２に記載のエッチング液。   The etching solution according to claim 1 or 2 whose pH is 3-6. 過酸化物が、過酸化水素である、請求項１〜３のいずれかに記載のエッチング液。   The etching solution according to claim 1, wherein the peroxide is hydrogen peroxide. さらにキレート剤を含有する、請求項４に記載のエッチング液。   Furthermore, the etching liquid of Claim 4 containing a chelating agent. キレート剤が、エチレンジアミン四酢酸およびそのアルカリ塩、またはジエチレントリアミン五酢酸およびそのアルカリ塩である、請求項５に記載のエッチング液。   The etching solution according to claim 5, wherein the chelating agent is ethylenediaminetetraacetic acid and an alkali salt thereof, or diethylenetriaminepentaacetic acid and an alkali salt thereof. 有機酸が、クエン酸またはグリシンである、請求項４〜６のいずれかに記載のエッチング液。   The etching solution according to any one of claims 4 to 6, wherein the organic acid is citric acid or glycine. 過酸化物が、過硫酸または過硫酸塩を含む、請求項１〜３のいずれかに記載のエッチング液。   The etching liquid in any one of Claims 1-3 in which a peroxide contains a persulfuric acid or a persulfate. 過硫酸塩が、ＫＨＳＯ５、ＮａＨＳＯ５、Ｋ２Ｓ２Ｏ８、Ｎａ２Ｓ２Ｏ８および（ＮＨ４）２Ｓ２Ｏ８からなる群から選択される、請求項８に記載のエッチング液。 Persulfate, KHSO 5, NaHSO 5, K 2 S 2 O 8, Na 2 S 2 O 8 and (NH 4) is selected from the group consisting of 2 S 2 O 8, the etching solution according to claim 8 . 有機酸が、酢酸である、請求項８または９に記載のエッチング液。   The etching solution according to claim 8 or 9, wherein the organic acid is acetic acid. 基板と接する銅酸化物層または銅合金酸化物層を含む、基板上の銅含有積層膜をエッチングする方法であって、
過酸化物および有機酸を含むエッチング液を用いてエッチングする工程を含む、前記方法。 A method for etching a copper-containing laminated film on a substrate, comprising a copper oxide layer or a copper alloy oxide layer in contact with the substrate,
The said method including the process of etching using the etching liquid containing a peroxide and an organic acid.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012156248A (en) * 2011-01-25 2012-08-16 Kanto Chem Co Inc Etchant composition for metal thin film containing copper as main component
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KR20130046295A (en) * 2011-10-27 2013-05-07 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61591A (en) * 1984-06-13 1986-01-06 Fujitsu Ltd Etching process of copper
JPH0718472A (en) * 1993-07-06 1995-01-20 Ebara Yuujiraito Kk Immersion etching solution for copper and copper alloy material
JP2001059191A (en) * 1999-06-18 2001-03-06 Furontekku:Kk Etching agent, production of substrate for electronic equipment using the same and electronic equipment
JP2002302780A (en) * 2000-12-20 2002-10-18 Lg Phillips Lcd Co Ltd Etching solution and array substrate for electronic apparatus having copper wiring patterned and formed by etching solution
JP2004193620A (en) * 2002-12-12 2004-07-08 Lg Phillips Lcd Co Ltd Etching solution for removing molybdenum residue from copper molybdenum film, and etching method therefore
JP2007005790A (en) * 2005-06-22 2007-01-11 Samsung Electronics Co Ltd Etchant, method for forming wiring using this, and method for manufacturing thin film transistor substrate
WO2008081805A1 (en) * 2006-12-28 2008-07-10 Ulvac, Inc. Method for forming wiring film, transistor, and electronic device
JP2008227508A (en) * 2007-03-15 2008-09-25 Dongjin Semichem Co Ltd Etching liquid composition of thin film transistor liquid crystal display
JP2008270235A (en) * 2007-04-16 2008-11-06 Ulvac Japan Ltd Etchant and manufacturing method of transistor
JP2009041082A (en) * 2007-08-10 2009-02-26 Ulvac Japan Ltd Thin film forming method
JP2009076601A (en) * 2007-09-19 2009-04-09 Nagase Chemtex Corp Etching solution
JP2010232486A (en) * 2009-03-27 2010-10-14 Nagase Chemtex Corp Composition for etching

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS533975B2 (en) * 1973-10-17 1978-02-13 Tokai Electro Chemical Co
DE102005041349A1 (en) * 2005-08-31 2007-03-01 Basf Ag Phosphate-free cleaning formulation, useful for dishwasher, comprises: copolymers from monoethylenic unsaturated monocarboxylic acids; complexing agent; nonionic surfactant, bleaching agent; builder; enzyme; and additives

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61591A (en) * 1984-06-13 1986-01-06 Fujitsu Ltd Etching process of copper
JPH0718472A (en) * 1993-07-06 1995-01-20 Ebara Yuujiraito Kk Immersion etching solution for copper and copper alloy material
JP2001059191A (en) * 1999-06-18 2001-03-06 Furontekku:Kk Etching agent, production of substrate for electronic equipment using the same and electronic equipment
JP2002302780A (en) * 2000-12-20 2002-10-18 Lg Phillips Lcd Co Ltd Etching solution and array substrate for electronic apparatus having copper wiring patterned and formed by etching solution
JP2004193620A (en) * 2002-12-12 2004-07-08 Lg Phillips Lcd Co Ltd Etching solution for removing molybdenum residue from copper molybdenum film, and etching method therefore
JP2007005790A (en) * 2005-06-22 2007-01-11 Samsung Electronics Co Ltd Etchant, method for forming wiring using this, and method for manufacturing thin film transistor substrate
WO2008081805A1 (en) * 2006-12-28 2008-07-10 Ulvac, Inc. Method for forming wiring film, transistor, and electronic device
JP2008227508A (en) * 2007-03-15 2008-09-25 Dongjin Semichem Co Ltd Etching liquid composition of thin film transistor liquid crystal display
JP2008270235A (en) * 2007-04-16 2008-11-06 Ulvac Japan Ltd Etchant and manufacturing method of transistor
JP2009041082A (en) * 2007-08-10 2009-02-26 Ulvac Japan Ltd Thin film forming method
JP2009076601A (en) * 2007-09-19 2009-04-09 Nagase Chemtex Corp Etching solution
JP2010232486A (en) * 2009-03-27 2010-10-14 Nagase Chemtex Corp Composition for etching

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012156248A (en) * 2011-01-25 2012-08-16 Kanto Chem Co Inc Etchant composition for metal thin film containing copper as main component
CN102995021A (en) * 2011-09-08 2013-03-27 关东化学株式会社 Etching solution composition and etching method for copper and copper alloy
JP2013058629A (en) * 2011-09-08 2013-03-28 Kanto Chem Co Inc Etchant for copper and copper alloy
KR101877987B1 (en) * 2011-10-27 2018-07-16 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display
KR20130046295A (en) * 2011-10-27 2013-05-07 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display
JP2013234351A (en) * 2012-05-08 2013-11-21 Showa Co Ltd Cleaning agent and cleaning method for inner face of copper tube
CN103806000A (en) * 2012-11-12 2014-05-21 东友Fine-Chem股份有限公司 Etchant composition, array substrate and method for manufacturing the array substrate
JP2015030809A (en) * 2013-08-05 2015-02-16 三和油化工業株式会社 Etchant composition
CN104611701A (en) * 2013-11-01 2015-05-13 达兴材料股份有限公司 Etching solution composition and etching method
JP2015130439A (en) * 2014-01-08 2015-07-16 株式会社荏原製作所 Etchant, etching method, and method of producing solder bump
JP2020088178A (en) * 2018-11-26 2020-06-04 株式会社Ｓｃｒｅｅｎホールディングス Substrate processing method and substrate processing apparatus
JP7261567B2 (en) 2018-11-26 2023-04-20 株式会社Ｓｃｒｅｅｎホールディングス Substrate processing method and substrate processing apparatus
JP7544899B2 (en) 2018-11-26 2024-09-03 株式会社Ｓｃｒｅｅｎホールディングス SUBSTRATE PROCESSING METHOD AND SUBSTRATE PROCESSING APPARATUS
WO2024034426A1 (en) * 2022-08-08 2024-02-15 奥野製薬工業株式会社 Copper etchant for removing copper seed layer

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