JPWO2013002283A1 - エッチング液及びそれを用いたエッチング方法 - Google Patents
エッチング液及びそれを用いたエッチング方法 Download PDFInfo
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- JPWO2013002283A1 JPWO2013002283A1 JP2013522911A JP2013522911A JPWO2013002283A1 JP WO2013002283 A1 JPWO2013002283 A1 JP WO2013002283A1 JP 2013522911 A JP2013522911 A JP 2013522911A JP 2013522911 A JP2013522911 A JP 2013522911A JP WO2013002283 A1 JPWO2013002283 A1 JP WO2013002283A1
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- Prior art keywords
- acid
- copper oxide
- etching solution
- etching
- copper
- Prior art date
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- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
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- C09K13/00—Etching, surface-brightening or pickling compositions
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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
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- G03F7/004—Photosensitive materials
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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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0041—Photosensitive materials providing an etching agent upon exposure
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
- G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
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- G—PHYSICS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
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- 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
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- C23F1/10—Etching compositions
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Abstract
Description
本発明のエッチング液のエッチング対象は銅の酸化物であり、例えば、熱反応型レジスト材料として銅の酸化物を主成分とする酸化銅含有層を用いてレーザー光で露光した場合に、露光・未露光部を選択的にエッチングする際に用いる。
図3は、膜厚20nmの酸化銅(II)膜を8重量%グリシン水溶液及び8重量%シュウ酸アンモニウム水溶液でそれぞれ溶解させた場合のエッチング時間と溶解速度の関係を示す図である。エッチング速度は、例えば以下の方法で求められる。ガラス上に膜厚20nmの酸化銅膜を製膜したものを複数用意する。次に、一定時間エッチング液を作用させる前後のそれぞれの膜内の銅含有量をX線光電子分光により求め、一定時間エッチング液を作用させたことによる溶解量を求める。エッチング時間と溶解量の関係をプロットし、その一次近似直線の傾きよりエッチング速度が求められる。図3から、アミノ酸であるグリシンは、キレート剤であるシュウ酸アンモニウムに比べて溶解速度が小さいことがわかる。すなわち、アミノ酸は比較的低いエッチング速度の領域においてエッチング速度の調整に有用であり、逆にキレート剤は比較的高いエッチング速度の領域においてエッチング速度の調整に有用である。
図4は、酸化銅(II)の熱重量測定結果を示す図である。酸化銅(II)の粉末に対して熱重量測定を行うと、1050℃において、酸化銅(II)の還元による吸熱が確認され(図4のDTA参照)、それに伴う酸素の放出に由来する重量の減少が観測される(図4のTG参照)。重量の減少割合から見積もって、酸化銅の価数は、2(加熱前)から、ほぼ1(加熱後)まで減少していることが分かる。この結果より、加熱によって酸化銅(II)が還元されて酸化数が減少し、酸化銅(I)を主成分とする含む銅の酸化物が生成することが分かる。なお、図4では価数1(酸化銅(I),CuO0.5)に減少後、再酸化が生じて価数1.5(CuO0.65)となっているように見えるが、後述するX線回折の結果では酸化銅(II)はほとんど観測されておらず、実質的には価数1の状態になっていると推定できる。
図6は、膜厚10nmの酸化銅(II)の膜を、3重量%のグリシン水溶液を用いて溶解させた場合と、同膜を露光により加熱して酸化銅(I)に変化させた後の膜を、同液を用いて溶解させた場合との、エッチング時間と溶解速度の関係を示す図である。図6より、3重量%のグリシン水溶液を作用させた場合、加熱変化後の酸化銅(I)は、変化前の酸化銅(II)に比べて約10倍の速度で溶解することがわかる。すなわち、このデータにより、アミノ酸水溶液を用いることで、酸化銅(II)と酸化銅(I)が混在した膜において、酸化銅(I)が選択的に溶解することがわかる。
50mmφのガラス平板基板上に、スパッタリング法を用いて、下記の条件にて酸化銅膜を成膜した。なお、成膜後の酸化銅膜の価数を、XPS測定から計算したところ、1.90を超えており、実質的に酸化銅の価数はIIと言える。
ターゲット:酸化銅(II)
電力(W):RF100
ガス種類:アルゴンと酸素の混合ガス(比率95:5)
圧力(Pa):0.1
膜厚(nm):20
露光用半導体レーザー波長:405nm
レンズ開口数:0.85
露光レーザーパワー:1〜10mW
送りピッチ:500nm
グリシン 1.2g
シュウ酸アンモニウム 1.2g
水 400g
pH 6.34
実施例1と同様の条件で成膜、露光した酸化銅を下記条件にて調製したエッチング液によってエッチングした。
グリシン 1.2g
シュウ酸アンモニウム 0.6g
水 400g
pH 6.15
実施例1と同様の条件で成膜、露光した酸化銅を下記条件にて調製したエッチング液によってエッチングした。
グリシン 1.2g
シュウ酸アンモニウム 0.4g
水 400g
pH 6.04
実施例1と同様の条件で成膜、露光した酸化銅を下記条件にて調製したエッチング液によってエッチングした。
グリシン 1.2g
シュウ酸アンモニウム 6g
水 400g
pH 6.36
実施例1と同様の条件で成膜、露光した酸化銅を、特許文献8に開示された、下記組成のエッチング液にてエッチングした。
グリシン4.5g
フッ化アンモニウム0.2g
1−ヒドロキシエチリデン−1,1−ジホスホン酸0.3g
ホスホン酸0.02g
プロピレングリコールモノメチルエーテル50g
水 400g
pH 2.58
実施例1と同様の条件で成膜、露光した酸化銅を、特許文献8に開示された、下記組成のエッチング液にてエッチングした。
シュウ酸4.5g
フッ化アンモニウム0.2g
1−ヒドロキシエチリデン−1,1−ジホスホン酸0.3g
ホスホン酸0.02g
プロピレングリコールモノメチルエーテル87.5g
水 400g
pH 2.73
Claims (13)
- 価数の異なる酸化銅を含有する酸化銅含有層から特定の価数の酸化銅を選択的に除去するための酸化銅のエッチング液であって、少なくともアミノ酸とキレート剤と水とを含み、アミノ酸の重量割合がキレート剤より多く、かつそのpHが3.5以上であることを特徴とするエッチング液。
- 前記アミノ酸が、アラニン、アルギニン、アスパラギン、アスパラギン酸、システイン、グルタミン、グルタミン酸、グリシン、ヒスチジン、イソロイシン、ロイシン、リジン、メチオニン、オルニチン、フェニルアラニン、セリン、トレオニン、トリプトファン、チロシン及びバリンからなる群より選択された少なくとも一種を含むことを特徴とする請求項1に記載のエッチング液。
- 前記アミノ酸が、グリシン、アラニン、メチオニン及びリジンからなる群より選択された少なくとも一種を含むことを特徴とする請求項1に記載のエッチング液。
- 前記アミノ酸が、グリシンであることを特徴とする請求項1に記載のエッチング液。
- 前記キレート剤が、酢酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、α,ω−ジアミン酢酸、α,ω−ジアミンコハク酸、α,ω−ジアミンプロピオン酸、1,2−ジアミノプロパン四酢酸、クエン酸、イソクエン酸、フマル酸、マレイン酸、グルタミン酸、リンゴ酸、酒石酸、バソクプロインジスルホン酸、及びそれらの塩、並びにアンモニア、ビピリジル、フェナントロリン及びこれらの誘導体からなる群より選択された少なくとも一種を含むことを特徴とする請求項1から4のいずれかに記載のエッチング液。
- 前記キレート剤が、シュウ酸、酢酸アンモニウム、シュウ酸アンモニウム、マロン酸アンモニウム、コハク酸アンモニウム、クエン酸、リンゴ酸、酒石酸、からなる群より選択された少なくとも一種を含むことを特徴とする請求項1から4のいずれかに記載のエッチング液。
- 前記キレート剤が、酢酸アンモニウム、シュウ酸アンモニウム、マロン酸アンモニウム及びコハク酸アンモニウムからなる群より選択された少なくとも一種を含むことを特徴とする請求項1から4のいずれかに記載のエッチング液。
- 前記キレート剤が、シュウ酸アンモニウムであることを特徴とする請求項1から4のいずれかに記載のエッチング液。
- エッチング液中の前記アミノ酸の割合が0.01重量%以上10重量%以下であることを特徴とする請求項1から請求項8のいずれかに記載のエッチング液。
- エッチング液中の前記キレート剤の割合が0.01重量%以上10重量%以下の範囲で前記記載のアミノ酸の割合以下であることを特徴とする請求項1から請求項9のいずれかに記載のエッチング液。
- 前記酸化銅含有層が、少なくとも熱分解された銅の酸化物を含む領域を有することを特徴とする請求項1から請求項10のいずれかに記載のエッチング液。
- 請求項1から請求項11のいずれかに記載のエッチング液を用いるエッチング方法であって、
銅の酸化物を含有する酸化銅含有層の銅の酸化物を熱分解する熱分解工程と、前記酸化銅含有層に前記エッチング液を供給し、前記酸化銅含有層から熱分解された銅の酸化物を除去するエッチング工程と、を含むことを特徴とするエッチング方法。 - 前記酸化銅含有層の熱分解は、前記酸化銅含有層にレーザー光を照射して行うことを特徴とする請求項12に記載のエッチング方法。
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