JP5884122B1 - 塩化銅の製造方法 - Google Patents
塩化銅の製造方法 Download PDFInfo
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- JP5884122B1 JP5884122B1 JP2015528480A JP2015528480A JP5884122B1 JP 5884122 B1 JP5884122 B1 JP 5884122B1 JP 2015528480 A JP2015528480 A JP 2015528480A JP 2015528480 A JP2015528480 A JP 2015528480A JP 5884122 B1 JP5884122 B1 JP 5884122B1
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 146
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 77
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 239000012535 impurity Substances 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 28
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 28
- 239000008151 electrolyte solution Substances 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 238000003487 electrochemical reaction Methods 0.000 claims description 23
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 15
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052785 arsenic Inorganic materials 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052745 lead Inorganic materials 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 229910052716 thallium Inorganic materials 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 238000005192 partition Methods 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940077239 chlorous acid Drugs 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims 2
- 125000002524 organometallic group Chemical group 0.000 abstract description 10
- 239000010408 film Substances 0.000 description 54
- 238000005229 chemical vapour deposition Methods 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000002243 precursor Substances 0.000 description 11
- 238000000231 atomic layer deposition Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 229960003280 cupric chloride Drugs 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 229940045803 cuprous chloride Drugs 0.000 description 6
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000003011 anion exchange membrane Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- -1 hydroxide ions Chemical class 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UBKGYAAMWMYRIG-UHFFFAOYSA-H [Cu](F)(F)(F)(F)(F)F Chemical compound [Cu](F)(F)(F)(F)(F)F UBKGYAAMWMYRIG-UHFFFAOYSA-H 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/05—Chlorides
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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- H—ELECTRICITY
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- 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
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- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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Abstract
Description
図1に示す装置を用いて、6N―Cuを原料アノードおよびカソードとし、希塩酸系電解液で電気化学反応を行った。カソード周囲をカソードボックスで覆い、カソードボックスはアノードに対向する面には陰イオン交換膜(隔膜)を貼り、アノードから溶出する6N−Cuがカソードに電着することを防ぐようにしながら、アノード上に塩化銅が析出するようにした。電解液のpHは1.5に調整しながら電解液温25℃で電気化学反応を行った。このとき、電解槽中の電解液のpHは、電解槽内でほぼ一様となっており、pH値の監視はアノード側の電解液(アノライト)で行ない、アノード表面に析出した析出物をアノードに振動を加えることにより電解液中に落下させた。落下した析出物を取り出して水洗、乾燥し、塩化銅(I)の粉体を得た。得られた粉体中の塩化銅(I)の純度は99.9999質量%であった。更に、得られた塩化銅(I)中の不純物含有量を、ICP質量分析(ICP−MS)法を用いて分析した。不純物の分析結果(単位はすべて「重量(wt)ppm」)を表1に示す。尚、表1において、不等号「<」は、ICP−MS法の検出限界値未満であることを意味し、本明細書の表2、3においても同様のことを意味する。
6N―Cuを原料アノードおよびカソードとし、希塩酸系電解液で電気化学反応を行った。カソード周囲をカソードボックスで覆い、該カソードボックスはアノード板に対向する面には陰イオン交換膜(隔膜)を貼り、アノードから溶出する6N−Cuがカソードに電着することを防ぐようにしながら、アノード上に塩化銅が析出するようにした。電解液のpHを9に調整しながら電解液温25℃で電気化学反応を行った。このとき、電解槽中の電解液のpHは、電解槽内でほぼ一様となっており、pH値の監視はアノード側のアノライトで行ない、電気化学反応によりアノード表面に析出した塩化銅(II)を含む電解溶液を取り出し、ろ過してろ物を水洗、乾燥させて、塩化銅(II)結晶の粉体を得た。得られた粉体中の塩化銅(II)の純度は99.9999質量%であった。更に、得られた粉体中の不純物含有量をICP質量分析装置を用いて分析した。不純物分析結果(単位はすべて「重量(wt)ppm」)を表2に示す。
実施例1において、電解液中に落下した塩化銅(I)を取り出して、塩酸と過酸化水素水からなる溶液に溶かして塩化銅溶液とし、真空下(10.1kPa=0.1atm)で250℃に加熱して、蒸発乾固して、加熱処理物を得た。この加熱処理物をXRD法によって価数分析したところ、塩化銅(II)が得られていることが分かった。また、得られた粉体中の不純物含有量を、ICP質量分析装置を用いて分析した結果を表3に示す。
実施例1において、電解液中に落下した塩化銅(I)を取り出して、塩酸と次亜塩素酸(HClO)からなる溶液に溶かして塩化銅溶液とし、塩素ガス雰囲気下(バランスガスとして窒素を98%含み、Cl2濃度として2%濃度の塩素ガスを使用して)、300℃に加熱して、蒸発乾固して、加熱処理物を得た。この加熱処理物をXRD法によって価数分析したところ、実施例3と同様に、本法によって、塩化銅(I)は十分に塩化銅(II)になっていることが確認できた。また、得られた粉体中の不純物含有量も実施例3と同程度であり、Agが0.38wtppmと検出され、他の元素については検出限界値未満で、6N以上の純度であった。
実施例1で得られた1価の塩化銅を用いてCVD原料としてアミジネート系プレカーサを作製した。得られたCVD原料を用いてSi基板上にCu膜を成膜して、チャンバ内に水素ガスを供給した場合と、水素ガスとアルゴンガスとの混合ガスを供給した場合について、得られたCu薄膜の表面性状を評価した。Si基板としては、長さ50mm、幅50mmの正方形状のSi基板を反応室内に配置して、Si基板の中心部の温度を温度センサで計測した。結果を表4に示す。
表5は、実施例6として実施例5の条件3で得られたCVD膜の膜厚と抵抗率の関係を、比較例1として市販のアミジネート系プレカーサ(塩化銅純度4N)を使用して得られた銅配線膜の膜厚と抵抗値の比較を示している。実施例5の銅配線膜の抵抗率は、160℃において、銅配線の膜厚が10〜200nmのとき、(1.7〜5.0)×10-8Ωmであり、比較例1の市販のアミジネート系プレカーサ(塩化銅純度4N)を使用して得られた銅配線膜の抵抗値より低い抵抗率が達成されている。また参考例1として、実施例5で作製された銅配線膜の16℃における抵抗率と、さらに参考例2として市販のアミジネート系プレカーサ(塩化銅純度4N)を使用して得られた銅配線膜の16℃における抵抗値を示す。16℃においても従来例に比べて低い抵抗値を実現できており、160℃においても従来例に比べて抵抗値を低く抑えられていることがわかる。
2…アノード
3…カソード
10a、10b…電解液
30…カソードボックス
31…陰イオン交換膜(隔膜)
32…循環ライン
33…カソライト槽
34…循環ポンプ
Claims (7)
- カソードとアノードとの間に隔壁を設け、原料アノードとして純度6N以上の純銅を使用し、塩酸系電解液中で電気化学反応を行い、アノードの表面上に析出した塩化物を取り出して、水洗して乾燥させることにより、純度6N以上で、且つAgの含有量が0.5wtppm以下の塩化銅を製造する塩化銅の製造方法。
- カソードとアノードとの間に隔壁を設け、原料アノードとして純度6N以上の純銅を使用し、塩酸系電解液中で電気化学反応を行い、アノードの表面上に析出した塩化物を取り出して、水洗して乾燥させることにより、純度6N以上で、且つNa、Mg、Ti、Cr、Mn、Fe、Co、Ni、Zn、As、Ag、Cd、In、Sn、Tl、Pbの群から選ばれる1種以上の不純物の含有量の合計が1.0wtppm以下の塩化銅を製造する塩化銅の製造方法。
- 前記電気化学反応において、電解液のpHを1〜3に調整して塩化銅(I)を製造することを含む請求項1又は2に記載の塩化銅の製造方法。
- 前記電気化学反応において、電解液のpHを9〜10に調整して塩化銅(II)を製造することを含む請求項1又は2に記載の塩化銅の製造方法。
- 前記電気化学反応によって作製された塩化銅(I)を酸化剤の存在下で酸に溶かし、加熱して蒸発乾固することにより、塩化銅(II)を製造することを含む請求項3に記載の塩化銅の製造方法。
- 前記塩化銅(I)を真空中、もしくは不活性ガス雰囲気中、もしくは大気中、もしくは塩素ガス雰囲気中で、200〜300℃で加熱することを含む請求項5に記載の塩化銅の製造方法。
- 前記酸が塩酸であり、前記酸化剤が過酸化水素(H2O2)もしくは次亜塩素酸(HClO)、亜塩素酸(HClO2)、塩素酸(HClO3)、過塩素酸(HClO4)のいずれか1以上の酸化剤からなる溶液であることを特徴とする請求項5又は6に記載の塩化銅の製造方法。
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