JP2022038823A - Method for producing composite structure and method for producing semiconductor device - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000004065 semiconductor Substances 0.000 title claims abstract description 13
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 114
- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 64
- 239000007864 aqueous solution Substances 0.000 claims abstract description 54
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 32
- 230000001678 irradiating effect Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 41
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 6
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- -1 for example Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- ZIQYWMNGCHHWLT-UHFFFAOYSA-K C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[W+4] Chemical compound C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[W+4] ZIQYWMNGCHHWLT-UHFFFAOYSA-K 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- MYYUWUVATCWCES-UHFFFAOYSA-L potassium;oxalate;titanium(4+);dihydrate Chemical compound O.O.[K+].[Ti+4].[O-]C(=O)C([O-])=O MYYUWUVATCWCES-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
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Abstract
Description
本発明は、窒化アルミニウム焼結体に金属層を備えた複合構造体の製造方法及び半導体装置の製造方法に関する。 The present invention relates to a method for manufacturing a composite structure having a metal layer on an aluminum nitride sintered body and a method for manufacturing a semiconductor device.
窒化アルミニウム（ＡｌＮ）は、６．２ｅＶの広いバンドギャップを有し、３２０Ｗ／ｍＫと高い熱伝導率を有し、電気機器の電気回路を形成する基材として注目されている。基材に電気回路を形成する材料としては、例えば銀ナノ粒子や銅ナノ粒子などの金属ナノ粒子が用いられている。 Aluminum nitride (AlN) has a wide bandgap of 6.2 eV, has a high thermal conductivity of 320 W / mK, and is attracting attention as a base material for forming an electric circuit of an electric device. As a material for forming an electric circuit on a base material, for example, metal nanoparticles such as silver nanoparticles and copper nanoparticles are used.
金属ナノ粒子は、例えば樹脂と混合されペーストとして、基材に塗布され、回路が形成される場合がある。また、金属ナノ粒子を用いることなく、回路を形成する金属塩を、水溶液又は有機溶液に混合し、金属イオンを含有する水溶液又は有機溶液を基材に塗布して金属塩の膜を形成する場合もある。 The metal nanoparticles may be mixed with a resin and applied as a paste to a substrate to form a circuit. Further, when a metal salt forming a circuit is mixed with an aqueous solution or an organic solution without using metal nanoparticles, and an aqueous solution or an organic solution containing metal ions is applied to a base material to form a metal salt film. There is also.
特許文献１には、ギ酸銅溶液を、インクジェットプリンタを用いて基板に塗布し、マイクロ波を照射して、銅トレースを形成する方法が開示されている。特許文献２には、ギ酸銅又はその水和物と、酢酸銅又はその水和物と、ジオール化合物と、ピぺリジン化合物と、有機溶剤と、を含有する銅膜形成用組成物が開示されている。 Patent Document 1 discloses a method of applying a copper formate solution to a substrate using an inkjet printer and irradiating it with microwaves to form a copper trace. Patent Document 2 discloses a composition for forming a copper film containing copper formate or a hydrate thereof, copper acetate or a hydrate thereof, a diol compound, a piperidine compound, and an organic solvent. ing.
しかしながら、金属イオンを含む水溶液を基材に塗布して金属層を形成する場合、基材の材質によっては、基材の表面の親水性が乏しく、金属イオンを含む水溶液を均一に塗布できず、均質な金属塩の膜が形成され難い場合がある。
そこで、窒化アルミニウム焼結体に金属塩の膜を備えた複合構造体の製造方法及び半導体装置の製造方法を提供することを目的とする。
However, when an aqueous solution containing metal ions is applied to a base material to form a metal layer, the hydrophilicity of the surface of the base material is poor depending on the material of the base material, and the aqueous solution containing metal ions cannot be uniformly applied. It may be difficult to form a uniform metal salt film.
Therefore, it is an object of the present invention to provide a method for manufacturing a composite structure in which a film of a metal salt is provided on an aluminum nitride sintered body and a method for manufacturing a semiconductor device.
本開示は、以下の態様を包含する。
本開示の第１態様は、窒化アルミニウム焼結体に、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で照射する工程と、前記光を照射した窒化アルミニウム焼結体に金属イオンを含む水溶液を塗布する工程を含む、窒化アルミニウム焼結体に金属塩の膜を備えた複合構造体の製造方法である。
The present disclosure includes the following aspects.
The first aspect of the present disclosure is a step of irradiating the aluminum nitride sintered body with light having an emission peak wavelength in the range of 497 nm or less at an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less, and the above-mentioned step. It is a method for manufacturing a composite structure in which a film of a metal salt is provided on an aluminum nitride sintered body, which comprises a step of applying an aqueous solution containing metal ions to the aluminum nitride sintered body irradiated with light.
本開示の第２態様は、前記複合構造体が基板であり、基板に電気回路を形成する工程を含む、半導体装置の製造方法である。 A second aspect of the present disclosure is a method for manufacturing a semiconductor device, wherein the composite structure is a substrate and includes a step of forming an electric circuit on the substrate.
上述の態様により、窒化アルミニウム焼結体に金属塩の膜を備えた複合構造体の製造方法及び半導体装置の製造方法を提供することができる。 According to the above-described aspect, it is possible to provide a method for manufacturing a composite structure in which a film of a metal salt is provided on an aluminum nitride sintered body and a method for manufacturing a semiconductor device.
以下、本開示に係る複合構造体の製造方法及び半導体装置の製造方法を実施形態に基づいて説明する。ただし、以下に示す実施形態は、本発明の技術思想を具体化するための例示であって、本発明は、以下の複合構造体の製造方法及び半導体装置の製造方法に限定されない。 Hereinafter, a method for manufacturing a composite structure and a method for manufacturing a semiconductor device according to the present disclosure will be described based on an embodiment. However, the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following method for manufacturing a composite structure and a method for manufacturing a semiconductor device.
複合構造体の製造方法
複合構造体の製造方法は、窒化アルミニウム焼結体に、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で照射する工程と、前記光を照射した窒化アルミニウム焼結体に金属イオンを含む水溶液を塗布する工程、を含み、窒化アルミニウム焼結体に金属塩の膜を備えた複合構造体を得る。
Manufacturing method of composite structure The manufacturing method of the composite structure is to apply light having an emission peak wavelength in the range of 497 nm or less to an aluminum nitride sintered body with an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less. A composite structure including a step of irradiating and a step of applying an aqueous solution containing metal ions to the aluminum nitride sintered body irradiated with light is obtained, and the aluminum nitride sintered body is provided with a film of a metal salt.
図１は、複合構造体の製造方法の一例を示すフローチャートである。複合構造体の製造方法は、窒化アルミニウム焼結体に４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射する光照射工程Ｓ１０２と、光を照射した窒化アルミニウム焼結体に金属イオンを含む水溶液を塗布する塗布工程Ｓ１０３を含む。図２は、複合構造体の製造方法の他の一例を示すフローチャートである。複合構造体の製造方法は、光照射工程Ｓ１０２の前に、窒化アルミニウム焼結体の表面を洗浄処理により前処理する前処理工程Ｓ１０１を含んでいてもよい。複合構造体の製造方法は、塗布工程Ｓ１０３の後に、金属イオンを含む水溶液を乾燥させて金属塩の膜を形成する乾燥工程Ｓ１０４を含んでいてもよい。さらに、複合構造体の製造方法は、乾燥工程Ｓ１０４の後に、金属塩の膜を熱処理又は金属塩の膜に光を照射して金属塩を分解させ、金属層を形成する金属層形成工程Ｓ１０５を含んでいてもよい。後述するように塗布工程Ｓ１０３と乾燥工程Ｓ１０４は、この順序で２回以上繰り返し行ってもよい。 FIG. 1 is a flowchart showing an example of a method for manufacturing a composite structure. The method for producing the composite structure includes a light irradiation step S102 of irradiating the aluminum nitride sintered body with light having an emission peak wavelength in the range of 497 nm or less, and an aqueous solution containing metal ions in the light-irradiated aluminum nitride sintered body. The coating step S103 for coating is included. FIG. 2 is a flowchart showing another example of the method for manufacturing the composite structure. The method for manufacturing the composite structure may include a pretreatment step S101 in which the surface of the aluminum nitride sintered body is pretreated by a cleaning treatment before the light irradiation step S102. The method for producing the composite structure may include a drying step S104 in which an aqueous solution containing metal ions is dried to form a film of a metal salt after the coating step S103. Further, as a method for producing the composite structure, after the drying step S104, a metal layer forming step S105 for forming a metal layer by heat-treating the metal salt film or irradiating the metal salt film with light to decompose the metal salt is performed. It may be included. As will be described later, the coating step S103 and the drying step S104 may be repeated twice or more in this order.
前処理工程
複合構造体の製造方法において、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射する前に、窒化アルミニウム焼結体を洗浄処理により前処理する前処理工程を含んでいてもよい。窒化アルミニウム焼結体の表面に有機物等が付着していると、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射した場合に、有機物の分解に光のエネルギーが使用され、後述する窒素とアルミニウムの結合が切断されにくくなる場合がある。窒化アルミニウム焼結体は、４９７ｎｍ以下の範囲に発光ピーク波長を有する光のエネルギーが、後述する窒素とアルミニウムの結合の切断に使用されるように、洗浄処理による前処理によって、窒化アルミニウム焼結体の表面に付着している有機物等を除去しておくことが好ましい。窒化アルミニウム焼結体の洗浄処理は、界面活性剤と脱イオン水を用いて洗浄した後、さらにエタノール等を用いて洗浄してもよい。
Pretreatment Step The method for producing a composite structure may include a pretreatment step of pretreating the aluminum nitride sintered body by a cleaning treatment before irradiating the light having an emission peak wavelength in the range of 497 nm or less. If organic matter or the like adheres to the surface of the aluminum nitride sintered body, the energy of light is used to decompose the organic matter when light having an emission peak wavelength is irradiated in the range of 497 nm or less, and nitrogen and aluminum described later are used. It may be difficult to break the bond. The aluminum nitride sintered body is an aluminum nitride sintered body by pretreatment by a cleaning treatment so that the energy of light having an emission peak wavelength in the range of 497 nm or less is used for breaking the bond between nitrogen and aluminum described later. It is preferable to remove organic substances and the like adhering to the surface of the aluminum. The aluminum nitride sintered body may be washed with a surfactant and deionized water, and then with ethanol or the like.
光照射工程
窒化アルミニウムは、比較的安定な物質であるため、窒化アルミニウム焼結体の表面に親水性基が吸着しにくく、親水性が低い。物体の表面の親水性は、物体の表面の水又は水溶液の濡れやすさを表し、物体の表面の親水性が低い場合は、水又は水溶液が濡れにくい。すなわち、物体の表面の親水性が低い場合は、撥水性が高く、物体の表面で水溶液がはじかれて水滴状の塊が形成され、水溶液を均一に塗布することができない。
Light irradiation step Since aluminum nitride is a relatively stable substance, hydrophilic groups are less likely to be adsorbed on the surface of the aluminum nitride sintered body, and the hydrophilicity is low. The hydrophilicity of the surface of the object represents the wettability of the water or the aqueous solution on the surface of the object, and when the hydrophilicity of the surface of the object is low, the water or the aqueous solution is difficult to get wet. That is, when the hydrophilicity of the surface of the object is low, the water repellency is high, the aqueous solution is repelled on the surface of the object to form a water droplet-like mass, and the aqueous solution cannot be uniformly applied.
物体の表面の親水性は、物体の表面に親水性基が存在することによって発現する。親水性基は、例えば水酸基、カルボキシル基、アミノ基等が挙げられる。水分子は、酸素原子と水素原子で構成され、水分子中で酸素原子側が負に帯電し、水素原子側が正に帯電する。帯電した水分子と、物体の表面に存在する親水性基が水素結合によって弱く結合することにより、親水性が発現する。 The hydrophilicity of the surface of an object is expressed by the presence of hydrophilic groups on the surface of the object. Examples of the hydrophilic group include a hydroxyl group, a carboxyl group, an amino group and the like. A water molecule is composed of an oxygen atom and a hydrogen atom, and the oxygen atom side is negatively charged and the hydrogen atom side is positively charged in the water molecule. Hydrophilicity is developed by weakly bonding the charged water molecule and the hydrophilic group existing on the surface of the object by hydrogen bonds.
窒素とアルミニウムの結合エネルギーは、２４０．５ｋＪ／ｍｏｌであり、このエネルギーに相当する光の波長に換算すると、４９７ｎｍである。４９７ｎｍ以下の範囲に発光ピーク波長を有する光を窒化アルミニウム焼結体に照射すると、窒素とアルミニウムの結合の一部を切断することができる。窒化アルミニウム焼結体の表面において、窒素とアルミニウムの結合の一部が切断されると、一部に格子欠陥等が生成され、物性が不安定となるため、窒化アルミニウムの表面が帯電し、親水性基が吸着されやすくなると推測される。窒化アルミニウム焼結体の表面に、４９７ｎｍ以下の範囲に発光ピーク波長を有する光が照射されると、窒化アルミニウム焼結体の表面の窒素とアルミニウムの結合の一部が切断され、親水性基が吸着されやすくなり、窒化アルミニウム焼結体の表面の親水性が高くなる。窒化アルミニウム焼結体の表面の親水性が高いと、窒化アルミニウム焼結体の表面が濡れやすくなり、金属イオンを含む水溶液を窒化アルミニウム焼結体の表面に均一に塗布することができ、均質な金属塩の膜を形成することができる。 The binding energy of nitrogen and aluminum is 240.5 kJ / mol, which is 497 nm when converted to the wavelength of light corresponding to this energy. When the aluminum nitride sintered body is irradiated with light having an emission peak wavelength in the range of 497 nm or less, a part of the bond between nitrogen and aluminum can be broken. When a part of the bond between nitrogen and aluminum is cut on the surface of the aluminum nitride sintered body, lattice defects and the like are generated in a part and the physical properties become unstable, so that the surface of the aluminum nitride becomes charged and hydrophilic. It is presumed that the sex group is easily adsorbed. When the surface of the aluminum nitride sintered body is irradiated with light having an emission peak wavelength in the range of 497 nm or less, a part of the bond between nitrogen and aluminum on the surface of the aluminum nitride sintered body is cut off, and a hydrophilic group is formed. It becomes easy to be adsorbed, and the hydrophilicity of the surface of the aluminum nitride sintered body becomes high. When the surface of the aluminum nitride sintered body is highly hydrophilic, the surface of the aluminum nitride sintered body becomes easy to get wet, and an aqueous solution containing metal ions can be uniformly applied to the surface of the aluminum nitride sintered body, which is homogeneous. A film of metal salt can be formed.
窒化アルミニウム焼結体は、窒化アルミニウム粉末を焼結して得られたものであってもよい。窒化アルミニウム粉末は、金属アルミニウムの粉末を窒素雰囲気中で燃焼合成させる燃焼合成法若しくは直接窒化法によって得られるものであってもよく、酸化アルミニウムの粉末を窒素中で加熱して還元させる還元窒化法によって得られるものであってもよい。窒化アルミニウム粉末は、有機アルミニウムとアンモニアの反応によって得られるものであってもよい。 The aluminum nitride sintered body may be obtained by sintering aluminum nitride powder. The aluminum nitride powder may be obtained by a combustion synthesis method in which metallic aluminum powder is burned and synthesized in a nitrogen atmosphere or a direct nitriding method, and a reduction nitriding method in which aluminum oxide powder is heated and reduced in nitrogen. It may be obtained by. The aluminum nitride powder may be obtained by the reaction of organoaluminum with ammonia.
窒化アルミニウム焼結体は、３次元構造を有していてもよい。窒化アルミニウム焼結体は、平板状の六面体構造であってもよく、例えば表面に凹凸構造を有する３次元構造を有していてもよい。窒化アルミニウム焼結体が３次元構造を有し、例えば、重力方向に対して平行な面を有する場合であっても、窒化アルミニウム焼結体の表面の親水性を高くすることができると、窒化アルミニウム焼結体の表面が濡れやすくなり、金属イオンを含む水溶液を塗布することによって、均質な金属塩の膜を形成しやすくなる。 The aluminum nitride sintered body may have a three-dimensional structure. The aluminum nitride sintered body may have a flat hexahedral structure, or may have, for example, a three-dimensional structure having a concavo-convex structure on the surface. Even when the aluminum nitride sintered body has a three-dimensional structure and has a surface parallel to the direction of gravity, for example, if the surface hydrophilicity of the aluminum nitride sintered body can be increased, the aluminum nitride sintered body is nitrided. The surface of the aluminum sintered body becomes easy to get wet, and by applying an aqueous solution containing metal ions, it becomes easy to form a uniform metal salt film.
４９７ｎｍ以下の範囲に発光ピーク波長を有する光は、１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で窒化アルミニウム焼結体に照射する。窒化アルミニウム焼結体に照射される４９７ｎｍ以下の範囲に発光ピーク波長を有する光のエネルギー密度が１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内であれば、窒素とアルミニウムの結合を切断して、窒化アルミニウム焼結体の表面を親水性基が吸着されやすくなり、親水性を高めることができる。４９７ｎｍ以下の範囲に発光ピーク波長を有する光のエネルギー密度が１０００ｍＪ／ｃｍ２を超えても、窒化アルミニウム焼結体の表面の窒素とアルミニウムの結合を切断することによって吸着される親水性基はそれほど増加しない。窒化アルミニウム焼結体に照射される４９７ｎｍ以下の範囲に発光ピーク波長を有する光のエネルギー密度は、１００ｍＪ／ｃｍ２以上９５０ｍＪ／ｃｍ２以下の範囲内でもよく、１２０ｍＪ／ｃｍ２以上９００ｍＪ／ｃｍ２以下の範囲内でもよい。 Light having an emission peak wavelength in the range of 497 nm or less irradiates the aluminum nitride sintered body with an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less. If the energy density of the light having an emission peak wavelength in the range of 497 nm or less irradiated to the aluminum nitride sintered body is in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less, the bond between nitrogen and aluminum is broken. , Hydrophilic groups are easily adsorbed on the surface of the aluminum nitride sintered body, and the hydrophilicity can be enhanced. Even if the energy density of light having an emission peak wavelength in the range of 497 nm or less exceeds 1000 mJ / cm 2 , the hydrophilic groups adsorbed by breaking the bond between nitrogen and aluminum on the surface of the aluminum nitride sintered body are not so much. Does not increase. The energy density of the light having an emission peak wavelength in the range of 497 nm or less irradiated to the aluminum nitride sintered body may be in the range of 100 mJ / cm 2 or more and 950 mJ / cm 2 or less, and 120 mJ / cm 2 or more and 900 mJ / cm 2 . It may be within the following range.
窒化アルミニウム焼結体に照射される光の発光ピーク波長の範囲は、窒素とアルミニウムの結合エネルギーを切断できる範囲であればよく、窒素とアルミニウムの結合エネルギーを切断できる波長範囲は４９７ｎｍ以下である。窒化アルミニウム焼結体に照射される光は、５ｎｍ以上４９７ｎｍ以下の範囲内に発光ピーク波長を有していてもよく、１０ｎｍ以上４５０ｎｍ以下の範囲内に発光ピーク波長を有していてもよく、４００ｎｍ以下の範囲内に発光ピーク波長を有していてもよい。 The range of the emission peak wavelength of the light irradiated to the aluminum nitride sintered body may be a range as long as it can cut the bond energy of nitrogen and aluminum, and the wavelength range of cutting the bond energy of nitrogen and aluminum is 497 nm or less. The light irradiated to the aluminum nitride sintered body may have an emission peak wavelength in the range of 5 nm or more and 497 nm or less, or may have an emission peak wavelength in the range of 10 nm or more and 450 nm or less. It may have an emission peak wavelength in the range of 400 nm or less.
４９７ｎｍ以下の範囲に発光ピーク波長を有する光を窒化アルミニウム焼結体に照射する時間は、光のエネルギー密度が１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内となる時間であればよい。４９７ｎｍ以下の範囲に発光ピーク波長を有する光を窒化アルミニウム焼結体に照射する時間は、０．００１秒以上６００秒以内でもよく、０．０１秒以上５００秒以内でもよく、０．１秒以上３００秒以内でもよい。 The time for irradiating the aluminum nitride sintered body with light having an emission peak wavelength in the range of 497 nm or less may be such that the energy density of the light is in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less. The time for irradiating the aluminum nitride sintered body with light having an emission peak wavelength in the range of 497 nm or less may be 0.001 seconds or more and 600 seconds or less, 0.01 seconds or more and 500 seconds or less, and 0.1 seconds or more. It may be within 300 seconds.
窒化アルミニウム焼結体には、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を、低圧水銀ランプを用いて照射してもよい。低圧水銀ランプは、水銀原子の波長２５４ｎｍの紫外線放射（共鳴線）を利用して紫外線光を照射する。４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射する光源としては、発光ダイオードを用いてもよく、エキシマランプを用いてもよい。 The aluminum nitride sintered body may be irradiated with light having an emission peak wavelength in the range of 497 nm or less by using a low-pressure mercury lamp. The low-pressure mercury lamp irradiates ultraviolet light by utilizing ultraviolet radiation (resonance line) having a wavelength of 254 nm of mercury atoms. As a light source for irradiating light having a emission peak wavelength in the range of 497 nm or less, a light emitting diode may be used or an excimer lamp may be used.
塗布工程
４９７ｎｍ以下の範囲に発光ピーク波長を有する光を１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で照射した窒化アルミニウム焼結体に、金属イオンを含む水溶液を塗布し、窒化アルミニウム焼結体に金属塩の膜を備えた複合構造体を形成する。４９７ｎｍ以下の範囲に発光ピーク波長を有する光を１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で照射した窒化アルミニウム焼結体は、窒化アルミニウム焼結体の表面が改質されて親水性が高くなっているため、窒化アルミニウム焼結体の表面が濡れやすく、金属イオンを含む水溶液を均一に塗布することができ、均質な金属塩の膜を形成することができる。
Coating step An aqueous solution containing metal ions is applied to an aluminum nitride sintered body irradiated with light having an emission peak wavelength in the range of 497 nm or less at an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less, and nitrided. A composite structure having a metal salt film is formed on the aluminum sintered body. The surface of the aluminum nitride sintered body is modified in the aluminum nitride sintered body obtained by irradiating light having an emission peak wavelength in the range of 497 nm or less with an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less. Since the hydrophilicity is high, the surface of the aluminum nitride sintered body is easily wetted, an aqueous solution containing metal ions can be uniformly applied, and a uniform metal salt film can be formed.
金属イオンを含む水溶液は、水溶性を有する金属塩を水に溶解することにより作製することができる。金属イオンの金属は、電気回路形成用の金属であることが好ましい。金属イオンの金属は、０℃における電気伝導率が１Ｓ／ｍ以上６５Ｓ／ｍ以下の範囲内の金属であることが好ましい。電気伝導率が１Ｓ／ｍ以上６５Ｓ／ｍ以下の範囲内の金属であれば、電気回路の形成に適した金属塩の膜を形成することができる。金属イオンの金属は、金、銀、銅、タングステン、チタン、パラジウム、モリブデン及びアルミニウムからなる群から選択される少なくとも１種であってもよく、金、銀、銅、タングステン及びチタンからなる群から選択される少なくとも１種であってもよい。水溶性を有する金属塩としては、例えば金属が銅の場合、ギ酸銅、酢酸銅、プロパン酸銅等のカルボン酸銅、水酸化銅等が挙げられる。例えば、金の場合、テトラクロロ金（ＩＩＩ）酸四水和物が挙げられる。銀の場合、硝酸銀、酢酸銀が挙げられる。タングステンの場合、クエン酸ナトリウムタングステン、タングステン酸カリウムが挙げられる。チタンの場合、ヘキサフルオロチタン（ＩＶ）酸カリウム、シュウ酸チタンカリウム二水和物が挙げられる。パラジウムの場合、テトラクロロパラジウム（ＩＩ）酸カリウム、ヘキサクロロパラジウム（ＩＶ）酸カリウムが挙げられる。モリブデンの場合、モリブデン（ＶＩ）酸アンモニウム四水和物、モリブデン酸リチウムが挙げられる。アルミニウムの場合、乳酸アルミニウム、硫酸アルミニウムが挙げられる。 An aqueous solution containing metal ions can be prepared by dissolving a water-soluble metal salt in water. The metal of the metal ion is preferably a metal for forming an electric circuit. The metal of the metal ion is preferably a metal having an electric conductivity in the range of 1 S / m or more and 65 S / m or less at 0 ° C. A metal salt film suitable for forming an electric circuit can be formed as long as the metal has an electric conductivity in the range of 1 S / m or more and 65 S / m or less. The metal of the metal ion may be at least one selected from the group consisting of gold, silver, copper, tungsten, titanium, palladium, molybdenum and aluminum, and may be from the group consisting of gold, silver, copper, tungsten and titanium. It may be at least one selected. Examples of the water-soluble metal salt include copper carboxylic acid such as copper formate, copper acetate and copper propanoate, and copper hydroxide when the metal is copper. For example, in the case of gold, tetrachloroauric acid (III) acid tetrahydrate can be mentioned. In the case of silver, silver nitrate and silver acetate can be mentioned. In the case of tungsten, sodium citrate tungsten and potassium tungstate can be mentioned. In the case of titanium, potassium hexafluorotitanium (IV) and potassium titanium oxalate dihydrate can be mentioned. In the case of palladium, examples thereof include potassium tetrachloropalladium (II) and potassium hexachloropalladium (IV). In the case of molybdenum, examples thereof include ammonium molybdenum (VI) tetrahydrate and lithium molybdate. In the case of aluminum, examples thereof include aluminum lactate and aluminum sulfate.
金属イオンを含む水溶液液中の金属イオンの濃度は、金属塩の膜を形成できる濃度であればよい。金属塩の濃度を高くすると乾燥後にち密な金属塩の膜が得られやすいため、金属塩の飽和溶液を使用することが望ましい。金属イオンの濃度が高すぎると、塗布時に金属塩が析出して均一な膜が得られないことがある。これを防ぐために濃度を調整してもよく、ギ酸銅の場合には、例えば、０．２ｍｏｌ／Ｌ以上０．６ｍｏｌ／Ｌ以下の範囲内とすることができる。金属イオンを含む水溶液の溶媒は、水、脱イオン水等を用いることができる。 The concentration of the metal ion in the aqueous solution containing the metal ion may be any concentration as long as it can form a film of the metal salt. It is desirable to use a saturated solution of the metal salt because a dense metal salt film can be easily obtained after drying when the concentration of the metal salt is increased. If the concentration of metal ions is too high, metal salts may precipitate during coating and a uniform film may not be obtained. In order to prevent this, the concentration may be adjusted, and in the case of copper formate, it can be, for example, in the range of 0.2 mol / L or more and 0.6 mol / L or less. As the solvent of the aqueous solution containing metal ions, water, deionized water or the like can be used.
金属イオンを含む水溶液を窒化アルミニウム焼結体に塗布する方法としては、ミストコート法、スプレーコート法、ディップ法、スピンコート法、フローコート法、カーテンコート法、ロールコート法、ナイフコート法、バーコート法、スリットコート法、スクリーン印刷法、グラビア印刷法、オフセット印刷法、インクジェット法、刷毛塗り等が挙げられる。窒化アルミニウム焼結体が３次元構造を有する場合、ミストコート法、スプレーコート法、又は、ディップコート法により金属イオンを含む水溶液を窒化アルミニウム焼結体に塗布することが好ましい。 As a method of applying an aqueous solution containing metal ions to an aluminum nitride sintered body, a mist coat method, a spray coat method, a dip method, a spin coat method, a flow coat method, a curtain coat method, a roll coat method, a knife coat method, and a bar Examples thereof include a coating method, a slit coating method, a screen printing method, a gravure printing method, an offset printing method, an inkjet method, and brush coating. When the aluminum nitride sintered body has a three-dimensional structure, it is preferable to apply an aqueous solution containing metal ions to the aluminum nitride sintered body by a mist coat method, a spray coat method, or a dip coat method.
窒化アルミニウム焼結体は、４９７ｎｍ以下の範囲に発光ピーク波長を有する光が１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で照射され、窒化アルミニウム焼結体の表面の親水性が高くなっているので、窒化アルミニウム焼結体の表面の濡れ性がよく、窒化アルミニウム焼結体の表面に均一に金属イオンを含む水溶液が塗布される。 The aluminum nitride sintered body is irradiated with light having an emission peak wavelength in the range of 497 nm or less with an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less, and the surface hydrophilicity of the aluminum nitride sintered body becomes high. Since the height is high, the surface of the aluminum nitride sintered body has good wettability, and an aqueous solution containing metal ions is uniformly applied to the surface of the aluminum nitride sintered body.
物体の表面の親水性又は疎水性は、物体の表面と水又は水溶液との接触角でも評価することができる。物体の表面と水又は水溶液との接触角が９０°未満であれば、濡れやすく、親水性である。物体の表面と水又は水溶液の接触角が９０°以上であると、濡れにくく、疎水性である。４９７ｎｍ以下の範囲に発光ピーク波長を有する光が１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で照射された後の窒化アルミニウム焼結体の表面と金属イオンを含む水溶液の接触角の上限値は、９０°未満であり、好ましくは８０°以下であり、より好ましくは６０°以下であり、さらに好ましくは５０°以下であり、４０°以下であってもよく、下限値は、２°以上であってもよい。４９７ｎｍ以下の範囲に発光ピーク波長を有する光が１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で照射された後の窒化アルミニウム焼結体の表面と水又は水溶液の接触角が９０°未満であれば、窒化アルミニウム焼結体の表面は親水性である。窒化アルミニウム焼結体の表面と水又は水溶液の接触角が小さくなるほど、窒化アルミニウム焼結体の表面の親水性が高くなる。 The hydrophilicity or hydrophobicity of the surface of an object can also be evaluated by the contact angle between the surface of the object and water or an aqueous solution. If the contact angle between the surface of the object and water or an aqueous solution is less than 90 °, it is easy to get wet and hydrophilic. When the contact angle between the surface of the object and water or an aqueous solution is 90 ° or more, it is difficult to get wet and is hydrophobic. Contact angle between the surface of the aluminum nitride sintered body and the aqueous solution containing metal ions after light having an emission peak wavelength in the range of 497 nm or less is irradiated with an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less. The upper limit value of is less than 90 °, preferably 80 ° or less, more preferably 60 ° or less, still more preferably 50 ° or less, and may be 40 ° or less, and the lower limit value is It may be 2 ° or more. The contact angle between the surface of the aluminum nitride sintered body and water or an aqueous solution is 90 after the light having an emission peak wavelength in the range of 497 nm or less is irradiated with an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less. If it is less than °, the surface of the aluminum nitride sintered body is hydrophilic. The smaller the contact angle between the surface of the aluminum nitride sintered body and water or an aqueous solution, the higher the hydrophilicity of the surface of the aluminum nitride sintered body.
乾燥工程
金属イオンを含む水溶液を窒化アルミニウム焼結体の表面に塗布した後、乾燥工程を含んでいてもよい。例えば、金属イオンを含む水溶液が均一に塗布された窒化アルミニウム焼結体を、４０℃以上１３０℃以下の温度範囲で、５分以上２４時間以内で乾燥し、均質な金属塩の膜を形成することができる。乾燥温度は、４０℃以上１３０℃以下の範囲内でもよく、５０℃以上１００℃以下の範囲内でもよい。乾燥温度が高すぎると、乾燥段階で金属塩が分解してしまうことがある。乾燥時間は、１０分以上１２時間以内でもよく、１５分以上１時間以内でもよい。乾燥は、減圧下、大気圧下で行ってもよく、０．０１ＭＰａ以上０．９ＭＰａ以下の加圧下で行ってもよい。送風することで効率よく乾燥することもできる。乾燥は、２０℃から３０℃程度の室温で大気雰囲気中に静置して自然乾燥を行ってもよい。
Drying step A drying step may be included after applying an aqueous solution containing metal ions to the surface of the aluminum nitride sintered body. For example, an aluminum nitride sintered body uniformly coated with an aqueous solution containing metal ions is dried in a temperature range of 40 ° C. or higher and 130 ° C. or lower within 5 minutes or more and 24 hours or less to form a uniform metal salt film. be able to. The drying temperature may be in the range of 40 ° C. or higher and 130 ° C. or lower, or may be in the range of 50 ° C. or higher and 100 ° C. or lower. If the drying temperature is too high, the metal salt may decompose during the drying stage. The drying time may be 10 minutes or more and 12 hours or less, or 15 minutes or more and 1 hour or less. Drying may be performed under reduced pressure and atmospheric pressure, or may be performed under pressure of 0.01 MPa or more and 0.9 MPa or less. It can also be dried efficiently by blowing air. For drying, it may be allowed to stand in an air atmosphere at a room temperature of about 20 ° C. to 30 ° C. for natural drying.
塗布工程と、乾燥工程は、この順序で２回以上繰り返して行ってもよく、３０回以下繰り返して行ってもよい。金属イオンを含む水溶液を塗布した窒化アルミニウム焼結体を乾燥し、窒化アルミニウム焼結体に金属塩の膜を備えた複合構造体が得られる。 The coating step and the drying step may be repeated twice or more in this order, or may be repeated 30 times or less. The aluminum nitride sintered body coated with the aqueous solution containing metal ions is dried to obtain a composite structure in which the aluminum nitride sintered body is provided with a film of a metal salt.
金属層形成工程
複合構造体の製造方法は、金属塩の膜を熱処理又は金属塩の膜に光を照射して金属塩を分解させ、金属層を形成する金属層形成工程を含んでいてもよい。窒化アルミニウム焼結体と金属塩の膜を備えた複合構造体を熱処理又は光照射することにより金属層を形成することができる。熱処理温度及び熱処理時間は金属塩が分解して金属層が形成される範囲で調整すればよい。また光照射のエネルギー密度及び時間は、金属塩が分解して金属層が形成される範囲で調整すればよい。
Metal layer forming step The method for producing a composite structure may include a metal layer forming step of heat-treating a metal salt film or irradiating a metal salt film with light to decompose the metal salt to form a metal layer. .. A metal layer can be formed by heat-treating or irradiating a composite structure provided with an aluminum nitride sintered body and a film of a metal salt. The heat treatment temperature and heat treatment time may be adjusted within the range in which the metal salt is decomposed and the metal layer is formed. Further, the energy density and time of light irradiation may be adjusted within the range in which the metal salt is decomposed and the metal layer is formed.
半導体装置の製造方法
窒化アルミニウム焼結体と金属層を含む複合構造体は、窒化アルミニウム焼結体と均質な金属塩の膜を含む複合構造体から形成されるため、例えば電気回路用の基板に用いることができる。
Manufacturing method of semiconductor device Since the composite structure including the aluminum nitride sintered body and the metal layer is formed from the composite structure containing the aluminum nitride sintered body and the uniform metal salt film, for example, it is used as a substrate for an electric circuit. Can be used.
窒化アルミニウム焼結体に形成された金属層に、例えばエッチングを施し、電気回路用のパターンを形成する工程を含んでいてもよい。例えば、金属層上に電気回路用のパターンの保護膜を形成し、エッチング液に浸漬し、露出している金属層をエッチングすることによって、窒化アルミニウム焼結体の金属層に電気回路用のパターンを形成することができる。電気回路が形成された複合構造体は、マザーボード用の配線基板、フリップチップ用の配線基板、パワー半導体素子搭載用の配線基板等に用いることができる。 The metal layer formed on the aluminum nitride sintered body may be subjected to, for example, etching to form a pattern for an electric circuit. For example, by forming a protective film for an electric circuit pattern on a metal layer, immersing it in an etching solution, and etching the exposed metal layer, a pattern for an electric circuit can be formed on the metal layer of the aluminum nitride sintered body. Can be formed. The composite structure in which the electric circuit is formed can be used as a wiring board for a motherboard, a wiring board for flip chips, a wiring board for mounting a power semiconductor element, and the like.
以下、本発明を実施例により具体的に説明する。本発明は、これらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples.
実施例１
前処理工程
縦５０．８ｍｍ×横５０．８ｍｍ×厚み０．２ｍｍの平板状の六面体構造を有する窒化アルミニウム焼結体（株式会社トクヤマ製）を用いた。窒化アルミニウム焼結体を界面活性剤と脱イオン水を用いて洗浄した。
光照射工程
次に、２５４ｎｍに発光ピーク波長を有する１１０Ｗの低圧水銀ランプを用いて、紫外線（ＵＶ）光を窒化アルミニウム焼結体に照射した。低圧水銀ランプと窒化アルミニウム焼結体の距離を２０ｍｍとした。窒化アルミニウム焼結体上の放射照度は５ｍＷ／ｃｍ２であった。窒化アルミニウム焼結体にＵＶ光を３０秒間照射した。窒化アルミニウム焼結体に３０秒間照射したＵＶ光のエネルギー密度は１５０ｍＪ／ｃｍ２であった。照射した光のエネルギー密度は、光源の放射照度から計算により求めた。
塗布工程
続いて窒化アルミニウム焼結体の表面に濃度０．５７６ｍｏｌ／Ｌのギ酸銅を含むギ酸銅水溶液を塗布し、接触角計（ＦＩＢＲＯ Ｓｙｓｔｅｍ ＡＢ社製、ＰＧ－Ｘ＋）を用いて、窒化アルミニウム焼結体とギ酸銅を含む水溶液の接触角を測定した。結果を表１に示す。
Example 1
Pretreatment Step An aluminum nitride sintered body (manufactured by Tokuyama Corporation) having a flat hexahedral structure having a length of 50.8 mm, a width of 50.8 mm, and a thickness of 0.2 mm was used. The aluminum nitride sintered body was washed with a surfactant and deionized water.
Light Irradiation Step Next, the aluminum nitride sintered body was irradiated with ultraviolet (UV) light using a 110 W low-pressure mercury lamp having an emission peak wavelength of 254 nm. The distance between the low-pressure mercury lamp and the aluminum nitride sintered body was set to 20 mm. The irradiance on the aluminum nitride sintered body was 5 mW / cm 2 . The aluminum nitride sintered body was irradiated with UV light for 30 seconds. The energy density of the UV light irradiated to the aluminum nitride sintered body for 30 seconds was 150 mJ / cm 2 . The energy density of the irradiated light was calculated from the irradiance of the light source.
Coating Step Subsequently, an aqueous solution of copper formate containing copper formate having a concentration of 0.576 mol / L is coated on the surface of the aluminum nitride sintered body, and aluminum nitride is used using a contact angle meter (FIBRO System AB, PG-X +). The contact angle between the sintered body and the aqueous solution containing copper nitride was measured. The results are shown in Table 1.
実施例２
光照射の時間を１８０秒に変更したこと以外は実施例１と同様に行った。結果を表１に示す。
Example 2
The procedure was the same as in Example 1 except that the light irradiation time was changed to 180 seconds. The results are shown in Table 1.
比較例１
実施例１と同様に窒化アルミニウム焼結体を界面活性剤と脱イオン水を用いて洗浄した。続いて、ＵＶ光の照射を行うことなく、実施例１と同様にしてギ酸銅水溶液を塗布し、接触角を測定した。結果を表１に示す。
Comparative Example 1
The aluminum nitride sintered body was washed with a surfactant and deionized water in the same manner as in Example 1. Subsequently, a copper formate aqueous solution was applied in the same manner as in Example 1 without irradiation with UV light, and the contact angle was measured. The results are shown in Table 1.
実施例１と実施例２において、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で照射した窒化アルミニウム焼結体の表面は、ギ酸銅水溶液との接触角が９０°未満となっており親水性を有していた。洗浄後光照射前の窒化アルミニウム焼結体の表面とギ酸銅水溶液の接触角は９１°であり、親水性を有していなかった。４９７ｎｍ以下の範囲に発光ピーク波長を有する光を１００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下の範囲内のエネルギー密度で照射した結果、窒化アルミニウム焼結体の表面が改質され、窒化アルミニウム焼結体の表面に親水性基が吸着されやすくなり、窒化アルミニウム焼結体の表面の親水性が高くなった。 In Examples 1 and 2, the surface of the aluminum nitride sintered body irradiated with light having an emission peak wavelength in the range of 497 nm or less with an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less is gilic acid. The contact angle with the copper aqueous solution was less than 90 °, and it was hydrophilic. The contact angle between the surface of the aluminum nitride sintered body and the copper formate aqueous solution after cleaning and before light irradiation was 91 °, and it did not have hydrophilicity. As a result of irradiating light having an emission peak wavelength in the range of 497 nm or less with an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less, the surface of the aluminum nitride sintered body is modified and the aluminum nitride sintered body is formed. The hydrophilic group was easily adsorbed on the surface of the aluminum nitride sintered body, and the surface of the aluminum nitride sintered body became more hydrophilic.
図３は、実施例１における４９７ｎｍ以下の範囲に発光ピーク波長を有する光を１５０ｍＪ／ｃｍ２のエネルギー密度で照射した後の窒化アルミニウム焼結体におけるギ酸銅水溶液の接触角を測定したときの写真である。図４は、実施例２における４９７ｎｍ以下の範囲に発光ピーク波長を有する光を９００ｍＪ／ｃｍ２のエネルギー密度で照射した後の窒化アルミニウム焼結体におけるギ酸銅水溶液の接触角を測定したときの写真である。図５は、実施例１における４９７ｎｍ以下の範囲に発光ピーク波長を有する光を１５０ｍＪ／ｃｍ２のエネルギー密度で照射した後の窒化アルミニウム焼結体にギ酸銅水溶液を塗布した状態の平面写真である。
図３から図５に示すように、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射した後の窒化アルミニウム焼結体の表面とギ酸銅水溶液の接触角は、９０°未満であり、窒化アルミニウム焼結体の表面は親水性を有していた。図５に示すように、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射した後の窒化アルミニウム焼結体の表面は、ギ酸銅水溶液の濡れ性がよく、ギ酸銅水溶液が均一に塗布されていた。ギ酸銅水溶液が均一に塗布できたことにより、例えばこれら窒化アルミニウム焼結体を乾燥することで、窒化アルミニウム焼結体に均質な金属塩の膜の形成が可能と考えられる。
FIG. 3 is a photograph of the contact angle of the copper formate aqueous solution in the aluminum nitride sintered body after being irradiated with light having an emission peak wavelength in the range of 497 nm or less in Example 1 at an energy density of 150 mJ / cm 2 . Is. FIG. 4 is a photograph of the contact angle of the copper formate aqueous solution in the aluminum nitride sintered body after being irradiated with light having an emission peak wavelength in the range of 497 nm or less in Example 2 at an energy density of 900 mJ / cm 2 . Is. FIG. 5 is a plan photograph of an aluminum nitride sintered body coated with an aqueous solution of copper formate after being irradiated with light having an emission peak wavelength in the range of 497 nm or less in Example 1 at an energy density of 150 mJ / cm 2 . ..
As shown in FIGS. 3 to 5, the contact angle between the surface of the aluminum nitride sintered body and the aqueous copper formate after irradiation with light having an emission peak wavelength in the range of 497 nm or less is less than 90 °, and aluminum nitride is used. The surface of the sintered body was hydrophilic. As shown in FIG. 5, the surface of the aluminum nitride sintered body after being irradiated with light having an emission peak wavelength in the range of 497 nm or less has good wettability of the copper formate aqueous solution, and the copper formate aqueous solution is uniformly applied. rice field. It is considered that the uniform application of the copper formate aqueous solution makes it possible to form a uniform metal salt film on the aluminum nitride sintered body, for example, by drying these aluminum nitride sintered bodies.
図６は、比較例１における４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射していない窒化アルミニウム焼結体におけるギ酸銅水溶液の接触角を測定したときの写真である。図７は、比較例１における４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射していない窒化アルミニウム焼結体にギ酸銅水溶液を塗布した状態の平面写真である。
図６及び図７に示すように、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射していない窒化アルミニウム焼結体の表面とギ酸銅水溶液の接触角は、９０°を超えており、窒化アルミニウム焼結体の表面は親水性を有していなかった。図７に示すように、４９７ｎｍ以下の範囲に発光ピーク波長を有する光を照射していない窒化アルミニウム焼結体の表面は、ギ酸銅水溶液をはじき、水滴状の塊となり、ギ酸銅水溶液が均一に塗布されていなかった。
FIG. 6 is a photograph of Comparative Example 1 in which the contact angle of the copper formate aqueous solution in the aluminum nitride sintered body not irradiated with light having an emission peak wavelength in the range of 497 nm or less was measured. FIG. 7 is a plan photograph of the aluminum nitride sintered body not irradiated with light having an emission peak wavelength in the range of 497 nm or less in Comparative Example 1 in which an aqueous solution of copper formate is applied.
As shown in FIGS. 6 and 7, the contact angle between the surface of the aluminum nitride sintered body not irradiated with light having an emission peak wavelength in the range of 497 nm or less and the aqueous copper formate solution exceeds 90 °, and the nitriding The surface of the aluminum sintered body did not have hydrophilicity. As shown in FIG. 7, the surface of the aluminum nitride sintered body that has not been irradiated with light having an emission peak wavelength in the range of 497 nm or less repels the copper formate aqueous solution to form a water droplet-like mass, and the copper formate aqueous solution becomes uniform. It was not applied.
本形態にかかる製造方法によって得られた複合構造体は、半導体装置の回路基板に用いることができる。本形態にかかる製造方法によって得られた複合構造体は、マザーボード用、フリップチップ用、又はパワー半導体素子搭載用の配線基板に用いることができる。 The composite structure obtained by the manufacturing method according to this embodiment can be used for a circuit board of a semiconductor device. The composite structure obtained by the manufacturing method according to this embodiment can be used for a wiring board for a motherboard, a flip chip, or a power semiconductor element.
Claims (9)
前記光を照射した窒化アルミニウム焼結体に金属イオンを含む水溶液を塗布する工程を含む、窒化アルミニウム焼結体に金属塩の膜を備えた複合構造体の製造方法。 A step of irradiating the aluminum nitride sintered body with light having an emission peak wavelength in the range of 497 nm or less with an energy density in the range of 100 mJ / cm 2 or more and 1000 mJ / cm 2 or less.
A method for producing a composite structure in which an aluminum nitride sintered body is provided with a metal salt film, which comprises a step of applying an aqueous solution containing metal ions to the aluminum nitride sintered body irradiated with light.
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