TWI605274B - Silver reflective film, light reflective member, and method of manufacturing light reflective member - Google Patents
Silver reflective film, light reflective member, and method of manufacturing light reflective member Download PDFInfo
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- TWI605274B TWI605274B TW102136286A TW102136286A TWI605274B TW I605274 B TWI605274 B TW I605274B TW 102136286 A TW102136286 A TW 102136286A TW 102136286 A TW102136286 A TW 102136286A TW I605274 B TWI605274 B TW I605274B
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- reflective film
- alloy
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 178
- 229910052709 silver Inorganic materials 0.000 title claims description 178
- 239000004332 silver Substances 0.000 title claims description 178
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000007747 plating Methods 0.000 claims description 77
- 239000000758 substrate Substances 0.000 claims description 77
- 239000013078 crystal Substances 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 26
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 24
- 230000003746 surface roughness Effects 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910000531 Co alloy Inorganic materials 0.000 claims description 8
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 115
- 238000010438 heat treatment Methods 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000001887 electron backscatter diffraction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910001152 Bi alloy Inorganic materials 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 229910001370 Se alloy Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- CCXYPVYRAOXCHB-UHFFFAOYSA-N bismuth silver Chemical compound [Ag].[Bi] CCXYPVYRAOXCHB-UHFFFAOYSA-N 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- KRRRBSZQCHDZMP-UHFFFAOYSA-N selanylidenesilver Chemical compound [Ag]=[Se] KRRRBSZQCHDZMP-UHFFFAOYSA-N 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- VDMJCVUEUHKGOY-JXMROGBWSA-N (1e)-4-fluoro-n-hydroxybenzenecarboximidoyl chloride Chemical compound O\N=C(\Cl)C1=CC=C(F)C=C1 VDMJCVUEUHKGOY-JXMROGBWSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910000691 Re alloy Inorganic materials 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 description 1
- QMTXMMSHFDUPLF-UHFFFAOYSA-N [Ag].[Re] Chemical compound [Ag].[Re] QMTXMMSHFDUPLF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- LGFYIAWZICUNLK-UHFFFAOYSA-N antimony silver Chemical compound [Ag].[Sb] LGFYIAWZICUNLK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/08—Mirrors; Reflectors
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
- G02B5/085—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/64—Heat extraction or cooling elements
- H01L33/647—Heat extraction or cooling elements the elements conducting electric current to or from the semiconductor body
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroplating Methods And Accessories (AREA)
- Optical Elements Other Than Lenses (AREA)
- Led Device Packages (AREA)
Description
本發明係關於一種由銀或銀合金構成之銀反射膜、以其作為被膜之引線框架等光反射構件及該光反射構件之製造方法。 The present invention relates to a silver reflective film made of silver or a silver alloy, a light reflecting member such as a lead frame as a film, and a method of manufacturing the light reflecting member.
銀反射膜由於具有在可見光區域之反射率高的特性，故被廣泛使用於LED用之引線框架等光反射構件(以下，亦稱為反射構件)。被使用於引線框架等之銀反射膜大多為對基材進行鍍敷或濺鍍而形成。 Since the silver reflective film has a high reflectance in the visible light region, it is widely used as a light reflecting member such as a lead frame for LEDs (hereinafter also referred to as a reflecting member). Many silver reflective films used for lead frames and the like are formed by plating or sputtering a substrate.
例如，專利文獻1中記載之技術係藉由濺鍍而形成銀合金反射膜。濺鍍具有可形成具有高均勻性之膜的優點，但製造成本高，生產性低。該專利文獻1中，記載有一種關於反射器用銀合金反射膜之技術，該反射器用銀合金反射膜即使在加熱環境下，表面平滑性亦優異且顯示出高反射率。於該方法中，成膜方法為濺鍍，表面粗糙度為Ra=2.0nm以下。 For example, the technique described in Patent Document 1 forms a silver alloy reflective film by sputtering. Sputtering has the advantage of being able to form a film having high uniformity, but is expensive to manufacture and low in productivity. Patent Document 1 describes a technique for a silver alloy reflective film for a reflector, which is excellent in surface smoothness and exhibits high reflectance even in a heated environment. In this method, the film formation method is sputtering, and the surface roughness is Ra = 2.0 nm or less.
專利文獻2中記載有一種關於在可見光低波長側之反射率高，且耐久性優異之可見光反射構件的技術。其係由成形於基板之銀薄膜與形成於上述銀薄膜上之氮化矽保護膜構成的反射構件，銀薄膜係以(111)面或(200)面作為主要面方位。 Patent Document 2 describes a technique of a visible light reflecting member having high reflectance on a low-wavelength side of visible light and excellent durability. This is a reflection member composed of a silver thin film formed on a substrate and a tantalum nitride protective film formed on the silver thin film, and the silver thin film has a (111) plane or a (200) plane as a main plane orientation.
專利文獻3中則記載有一種關於如下銀反射膜之技術，該銀反射膜其最表面之結晶粒徑在0.5μm以上30μm以下之範圍內，銀鍍敷層具有1μm以上之膜厚，基底材料由銅形成，基底材料之表面粗糙度為0.5μm以上，且對波長400nm之光的反射率為90%以上。 Patent Document 3 describes a technique for a silver reflective film having a crystal grain size on the outermost surface of 0.5 μm or more and 30 μm or less, and a silver plating layer having a film thickness of 1 μm or more, and a base material. It is formed of copper, and the base material has a surface roughness of 0.5 μm or more and a reflectance of 90% or more for light having a wavelength of 400 nm.
然而，作為將銀反射膜用於引線框架等光反射構件時的重要 問題之一，可舉銀反射膜之耐熱性的問題。銀反射膜雖然顯示出高反射率，但有反射率會因熱而發生變化之缺點。例如，於引線框架等光反射構件中，當將銀反射膜用於LED用基板時會暴露於焊接或線接合等之加熱環境。因此，耐熱性可謂重要物性之一。然而，銀反射膜之熱歷程與反射率之關係複雜，至今未弄清明確之機制，而且一般而言，反射率具有因加熱而下降之傾向。因此，期望開發一種在加熱前後亦顯示良好反射率之銀反射膜。並且，近年來銀反射膜亦被指出會有因常溫時效而軟化之問題。因此，亦要求銀反射膜之硬度不易經時變化。 However, it is important as a silver reflective film for use in a light reflecting member such as a lead frame. One of the problems is the problem of the heat resistance of the silver reflective film. Although the silver reflective film exhibits high reflectance, there is a disadvantage that the reflectance changes due to heat. For example, in a light reflection member such as a lead frame, when a silver reflective film is used for a substrate for an LED, it is exposed to a heating environment such as soldering or wire bonding. Therefore, heat resistance is one of the important physical properties. However, the relationship between the thermal history of the silver reflective film and the reflectance is complicated, and the clear mechanism has not yet been clarified, and in general, the reflectance tends to decrease due to heating. Therefore, it is desired to develop a silver reflective film which also exhibits good reflectance before and after heating. Moreover, in recent years, the silver reflective film has also been pointed out to have a problem of softening due to room temperature aging. Therefore, it is also required that the hardness of the silver reflective film is not easily changed with time.
[專利文獻1]日本專利特開2005-029849號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-029849
[專利文獻2]日本專利特開2007-058194號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-058194
[專利文獻3]日本專利第4367457號說明書 [Patent Document 3] Japanese Patent No. 4367457
因此，本發明之課題在於提供一種反射率高、於加熱前後反射率亦不易變化且不易在常溫軟化之銀反射膜。並且，本發明之課題在於提供一種使用該銀反射膜作為被膜之光反射構件。又，本發明之課題在於以低成本且生產性良好地提供此種銀反射膜及光反射構件。進而，本發明之課題在於藉由鍍敷法提供具有耐熱性良好之鍍銀反射膜與導電性基材之光反射構件，及其製造方法。 Therefore, an object of the present invention is to provide a silver reflective film which has a high reflectance and which does not easily change in reflectance before and after heating and which is not easily softened at room temperature. Further, an object of the present invention is to provide a light reflecting member using the silver reflective film as a film. Further, an object of the present invention is to provide such a silver reflective film and a light reflecting member at low cost and with good productivity. Further, an object of the present invention is to provide a light-reflecting member having a silver-plated reflective film having good heat resistance and a conductive substrate by a plating method, and a method for producing the same.
本發明人等有鑒於上述背景技術之問題而進行潛心研究後，結果發現：使銀反射膜之銀結晶的配向方向以(100)配向為主，且使面內存在顯示(221)配向之區域，藉此可使耐熱性提高等。並且發現：可不利用濺鍍而以鍍敷法解決該等課題。 The inventors of the present invention conducted intensive studies in view of the problems of the above-described background art, and as a result, found that the alignment direction of the silver crystal of the silver reflective film is mainly aligned by (100), and the area where the surface is displayed (221) is present in the surface. Thereby, heat resistance can be improved and the like. It has also been found that these problems can be solved by plating without using sputtering.
本發明係基於該等見解而完成者。 The present invention has been completed based on these findings.
即，根據本發明，提供以下手段。 That is, according to the present invention, the following means are provided.
<1>一種銀反射膜，係由銀或銀合金構成，其特徵在於：於上述銀反射膜之表面，上述銀反射膜之結晶之(100)面配向於上述銀反射膜之反射面法線方向的區域有50%以上，且存在上述銀反射膜之結晶之(221)面配向於上述銀反射膜之反射面法線方向的區域。 <1> A silver reflective film comprising silver or a silver alloy, wherein a surface of the silver reflective film is aligned on a surface of the silver reflective film by a (100) plane of the silver reflective film The region in the direction is 50% or more, and the (221) plane in which the crystal of the silver reflective film is present is aligned in the normal direction of the reflecting surface of the silver reflecting film.
<2>如<1>記載之銀反射膜，其中，於上述銀反射膜表面，上述銀反射膜之結晶之(221)面配向於上述銀反射膜之反射面法線方向的區域有10%以上。 The silver reflective film of the above-mentioned silver reflective film, wherein the (221) plane of the crystal of the silver reflective film is aligned with the normal direction of the reflecting surface of the silver reflecting film by 10%. the above.
<3>如<1>或<2>記載之銀反射膜，其中，於上述銀反射膜表面，在上述銀反射膜之反射面法線方向上，與上述銀反射膜之結晶之(100)配向接觸的重合晶界Σ 3每單位面積之長度為0.4μm/μm2以上。 <3> The silver reflective film according to <1>, wherein the surface of the silver reflective film is crystallized with the silver reflective film in a direction normal to a reflection surface of the silver reflective film. The length of the coincident grain boundary Σ 3 of the alignment contact is 0.4 μm/μm 2 or more per unit area.
<4>一種光反射構件，在導電性基材上將<1>至<3>中任一項所記載之銀反射膜作為被膜。 <4> A light-reflecting member, wherein the silver reflective film according to any one of <1> to <3> is used as a film on the conductive substrate.
<5>如<4>記載之光反射構件，其中，上述導電性基材之表面粗糙度Ry為0.5μm以下。 <5> The light-reflecting member according to <4>, wherein the conductive substrate has a surface roughness Ry of 0.5 μm or less.
<6>如<4>或<5>記載之光反射構件，其中，於上述導電性基材與上述銀反射膜之間，設有以選自由鎳、鎳合金、鈷、鈷合金、銅、及銅合金組成之群中之金屬或合金構成的至少1層中間層。 The light-reflecting member of the above-mentioned electroconductive base material and the said silver reflective film are selected from nickel, nickel alloy, cobalt, cobalt alloy, copper, and And at least one intermediate layer composed of a metal or an alloy in a group of copper alloy compositions.
<7>一種光反射構件之製造方法，係藉由對導電性基材實施鍍敷處理，而將由銀或銀合金構成之銀反射膜製成皮膜，其特徵在於：於上述鍍敷處理中使上述基材搖晃。 <7> A method for producing a light-reflecting member, wherein a silver reflective film made of silver or a silver alloy is formed by a plating treatment on a conductive substrate, and is characterized in that the plating treatment is performed. The above substrate was shaken.
<8>如<7>記載之光反射構件之製造方法，其中，藉由對上述導電性基材實施鍍敷處理，而設置以選自由鎳、鎳合金、鈷、鈷合金、銅、及銅合金組成之群中之金屬或合金構成的至少1層中間層，並藉由對上述中間層實施鍍敷處理，而將由銀或銀合金構成之銀反射膜製成皮膜。 <8> The method for producing a light-reflecting member according to <7>, wherein the conductive substrate is subjected to a plating treatment selected from the group consisting of nickel, a nickel alloy, cobalt, a cobalt alloy, copper, and copper. At least one intermediate layer composed of a metal or an alloy in a group of alloy compositions, and a silver reflective film made of silver or a silver alloy is formed into a film by performing a plating treatment on the intermediate layer.
<9>如<7>或<8>記載之光反射構件之製造方法，其中，以振幅1 ~10mm、振動頻率10~100Hz進行搖晃。 <9> A method of manufacturing a light-reflecting member according to <7> or <8>, wherein the amplitude is 1 Shake for ~10mm and vibration frequency of 10~100Hz.
本發明之銀反射膜於300~800nm之波段顯示良好之反射率，尤其是於450~600nm之區域具有90%以上之反射率。並且，本發明之銀反射膜即使於200℃進行2小時加熱後，亦同樣地可於450~600nm之區域維持90%以上之反射率，耐熱性優異。該銀反射膜可藉由電鍍而以相對較低之成本，生產性良好地提供。並且，本發明可藉由鍍敷法而提供具有耐熱性良好之鍍銀反射膜及導電性基材的光反射構件及LED用基板。 The silver reflective film of the present invention exhibits a good reflectance in the wavelength range of 300 to 800 nm, and particularly has a reflectance of 90% or more in the region of 450 to 600 nm. Further, the silver reflective film of the present invention can maintain a reflectance of 90% or more in a region of 450 to 600 nm in the same manner even after heating at 200 ° C for 2 hours, and is excellent in heat resistance. The silver reflective film can be provided with good productivity by electroplating at a relatively low cost. Further, in the present invention, a light-reflecting member and a substrate for LED having a silver-plated reflective film and a conductive substrate having excellent heat resistance can be provided by a plating method.
本發明之上述及其他特徵及優點可由下述記載而清楚得知。 The above and other features and advantages of the invention will be apparent from the description.
本發明之銀反射膜可提供如下光反射構件，該光反射構件係於導電性基材上之最表面具有形成為由銀或銀合金構成之鍍敷層且反射率經提高的反射層。 The silver reflective film of the present invention can provide a light reflecting member which is a reflective layer having a plating layer formed of silver or a silver alloy and having a high reflectance on the outermost surface of the conductive substrate.
用於本發明之銀反射膜及光反射構件中之反射層的銀或銀合金，係以選自由銀、銀-錫合金、銀-銦合金、銀-銠合金、銀-釕合金、銀-金合金、銀-鈀合金、銀-鎳合金、銀-硒合金、銀-銻合金、及銀-鉑合金組成之群中的材料構成。上述之中，尤其是就反射率提高之觀點而言，較佳為銀、銀-錫合金、銀-銦合金、銀-鈀合金、銀-硒合金、或銀-銻合金。藉由將此種銀或銀合金用於銀反射膜，可獲得反射率良好且生產性佳之銀反射膜、與具有該銀反射膜而形成之引線框架及LED用基板等光反射構件。 The silver or silver alloy used for the reflective layer in the silver reflective film and the light-reflecting member of the present invention is selected from the group consisting of silver, silver-tin alloy, silver-indium alloy, silver-antimony alloy, silver-bismuth alloy, silver- A material composition of a group consisting of a gold alloy, a silver-palladium alloy, a silver-nickel alloy, a silver-selenium alloy, a silver-bismuth alloy, and a silver-platinum alloy. Among the above, in particular, from the viewpoint of improving the reflectance, silver, a silver-tin alloy, a silver-indium alloy, a silver-palladium alloy, a silver-selenium alloy, or a silver-rhenium alloy is preferable. By using such a silver or silver alloy for the silver reflective film, a silver reflective film having good reflectance and excellent productivity, a light-reflecting member such as a lead frame formed of the silver reflective film, and a substrate for LED can be obtained.
又，本發明之光反射構件中，關於由銀或銀合金構成之反射層的厚度(銀反射膜的厚度)並無特別限定。該反射層之厚度，例如藉由 將下限值設為0.5μm以上，可使反射率穩定地提高。又，藉由形成該反射層厚，而於製成半導體裝置用引線框架之情形時，可抑制因後續步驟即線接合及利用樹脂或玻璃進行密封等中的加熱所導致之劣化。如果於反射層之厚度過薄時(例如0.1μm)，將使得會因加熱發生變色之導電性基材容易露出。因此，為了更加穩定地防止由加熱或加工所致之變色，反射層之厚度較佳為0.5μm以上，更佳為1.0μm以上。另一方面，就削減貴金屬銀或抑制鍍敷加工費等觀點而言，該反射層之厚度上限值較佳為30μm以下，更佳為10μm以下，再更佳為5μm以下。 Further, in the light reflecting member of the present invention, the thickness of the reflecting layer made of silver or a silver alloy (the thickness of the silver reflecting film) is not particularly limited. The thickness of the reflective layer, for example by When the lower limit is 0.5 μm or more, the reflectance can be stably improved. Further, when the thickness of the reflective layer is formed, it is possible to suppress deterioration due to heating in the subsequent step, that is, wire bonding and sealing by resin or glass, in the case of forming a lead frame for a semiconductor device. If the thickness of the reflective layer is too thin (for example, 0.1 μm), the conductive substrate which is discolored by heating is easily exposed. Therefore, in order to more stably prevent discoloration caused by heating or processing, the thickness of the reflective layer is preferably 0.5 μm or more, and more preferably 1.0 μm or more. On the other hand, the upper limit of the thickness of the reflective layer is preferably 30 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less from the viewpoint of reducing the amount of precious metal silver or suppressing the plating processing cost.
於該光反射構件中，為了利用銀或銀合金鍍敷達成於可見光區域具有高反射率之銀反射膜，藉由使用平滑之基材及光澤劑，並適當地控制鍍敷條件，而使反射層之表面織構的配向性具有規則性，藉此可進行更高反射率化。 In the light-reflecting member, in order to achieve a silver reflective film having high reflectance in a visible light region by silver or silver alloy plating, reflection is performed by using a smooth substrate and a gloss agent, and appropriately controlling plating conditions. The alignment of the surface texture of the layer is regular, whereby higher reflectance can be achieved.
所謂平滑之基材，係指具有以表面粗糙度計Ry=0.5μm以下之特性者。導電性基材表面之表面粗糙度Ry較佳為0.3μm以下。導電性基材表面之表面粗糙度Ry之下限值並無特別限制，通常為0.05μm以上。 The smooth substrate refers to a property having a surface roughness of Ry = 0.5 μm or less. The surface roughness Ry of the surface of the conductive substrate is preferably 0.3 μm or less. The lower limit of the surface roughness Ry of the surface of the conductive substrate is not particularly limited, and is usually 0.05 μm or more.
此處，所謂表面粗糙度Ry，係指JIS B0601：1994規定之最大高度，其於現在之標準中相當於JIS B0601：2013規定之輪廓曲線要素之高度Zt。 Here, the surface roughness Ry refers to the maximum height specified by JIS B0601:1994, which corresponds to the height Zt of the contour curve element defined by JIS B0601:2013 in the current standard.
作為光澤劑，可使用鍍敷處理時所使用之通常的光澤劑，例如亞硒酸、硒氰酸鉀等Se系光澤劑或穩定劑、界面活性劑等。光澤劑之添加量較佳為10~30ml/L。 As the glossing agent, a usual brightening agent used in the plating treatment, for example, a Se-based brightening agent such as selenite or potassium selenocyanate, a stabilizer, a surfactant, or the like can be used. The amount of the gloss agent added is preferably 10 to 30 ml/L.
關於鍍敷條件之詳細內容，於稍後敍述。 Details of the plating conditions will be described later.
並且，根據本發明之光反射構件，不僅可於近紫外線區域即波長340~400nm，亦可於可見光區域即波長400~800nm中具有接近銀反射率之物理理論值的值。 Further, the light-reflecting member according to the present invention may have a value close to the physical theoretical value of the silver reflectance in the near-ultraviolet region, that is, the wavelength of 340 to 400 nm, or in the visible light region, that is, the wavelength of 400 to 800 nm.
又，本發明之光反射構件中由銀或銀合金構成之反射層(銀 反射膜)至少形成於有助於光之反射的部分(亦即，例如於引線框架或光半導體裝置中，至少會將光半導體元件所發出之光反射的區域)之最表面即可。於其他部分，反射層可設或亦可不設，又，即便形成有反射層以外之層，就反射率之觀點而言亦無特別問題。 Further, in the light reflecting member of the present invention, a reflective layer composed of silver or a silver alloy (silver The reflective film may be formed at least on the outermost surface of a portion that contributes to light reflection (that is, a region that reflects at least light emitted from the optical semiconductor element, for example, in a lead frame or an optical semiconductor device). In other portions, the reflective layer may or may not be provided, and even if a layer other than the reflective layer is formed, there is no particular problem in terms of reflectance.
又，關於本發明之光反射構件之導電性基材的材料，並無特別限制，例如可使用銅或銅合金、鐵或鐵合金、或者鋁或鋁合金。藉由選擇該等材料作為導電性基材，可提供反射率特性良好且易於形成反射層或中間層之皮膜、亦有助於降低成本的光反射構件(亦即，LED用基板，以及引線框架)。又，將該等金屬或合金作為導電性基材之引線框架，散熱特性優異，可經由引線框架將發光體發光時產生之熱能順利地釋放至外部，而可預見發光元件的長壽命化及長期之反射率特性的穩定化。此取決於導電性基材之導電率，以IACS(International Annealed Copper Standard)計較佳為至少有10%以上，更佳為50%以上。 Further, the material of the conductive substrate of the light-reflecting member of the present invention is not particularly limited, and for example, copper or a copper alloy, iron or an iron alloy, or aluminum or an aluminum alloy can be used. By selecting these materials as the conductive substrate, it is possible to provide a light-reflecting member (that is, a substrate for an LED, and a lead frame) which has good reflectance characteristics and is easy to form a film of a reflective layer or an intermediate layer, and also contributes to cost reduction. ). Further, the metal or alloy is used as the lead frame of the conductive substrate, and the heat dissipation property is excellent, and the heat energy generated when the illuminator emits light can be smoothly released to the outside through the lead frame, and the long life and long-term of the light-emitting element can be expected. The stabilization of the reflectance characteristics. This depends on the conductivity of the conductive substrate, and is preferably at least 10% or more, more preferably 50% or more, based on IACS (International Annealed Copper Standard).
又，於使用有本發明之光反射構件的光反射構件(例如，引線框架)，亦可於導電性基材與由銀或銀合金構成的反射層之間，設置以選自由鎳、鎳合金、鈷、鈷合金、銅、及銅合金組成之群中之金屬或合金構成的至少1層中間層。中間層例如藉由鍍敷而較佳地形成。 Further, a light reflecting member (for example, a lead frame) using the light reflecting member of the present invention may be disposed between the conductive substrate and the reflective layer composed of silver or a silver alloy, selected from the group consisting of nickel and nickel alloys. At least one intermediate layer composed of a metal or an alloy of a group consisting of cobalt, cobalt alloy, copper, and copper alloy. The intermediate layer is preferably formed, for example, by plating.
例如，於使用有鐵系導電性基材之情形，由於材料之導熱率相對較低，故藉由設置銅或銅合金層作為中間層，而可在不損害反射率下，提高散熱性。並且，作為上述中間層之為銅或銅合金層的鍍敷層，由於亦有助於提高鍍敷密合性，故可防止因發光元件發光時之發熱所導致的密合性劣化。 For example, in the case of using an iron-based conductive substrate, since the thermal conductivity of the material is relatively low, by providing a copper or copper alloy layer as an intermediate layer, heat dissipation can be improved without impairing the reflectance. Further, since the plating layer which is the copper or copper alloy layer of the intermediate layer contributes to the improvement of the plating adhesion, it is possible to prevent deterioration of adhesion due to heat generation when the light-emitting element emits light.
於使用銅或銅合金作為導電性基材之情形，為了抑制因發光元件發光時之發熱所導致之導電性基材成分向反射層擴散，設置鎳、鎳合金、鈷、或鈷合金之中間層作為中間層是有效的。 In the case where copper or a copper alloy is used as the conductive substrate, an intermediate layer of nickel, a nickel alloy, cobalt, or a cobalt alloy is provided in order to suppress diffusion of the conductive substrate component to the reflective layer due to heat generation during light emission of the light-emitting element. It is effective as an intermediate layer.
該等中間層之厚度於本發明中並無特別限定，較佳為0.025~2.0μm之範圍，更佳為0.2~1.0μm之範圍。 The thickness of the intermediate layer is not particularly limited in the present invention, and is preferably in the range of 0.025 to 2.0 μm, more preferably in the range of 0.2 to 1.0 μm.
又，為了於引線框架中提高導電性基材與反射層之密合性，較佳使用銅或銅合金作為構成中間層之材質。並且，亦可於鍍銅(Cu)後實施鍍鎳(Ni)等，而將由2層構成之中間層作為反射層之基底。 Further, in order to improve the adhesion between the conductive substrate and the reflective layer in the lead frame, copper or a copper alloy is preferably used as the material constituting the intermediate layer. Further, nickel plating (Ni) or the like may be performed after copper plating (Cu), and an intermediate layer composed of two layers may be used as a base of the reflective layer.
關於上述中間層之使用，LED用基板之情形亦相同。 Regarding the use of the above intermediate layer, the case of the LED substrate is also the same.
本發明中之反射層(銀反射膜)之結晶方位的分析，係使用EBSD法。所謂EBSD，係Electron BackScatter Diffraction(電子背向散射繞射)之簡稱，為一種利用掃描電子顯微鏡(Scanning Electron Microscope：SEM)內對試樣照射電子束時產生之反射電子菊池線繞射(菊池圖案)的結晶方位分析技術。本發明中，對包含200個以上結晶粒之80μm×200μm之試樣面積以0.2μm之步進進行掃描來分析方位。再者，電子束係以來自掃描電子顯微鏡之鎢絲的熱電子作為產生源。作為EBSD法之測定裝置，使用TSL Solutions股份有限公司製造之OIM5.0(商品名)。 The analysis of the crystal orientation of the reflective layer (silver reflective film) in the present invention uses the EBSD method. The so-called EBSD, referred to as Electron BackScatter Diffraction, is a kind of reflected electron Kikuchi line diffraction generated by irradiating an electron beam on a sample in a scanning electron microscope (SEM) (Kikuchi pattern) Crystal orientation analysis technique. In the present invention, a sample area of 80 μm × 200 μm containing 200 or more crystal grains is scanned at a step of 0.2 μm to analyze the orientation. Further, the electron beam system uses hot electrons from a tungsten wire of a scanning electron microscope as a generation source. As the measuring device of the EBSD method, OIM 5.0 (trade name) manufactured by TSL Solutions Co., Ltd. was used.
本發明中，於銀反射膜之表面，上述銀反射膜之結晶之(100)面配向於銀反射膜之反射面法線方向的區域存在50%以上。且，於銀反射膜之表面，存在上述銀反射膜之結晶之(221)面配向於上述銀反射膜之反射面法線方向的區域。(100)面配向之區域為50%以上，較佳為60%以上。該值較佳為90%以下。 In the present invention, on the surface of the silver reflective film, the (100) plane of the crystal of the silver reflective film is aligned with 50% or more in the normal direction of the reflecting surface of the silver reflecting film. Further, on the surface of the silver reflective film, the (221) plane of the crystal of the silver reflective film is aligned with the normal direction of the reflecting surface of the silver reflecting film. The area of the (100) face alignment is 50% or more, preferably 60% or more. This value is preferably 90% or less.
本說明書中，所謂「上述銀反射膜之結晶之(100)面配向於銀反射膜之反射面法線方向的區域」，係指於銀反射膜之反射面表面，銀或銀合金母相之結晶的<100>方向朝向反射面法線方向的區域。亦即，係指銀或銀合金之(100)面朝向反射膜表面的區域。再者，容許±15°以內之偏差(反射面表面之法線方向與<100>方向之交叉角度為15°以內)。此種 區域以一定比率存在於銀反射膜之整個反射面表面。再者，關於區域之比率的計算，為方便起見將利用EBSD法之測定區域簡便地記作該「區域」而進行評價。如上所述，以80μm×200μm作為最小單位區域進行計算。 In the present specification, the "region in which the (100) plane of the crystal of the silver reflective film is aligned with the normal direction of the reflecting surface of the silver reflecting film" means the surface of the reflecting surface of the silver reflecting film, and the silver or silver alloy mother phase. The <100> direction of the crystal faces the area in the normal direction of the reflecting surface. That is, the area where the (100) face of the silver or silver alloy faces the surface of the reflective film. Furthermore, the deviation within ±15° is allowed (the angle between the normal direction of the surface of the reflecting surface and the <100> direction is within 15°). Such The region exists in a certain ratio on the entire reflective surface of the silver reflective film. In addition, regarding the calculation of the ratio of the area, the measurement area by the EBSD method is simply referred to as the "region" for the sake of convenience. As described above, the calculation was performed with 80 μm × 200 μm as the minimum unit area.
於本發明中，發現若以上述方式控制反射膜之結晶配向，則可獲得反射率高之銀膜。認為其原因在於：因銀膜之(100)配向有50%以上，故表面之平滑性較以往高。 In the present invention, it has been found that when the crystal alignment of the reflective film is controlled in the above manner, a silver film having a high reflectance can be obtained. The reason is considered to be that since the (100) alignment of the silver film is 50% or more, the smoothness of the surface is higher than in the past.
又，本發明中，於銀反射膜之表面，較佳為上述銀反射膜之結晶之(221)面配向於銀反射膜之反射面法線方向的區域存在10%以上。更佳為20%以上。該值之上限雖無特別限制，但為30%以下。 Further, in the present invention, in the surface of the silver reflective film, it is preferable that the (221) plane of the crystal of the silver reflective film is aligned in the normal direction of the reflecting surface of the silver reflecting film by 10% or more. More preferably 20% or more. The upper limit of the value is not particularly limited, but is 30% or less.
並且，本發明之特徵在於：上述銀反射膜之結晶之(100)面配向於銀反射膜之反射面法線方向的區域有50%以上，且存在上述銀反射膜之結晶之(221)面配向於上述銀反射膜之反射面法線方向的區域。藉此，即便是進行加熱之情形，由於(221)面配向於銀反射膜之反射面法線方向的結晶會防止(100)面配向之結晶粒再結晶或粗大化，故可提高耐熱性。認為此亦具有防止銀反射膜因常溫時效而軟化的效果。 Further, the present invention is characterized in that the (100) plane of the crystal of the silver reflective film has a region in the normal direction of the reflecting surface of the silver reflecting film of 50% or more, and the (221) surface of the crystal of the silver reflecting film exists. A region that is oriented in the normal direction of the reflecting surface of the silver reflective film. Therefore, even in the case of heating, since the (221) surface is aligned with the crystal in the normal direction of the reflecting surface of the silver reflecting film, the crystal grains of the (100) surface alignment are prevented from being recrystallized or coarsened, so that heat resistance can be improved. It is considered that this also has an effect of preventing the silver reflective film from softening due to room temperature aging.
並且，關於本發明中之反射層(銀反射膜)，於銀反射膜表面，在銀反射膜之反射面法線方向上，與上述銀反射膜之結晶之(100)配向接觸的重合晶界Σ 3每單位面積之長度較佳為0.4μm/μm2以上，更佳為0.5μm/μm2以上。該值之上限值並無特別限制，通常為2.0μm/μm2以下。 Further, in the reflective layer (silver reflective film) of the present invention, on the surface of the silver reflective film, in the normal direction of the reflecting surface of the silver reflecting film, the coincident grain boundary of the (100) alignment of the crystal of the silver reflecting film The length per unit area of Σ 3 is preferably 0.4 μm/μm 2 or more, more preferably 0.5 μm/μm 2 or more. The upper limit of the value is not particularly limited, but is usually 2.0 μm/μm 2 or less.
此處，所謂重合晶界，即幾何學上整合性高之特殊晶界，被定義為重合晶格點密度之倒數的Σ值越小，意味著其整合性越高。其中，已知重合晶界Σ 3於晶界中之規則性之混亂小，晶界能量低。尤其是於組織內促進應力緩和之缺陷少，故耐熱性更為優異。再者，重合晶界Σ 3亦已知為雙晶。 Here, the so-called coincidence grain boundary, that is, the special grain boundary with high geometric integration, is defined as the smaller the Σ value of the reciprocal of the coincident lattice point density, which means that the integration is higher. Among them, it is known that the regularity of the grain boundary Σ 3 in the grain boundary is small, and the grain boundary energy is low. In particular, since the defects which promote stress relaxation in the tissue are small, heat resistance is further excellent. Further, the coincident grain boundary Σ 3 is also known as a twin crystal.
重合晶界Σ 3相當於(100)面配向於反射面法線方向之結晶、與(221)面配向於反射面法線方向之結晶的晶界。亦即，存在一定量之重合晶界Σ 3，意指存在一定量(100)面配向之結晶粒與(221)面配向之結晶粒接觸的區域。如之前所說明，本發明中，(221)面配向之存在由於會防止(100)面配向之結晶粒再結晶及/或粗大化，故較佳為該等結晶粒接觸。為了可定量地掌握，重合晶界Σ 3每單位面積之長度的總量係成為一個指標。 The superposition grain boundary Σ 3 corresponds to a crystal grain in which the (100) plane is aligned with the crystal in the normal direction of the reflecting surface and the (221) plane is aligned with the crystal in the normal direction of the reflecting surface. That is, there is a certain amount of coincident grain boundary Σ 3, which means that there is a region where a certain amount of (100) plane-aligned crystal grains are in contact with (221) surface-aligned crystal grains. As described above, in the present invention, since the presence of the (221) surface alignment is such that the crystal grains of the (100) plane alignment are prevented from being recrystallized and/or coarsened, it is preferred that the crystal grains are in contact. In order to be quantitatively grasped, the total amount of the length of the grain boundary Σ 3 per unit area becomes an index.
重合晶界Σ 3之分析係使用EDAX TSL公司製造之軟體「Orientation Imaging Microscopy v5」(商品名)，藉由CSL(Coincidence Site Lattice boundary)分析而進行。重合晶界Σ 3例如為相鄰粒子以<111>之旋轉軸為基礎具有60°旋轉角之關係的晶界。因此，使用該軟體，根據鄰接之晶界的方位關係分析相當於重合晶界Σ 3之晶界。並且，對測定範圍中之壓延面的總晶界長及重合晶界Σ 3進行測定，將(重合晶界Σ 3之長度)/(總晶界長)×100(%)定義為重合晶界Σ 3之比率(百分率)。再者，於使用該軟體之測定時，將相鄰像素具有15°以上傾斜(偏差)之情形判斷為結晶晶界。 The analysis of the coincidence grain boundary Σ 3 was carried out by using CSL (Coincidence Site Lattice boundary) analysis using the software "Orientation Imaging Microscopy v5" (trade name) manufactured by EDAX TSL. The coincident grain boundary Σ 3 is, for example, a grain boundary having a relationship of a rotation angle of 60° on the basis of the rotation axis of <111>. Therefore, using the soft body, the grain boundary corresponding to the grain boundary Σ 3 is analyzed based on the orientation relationship of the adjacent grain boundaries. Further, the total grain boundary length and the coincidence grain boundary Σ 3 of the rolled surface in the measurement range are measured, and (the length of the coincident grain boundary Σ 3) / (total grain boundary length) × 100 (%) is defined as a coincident grain boundary. Σ 3 ratio (percentage). Further, in the measurement using the soft body, the case where the adjacent pixels have an inclination (deviation) of 15 or more is determined as the crystal grain boundary.
於本發明之光反射構件的銀反射膜中，由於存在一定量(100)面配向之結晶粒與(221)面配向之結晶粒接觸的區域，故銀反射膜之銀或銀合金不易因常溫時效而軟化。可認為此係基於防止(100)面配向之結晶粒再結晶及/或粗大化。本發明之光反射構件之銀反射膜的硬度，以努氏硬度(Hk)計較佳為100Hk以上。更佳為105Hk以上，再更佳為110Hk以上。又，作為不易因常溫時效而軟化之標準，經過30天(30天×24小時)後之硬度的變化率以努氏硬度之變化率計較佳為15%以下。更佳為10%以下，再更佳為8%以下。 In the silver reflective film of the light-reflecting member of the present invention, since a certain amount of (100) surface-aligned crystal grains are in contact with the (221) surface-aligned crystal grains, the silver or silver alloy of the silver reflective film is not easily exposed to normal temperature. Timeliness and softening. This is considered to be based on prevention of recrystallization and/or coarsening of crystal grains of the (100) plane alignment. The hardness of the silver reflective film of the light-reflecting member of the present invention is preferably 100 Hk or more in terms of Knoop hardness (Hk). More preferably, it is 105 Hk or more, and even more preferably 110 Hk or more. Moreover, as a standard which is hard to soften by normal temperature aging, the rate of change of hardness after 30 days (30 days x 24 hours) is preferably 15% or less in terms of a change rate of Knoop hardness. More preferably, it is 10% or less, and even more preferably 8% or less.
此處，努氏硬度之變化率，以[{初期努氏硬度(Hk)-經過30天後之努氏硬度(Hk)}/初期努氏硬度(Hk)]×100(%)表示。 Here, the rate of change of Knoop hardness is expressed by [{initial Knoop hardness (Hk) - Knoop hardness (Hk) after 30 days} / initial Knoop hardness (Hk)] × 100 (%).
說明本發明之光反射構件的製造方法。 A method of manufacturing the light reflecting member of the present invention will be described.
本發明之光反射構件可藉由如下方式進行製造：對導電性基材實施鍍敷處理，藉此形成由銀或銀合金構成之銀反射膜(反射層)作為皮膜。此處，可於上述鍍敷處理中使上述基材搖晃。關於搖晃之條件，較佳為以振幅1~10mm、振動頻率10~100Hz使導電性基材或鍍敷液本身搖晃。關於搖晃之條件，更佳為以振幅2~8mm、振動頻率20~80Hz使導電性基材搖晃。於銀或銀合金鍍浴中，較佳添加上述光澤劑。 The light-reflecting member of the present invention can be produced by subjecting a conductive substrate to a plating treatment, thereby forming a silver reflective film (reflective layer) composed of silver or a silver alloy as a film. Here, the base material may be shaken in the plating treatment described above. The shaking condition is preferably such that the conductive substrate or the plating solution itself is shaken with an amplitude of 1 to 10 mm and a vibration frequency of 10 to 100 Hz. Regarding the shaking condition, it is more preferable to shake the conductive substrate with an amplitude of 2 to 8 mm and a vibration frequency of 20 to 80 Hz. In the silver or silver alloy plating bath, the above brightener is preferably added.
並且，關於本發明之光反射構件，作為其一實施形態，亦可藉由如下方式進行製造：藉由對上述導電性基材實施鍍敷處理，而於上述基材上設置以選自由鎳、鎳合金、鈷、鈷合金、銅、及銅合金組成之群中之金屬或合金構成的至少一層中間層，並藉由對上述中間層實施銀或銀合金鍍敷處理，而設置由上述銀或銀合金構成之銀反射膜作為中間層上之皮膜。 Further, the light-reflecting member of the present invention may be manufactured as follows: by subjecting the conductive substrate to a plating treatment, the substrate is provided with a material selected from the group consisting of nickel, At least one intermediate layer composed of a metal or an alloy of a group consisting of a nickel alloy, a cobalt alloy, a cobalt alloy, a copper alloy, and a copper alloy, and is provided with silver or a silver alloy plating treatment on the intermediate layer, and is provided by the above silver or A silver reflective film composed of a silver alloy serves as a film on the intermediate layer.
本發明中，結晶方位之控制係藉由在鍍敷中使基材等搖晃而進行。本發明人等發現：藉由一面以振幅1~10mm、振動頻率10~100Hz使基材或鍍敷液搖晃，一面進行銀或銀合金鍍敷，可適當地輕易控制反射層(銀反射膜)之結晶方位。雖然振動頻率亦取決於與振幅之平衡，但若振動頻率過高，則基材與電極間會過於靠近，因而使得鍍敷厚度變得不均勻，且(100)面配向之比率亦會減小，導致反射率降低。又，亦有鍍敷液飛濺等危險性，故而期望搖晃係於上述範圍內進行操作。若搖晃之振動頻率過低，則會有(100)面及(221)面配向之操作困難而無法進行充分控制之情形。 In the present invention, the control of the crystal orientation is carried out by shaking a substrate or the like during plating. The present inventors have found that by irradiating a substrate or a plating solution with an amplitude of 1 to 10 mm and a vibration frequency of 10 to 100 Hz, silver or silver alloy plating can appropriately control the reflective layer (silver reflective film). Crystal orientation. Although the vibration frequency is also dependent on the balance with the amplitude, if the vibration frequency is too high, the substrate and the electrode will be too close together, so that the plating thickness becomes uneven, and the ratio of the (100) plane alignment is also reduced. , causing a decrease in reflectance. Further, there is also a risk of splashing of the plating solution, and therefore it is desirable to operate the shake within the above range. If the vibration frequency of the shaking is too low, there is a case where the operation of the (100) plane and the (221) plane alignment is difficult and sufficient control cannot be performed.
再者，本發明中所謂反射率優異或所謂高反射率，係指當在 分光光度計(例如，V660(商品名，日本分光股份有限公司製造))中，橫跨自紫外線區域至可見光區域之波長300nm~800nm連續測定將硫酸鋇標準板設為100%時之總反射率的情形時，於可見光區域短波長端(近紫外線區域之長波長端)之波長400nm的反射率為85%以上，於可見光區域之波長450nm的反射率為90%以上，於波長600nm時為90%以上。反射率之上限值並無特別限制，通常為100%以下。 Furthermore, in the present invention, the so-called excellent reflectance or so-called high reflectance means when In a spectrophotometer (for example, V660 (trade name, manufactured by JASCO Corporation)), the total reflectance when the barium sulfate standard plate is set to 100% is continuously measured across the wavelength range from 300 nm to 800 nm from the ultraviolet region to the visible region. In the case of the short-wavelength end of the visible light region (the long-wavelength end of the near-ultraviolet region), the reflectance at a wavelength of 400 nm is 85% or more, the reflectance at a wavelength of 450 nm in the visible light region is 90% or more, and 90 at a wavelength of 600 nm. %the above. The upper limit of the reflectance is not particularly limited and is usually 100% or less.
以下，基於實施例進一步詳細地說明本發明，但本發明並不限定於此。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
準備表面粗糙度Ry為0.5μm以下之金屬基板作為導電性基材，並於Ag鍍敷液使用硒系光澤劑進行鍍敷。於上述導電性基材上，為了提高密合性或耐熱性，亦可進行Cu鍍敷或Ni鍍敷等作為基底鍍敷。又，以下之實施例雖然得到的是光反射構件，但藉由以適當之方法將銀膜部位自基材切開，可獲得銀反射膜。 A metal substrate having a surface roughness Ry of 0.5 μm or less is prepared as a conductive substrate, and is plated with a selenium-based brightener in the Ag plating solution. In order to improve adhesion or heat resistance on the above-mentioned conductive substrate, Cu plating or Ni plating may be used as the base plating. Further, although the light reflection member was obtained in the following examples, the silver reflection film can be obtained by cutting the silver film portion from the substrate by an appropriate method.
實施例1中，使用表面粗糙度Ry為0.2μm之銅合金C18045作為導電性基材，於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Example 1, a copper alloy C18045 having a surface roughness Ry of 0.2 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(優美科日本(Umicore Japan)製造)濃度22ml/L、溫度30℃、電流密度4A/dm2、攪拌數1000rpm、振幅2mm、振動頻率20Hz之條件實施70秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得實施例1之光反射構件。 Silver plating is a silver concentration of 60 g/L, a gloss agent (manufactured by Umicore Japan), a concentration of 22 ml/L, a temperature of 30 ° C, a current density of 4 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 2 mm, and a vibration frequency of 20 Hz. The condition was carried out for 70 seconds, whereby a silver reflective film having a layer thickness of 3 μm was formed on the intermediate layer, and the light-reflecting member of Example 1 was obtained.
實施例2中，使用表面粗糙度Ry為0.3μm之銅合金C18045作為導電性基材，並於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Example 2, a copper alloy C18045 having a surface roughness Ry of 0.3 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、 溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅5mm、振動頻率60Hz之條件實施50秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得實施例2之光反射構件。 Silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 5 mm, and a vibration frequency of 60 Hz. After a second plating treatment, a silver reflective film having a layer thickness of 3 μm was formed on the intermediate layer, and the light-reflecting member of Example 2 was obtained.
實施例3中，使用表面粗糙度Ry為0.2μm之銅合金C18045作為導電性基材，並於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Example 3, a copper alloy C18045 having a surface roughness Ry of 0.2 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅3mm、振動頻率60Hz之條件實施50秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得實施例3之反射構件。 Silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 3 mm, and a vibration frequency of 60 Hz. The plating treatment was carried out for a second, whereby a silver reflective film having a layer thickness of 3 μm was formed on the intermediate layer, and the reflective member of Example 3 was obtained.
實施例4中，使用表面粗糙度Ry為0.5μm之銅合金C14410作為導電性基材，並於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Example 4, a copper alloy C14410 having a surface roughness Ry of 0.5 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅5mm、振動頻率40Hz之條件實施50秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得實施例4之反射構件。 Silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 5 mm, and a vibration frequency of 40 Hz. After a second plating treatment, a silver reflective film having a layer thickness of 3 μm was formed on the intermediate layer, and the reflective member of Example 4 was obtained.
實施例5中，使用表面粗糙度Ry為0.3μm之銅合金C14410作為導電性基材，並於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Example 5, a copper alloy C14410 having a surface roughness Ry of 0.3 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅5mm、振動頻率40Hz之條件實施50秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得實施例5之反射構件。 Silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 5 mm, and a vibration frequency of 40 Hz. After a second plating treatment, a silver reflective film having a layer thickness of 3 μm was formed on the intermediate layer, and the reflective member of Example 5 was obtained.
實施例6中，使用表面粗糙度Ry為0.2μm之銅合金C18045作為導電性基材，並於導電性基材上形成0.025μm厚之Ni鍍層作為中間層。 In Example 6, a copper alloy C18045 having a surface roughness Ry of 0.2 μm was used as a conductive substrate, and a 0.025 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅5mm、振動頻率60Hz之條件實施50秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得實施例6之反射構件。 Silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 5 mm, and a vibration frequency of 60 Hz. The plating treatment was carried out for a second, whereby a silver reflective film having a layer thickness of 3 μm was formed on the intermediate layer, and the reflective member of Example 6 was obtained.
實施例7中，使用表面粗糙度Ry為0.2μm之銅合金C18045作為導電性基材，並於導電性基材上形成0.2μm厚之Ni鍍層作為中間層。 In Example 7, a copper alloy C18045 having a surface roughness Ry of 0.2 μm was used as a conductive substrate, and a 0.2 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅5mm、振動頻率60Hz之條件實施9秒鐘電鍍處理，藉此於中間層上形成層厚0.5μm之銀反射膜，而獲得實施例7之反射構件。 The silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 5 mm, and a vibration frequency of 60 Hz. After a second plating treatment, a silver reflective film having a layer thickness of 0.5 μm was formed on the intermediate layer, and the reflective member of Example 7 was obtained.
實施例8中，使用表面粗糙度Ry為0.2μm之銅合金C18045作為導電性基材，並於導電性基材上形成0.2μm厚之Ni鍍層作為中間層。 In Example 8, a copper alloy C18045 having a surface roughness Ry of 0.2 μm was used as a conductive substrate, and a 0.2 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅5mm、振動頻率60Hz之條件實施17秒鐘電鍍處理，藉此於中間層上形成層厚1μm之銀反射膜，而獲得實施例8之反射構件。 Silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 5 mm, and a vibration frequency of 60 Hz. In the second plating treatment, a silver reflective film having a layer thickness of 1 μm was formed on the intermediate layer, and the reflective member of Example 8 was obtained.
實施例9中，使用表面粗糙度Ry為0.2μm之銅合金C18045作為導電性基材，並於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Example 9, a copper alloy C18045 having a surface roughness Ry of 0.2 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅5mm、振動頻率60Hz 之條件實施17秒鐘電鍍處理，藉此於中間層上形成層厚1μm之銀反射膜，而獲得實施例9之反射構件。 Silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 5 mm, and a vibration frequency of 60 Hz. The plating treatment was carried out for a second, whereby a silver reflective film having a layer thickness of 1 μm was formed on the intermediate layer, and the reflective member of Example 9 was obtained.
實施例10中，使用表面粗糙度Ry為0.3μm之銅合金C14410作為導電性基材，並於導電性基材上形成0.2μm厚之Ni鍍層作為中間層。 In Example 10, a copper alloy C14410 having a surface roughness Ry of 0.3 μm was used as a conductive substrate, and a 0.2 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅5mm、振動頻率60Hz之條件實施25秒鐘電鍍處理，藉此於中間層上形成層厚2μm之銀反射膜，而獲得實施例10之反射構件。 Silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 5 mm, and a vibration frequency of 60 Hz. The plating treatment was carried out for a second, whereby a silver reflective film having a layer thickness of 2 μm was formed on the intermediate layer, and the reflective member of Example 10 was obtained.
實施例11中，使用表面粗糙度Ry為0.2μm之銅合金C18045作為導電性基材。 In Example 11, a copper alloy C18045 having a surface roughness Ry of 0.2 μm was used as the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數1000rpm、振幅5mm、振動頻率60Hz之條件實施50秒鐘電鍍處理，藉此於導電性基材上形成層厚3μm之銀反射膜，而獲得實施例11之反射構件。 Silver plating was carried out under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 1000 rpm, an amplitude of 5 mm, and a vibration frequency of 60 Hz. In the second plating treatment, a silver reflective film having a layer thickness of 3 μm was formed on the conductive substrate to obtain a reflecting member of Example 11.
比較例1中，使用表面粗糙度Ry為0.6μm之銅合金C19210作為導電性基材，並於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Comparative Example 1, a copper alloy C19210 having a surface roughness Ry of 0.6 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑(美泰樂製造)濃度20ml/L、溫度25℃、電流密度6A/dm2、攪拌數500rpm之條件實施50秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得比較例1之光反射構件。 Silver plating was carried out for 50 seconds under the conditions of a silver concentration of 60 g/L, a gloss agent (manufactured by Metalol) concentration of 20 ml/L, a temperature of 25 ° C, a current density of 6 A/dm 2 , and a stirring number of 500 rpm. A silver reflective film having a layer thickness of 3 μm was formed on the intermediate layer, and the light-reflecting member of Comparative Example 1 was obtained.
比較例2中，使用表面粗糙度Ry為0.7μm之銅合金C19400作為導電性基材，並於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Comparative Example 2, a copper alloy C19400 having a surface roughness Ry of 0.7 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度60g/L、光澤劑濃度0ml/L(不使用)、溫度25℃、電流密度6A/dm2、攪拌數500rpm、振幅5mm、振動頻率60Hz之條件實施50秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得比較例2之光反射構件。 Silver plating was carried out for 50 seconds under the conditions of a silver concentration of 60 g/L, a gloss agent concentration of 0 ml/L (not used), a temperature of 25 ° C, a current density of 6 A/dm 2 , a stirring number of 500 rpm, an amplitude of 5 mm, and a vibration frequency of 60 Hz. By electroplating, a silver reflective film having a layer thickness of 3 μm was formed on the intermediate layer, and the light-reflecting member of Comparative Example 2 was obtained.
習知例1中，使用表面粗糙度Ry為0.7μm之銅合金C19400作為導電性基材，並於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Conventional Example 1, a copper alloy C19400 having a surface roughness Ry of 0.7 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度32g/L、光澤劑(EEJA製造)濃度10ml/L、溫度25℃、電流密度1A/dm2、攪拌數200rpm之條件實施306秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得習知例1之光反射構件。 Silver plating was carried out for 306 seconds under the conditions of a silver concentration of 32 g/L, a gloss agent (manufactured by EEJA) of 10 ml/L, a temperature of 25 ° C, a current density of 1 A/dm 2 , and a stirring number of 200 rpm. A silver reflective film having a layer thickness of 3 μm was formed on the layer to obtain a light-reflecting member of Conventional Example 1.
習知例2中，使用表面粗糙度Ry為0.7μm之銅合金C19400作為導電性基材，並於導電性基材上形成1.0μm厚之Ni鍍層作為中間層。 In Conventional Example 2, a copper alloy C19400 having a surface roughness Ry of 0.7 μm was used as a conductive substrate, and a 1.0 μm thick Ni plating layer was formed as an intermediate layer on the conductive substrate.
作為鍍銀，係以銀濃度36g/L、光澤劑(美錄德製造)濃度15ml/L、溫度25℃、電流密度2A/dm2、攪拌數200rpm之條件實施180秒鐘電鍍處理，藉此於中間層上形成層厚3μm之銀反射膜，而獲得習知例2之光反射構件。 Silver plating was carried out for 180 seconds under the conditions of a silver concentration of 36 g/L, a gloss agent (manufactured by Meite) of 15 ml/L, a temperature of 25 ° C, a current density of 2 A/dm 2 , and a stirring number of 200 rpm. A silver reflective film having a layer thickness of 3 μm was formed on the intermediate layer, and a light reflecting member of Conventional Example 2 was obtained.
各測定之結果顯示於表1之狀態「AS」欄。 The results of the respective measurements are shown in the "AS" column of the state of Table 1.
對以上述方式製作之反射構件，使用分光光度計(日本分光公司製造，V-660(商品名))進行300nm~800nm為止之總反射率的連續測定。將各反射構件之反射率值示於表1。實施例1~11中，於可見光區域內具有高反射率，於400nm均為85%以上，於450nm與600nm均為90%以上。尤其是實施例1~3於450nm與600nm之反射率均顯示95%以上。另一方面，比較 例1~2、習知例1~2於400nm之反射率均未達85%，於450nm之反射率均為84~87%左右，顯示低於各實施例之值。 For the reflection member produced in the above manner, a total measurement of the total reflectance from 300 nm to 800 nm was carried out using a spectrophotometer (manufactured by JASCO Corporation, V-660 (trade name)). The reflectance values of the respective reflecting members are shown in Table 1. In Examples 1 to 11, the high reflectance in the visible light region was 85% or more at 400 nm, and was 90% or more at 450 nm and 600 nm. In particular, in Examples 1 to 3, the reflectances at 450 nm and 600 nm were both 95% or more. On the other hand, compare In Examples 1 to 2, the reflectances of the conventional examples 1 and 2 were less than 85% at 400 nm, and the reflectance at 450 nm was about 84 to 87%, which was lower than the values of the respective examples.
又，對上述反射構件進行電子背向散射繞射(EBSD)，觀察表面(即銀反射膜之表面)之銀反射膜的結晶方位。實施例1~11中，於反射構件表面之法線方向以(100)配向為主，即，反射面之法線方向與<100>方向大致平行之結晶的比率於特定視野為50%以上。且，(100)配向內存在多個雙晶即(221)配向，即，重合晶界Σ 3長度相對於測定面積之比(重合晶界Σ 3每單位面積之長度)為0.4μm/μm2以上。另一方面，例如，比較例1中，(100)配向雖多，但其區域之比率未達50%，且，(100)配向內之雙晶較實施例1~11少。又，習知例1中，未觀察到特定之配向依存性，結晶粒小。 Further, the reflective member was subjected to electron backscatter diffraction (EBSD) to observe the crystal orientation of the silver reflective film on the surface (i.e., the surface of the silver reflective film). In the first to eleventh embodiments, the normal direction of the surface of the reflecting member is mainly (100), that is, the ratio of the crystal whose normal direction of the reflecting surface is substantially parallel to the <100> direction is 50% or more in the specific field of view. Further, (100) alignment exists in a plurality of twin crystals, that is, (221) alignment, that is, the ratio of the length of the coincident grain boundary Σ 3 to the measured area (the length of the coincident grain boundary Σ 3 per unit area) is 0.4 μm/μm 2 the above. On the other hand, for example, in Comparative Example 1, although the (100) orientation is large, the ratio of the regions is less than 50%, and the twin crystals in the (100) alignment are smaller than those in the examples 1 to 11. Further, in Conventional Example 1, no specific alignment dependency was observed, and crystal grains were small.
將上述反射構件根據EBSD圖案而獲得之(100)配向的比率、及(100)面之雙晶即(221)面的比率示於表1。(100)配向之比率，例如於實施例1中顯示82%，實施例2中顯示53%，比較例1中顯示47%，習知例1中顯示18%，具有波長450nm時之反射率越大，(100)配向之比率越大的傾向。 The ratio of the (100) alignment obtained by the above-mentioned reflection member according to the EBSD pattern and the ratio of the (221) plane of the (100) plane are shown in Table 1. (100) Ratio of alignment, for example, 82% is shown in Example 1, 53% is shown in Example 2, 47% is shown in Comparative Example 1, and 18% is shown in Conventional Example 1, and the reflectance is higher at a wavelength of 450 nm. Large, (100) the tendency of the ratio of the alignment.
將實施例1~11、比較例1及2、以及習知例1及2之各反射構件利用恆溫槽於200℃進行2小時大氣加熱，並以與上述相同之方式進行反射率與EBSD測定。各測定之結果匯總示於表1之狀態「200℃_2hr」欄。 Each of the reflection members of Examples 1 to 11, Comparative Examples 1 and 2, and Conventional Examples 1 and 2 was subjected to atmospheric heating at 200 ° C for 2 hours in a thermostatic chamber, and reflectance and EBSD measurement were performed in the same manner as above. The results of the respective measurements are collectively shown in the column "200 ° C_2hr" in Table 1.
實施例1~11中，均顯示與加熱前相比大致同等之高反射率。相對於此，比較例1~2、習知例1~2中，均較加熱前之反射率降低。例如，比較例1中，與加熱前相比，反射率降低，於400nm之加熱後的反射率未達80%，顯示較加熱前低5%左右之值。又，習知例1於400nm之加熱後的反射率顯示低至74%左右之值。 In all of Examples 1 to 11, high reflectances which are substantially equal to those before heating were shown. On the other hand, in Comparative Examples 1 to 2 and 2 to 2, the reflectance before heating was lowered. For example, in Comparative Example 1, the reflectance was lowered as compared with that before heating, and the reflectance after heating at 400 nm was less than 80%, indicating a value lower by about 5% than before heating. Further, the reflectance of the conventional example 1 after heating at 400 nm showed a value as low as about 74%.
藉由EBSD測定，於實施例1~11中，與加熱前相同地以 (100)配向為主，且(100)配向內之雙晶的比率較加熱前稍微變小，或者，亦有變大之情形。比較例1中，(100)配向在加熱前雖多，但加熱後未觀察到特定之配向依存性。習知例1中，顯著可見結晶粒之粗大化，但未觀察到特定之配向依存性。 By the EBSD measurement, in Examples 1 to 11, the same as before heating, (100) The alignment is dominant, and the ratio of the twin crystals in the (100) alignment is slightly smaller than before heating, or it may be increased. In Comparative Example 1, although the (100) alignment was large before heating, no specific alignment dependency was observed after heating. In Conventional Example 1, the coarsening of crystal grains was remarkably observed, but no specific alignment dependency was observed.
又，將上述反射構件之加熱前後根據EBSD圖案而獲得之(100)配向的比率、及與(100)配向接觸之重合晶界Σ 3密度示於表1。從表1顯示出重合晶界Σ 3密度越大耐熱性越高之傾向。因此，認為藉由使重合晶界Σ 3存在於(100)配向，可抑制加熱所導致之(100)配向的再結晶，加熱後亦有高反射率。 Further, the ratio of the (100) alignment obtained by the EBSD pattern before and after the heating of the reflection member, and the coincidence grain boundary Σ 3 density in the (100) alignment contact are shown in Table 1. From Table 1, it is shown that the higher the density of the grain boundary Σ 3 is, the higher the heat resistance tends to be. Therefore, it is considered that by the presence of the coincident grain boundary Σ 3 in the (100) alignment, recrystallization of the (100) alignment caused by heating can be suppressed, and high reflectance is also obtained after heating.
以努氏硬度(Hk)評價實施例1~11、比較例1及2、以及習知例1及2之各光反射構件的銀反射膜硬度。評價係根據JIS Z 2251，以荷重10gf於荷重保持時間15秒之條件下進行測定。對於硬度，係評價初期狀態之硬度與30天後(30天×24小時後)之硬度，並示於表1之狀態「AS」欄。又，將實施例1~11、比較例1及2、以及習知例1及2之各光反射構件利用恆溫槽於200℃進行2小時大氣加熱，並對冷卻後之狀態(初期狀態)的硬度與自該狀態起30天後的硬度以同樣之方式進行試驗、評價，並匯總示於表1之狀態「200℃_2hr」欄。 The silver reflective film hardness of each of the light-reflecting members of Examples 1 to 11, Comparative Examples 1 and 2, and Conventional Examples 1 and 2 was evaluated by Knoop hardness (Hk). The evaluation was carried out in accordance with JIS Z 2251 under the conditions of a load of 10 gf for 15 seconds. For the hardness, the hardness in the initial state and the hardness after 30 days (30 days × 24 hours) were evaluated and shown in the state "AS" column of Table 1. Further, each of the light-reflecting members of Examples 1 to 11, Comparative Examples 1 and 2, and Conventional Examples 1 and 2 was air-heated at 200 ° C for 2 hours in a constant temperature bath, and was cooled (state of initial state). The hardness and the hardness after 30 days from this state were tested and evaluated in the same manner, and are collectively shown in the column "200 ° C_2 hr" in Table 1.
實施例1~11中，均顯示與初期硬度大致同等之硬度。相對於此，比較例1~2、習知例1~2中，硬度降低。再者，關於實施加熱試驗(200℃、2hr)者，未見到重大變化。 In each of Examples 1 to 11, the hardness was approximately equal to the initial hardness. On the other hand, in Comparative Examples 1 to 2 and 2 to 2, the hardness was lowered. Further, no significant change was observed in the heating test (200 ° C, 2 hr).
已將本發明與其實施形態一併加以說明，但只要本發明未特別指定，則即使在說明本發明之任一細部中，皆非用以限定本發明，只要在不違反本案申請專利範圍所示之發明其精神與範圍下，應作最大範圍的解釋。 The present invention has been described in connection with the embodiments thereof, and the present invention is not limited to the details of the present invention, as long as it is not specified, as long as it does not violate the scope of the patent application. The invention should be interpreted to the fullest extent within its spirit and scope.
本申請案係主張基於2012年10月5日在日本提出專利申請之特願2012-223425之優先權者，本案係參照此申請案並將其內容加入作為本說明書記載之一部分。 The present application claims the priority of Japanese Patent Application No. 2012-223425, the entire disclosure of which is hereby incorporated by reference.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2012223425 | 2012-10-05 |
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| TWI605274B true TWI605274B (en) | 2017-11-11 |
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| JP (1) | JP5684431B2 (en) |
| KR (1) | KR102088267B1 (en) |
| CN (1) | CN104685108B (en) |
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| JP6380174B2 (en) * | 2015-03-10 | 2018-08-29 | 三菱マテリアル株式会社 | Silver plated copper terminal material and terminal |
| JP6789965B2 (en) * | 2015-11-05 | 2020-11-25 | 古河電気工業株式会社 | Lead frame material and its manufacturing method |
| JP6383379B2 (en) * | 2016-04-27 | 2018-08-29 | 矢崎総業株式会社 | Plating material and terminals using this plating material |
| JP2019002056A (en) * | 2017-06-19 | 2019-01-10 | 古河電気工業株式会社 | Metallic material |
| CN107747116A (en) * | 2017-10-26 | 2018-03-02 | 防城港市奥氏蓝科技有限公司 | A kind of preparation method of electrosilvering reflection and heat insulation glued membrane |
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| JPH09249991A (en) * | 1996-03-13 | 1997-09-22 | Nikko Kinzoku Kk | Surface treatment of silver plated material |
| US6261435B1 (en) * | 1997-10-21 | 2001-07-17 | Nihon Techno Kabushiki Kaisha | Plating method |
| JP2988624B2 (en) * | 1997-10-21 | 1999-12-13 | 日本テクノ株式会社 | Plating method |
| JP2005029849A (en) | 2003-07-07 | 2005-02-03 | Kobe Steel Ltd | Ag ALLOY REFLECTIVE FILM FOR REFLECTOR, REFLECTOR USING THE Ag ALLOY REFLECTIVE FILM, AND Ag ALLOY SPUTTERING TARGET FOR DEPOSITING THE Ag ALLOY REFLECTIVE FILM |
| JP2007058194A (en) * | 2005-07-26 | 2007-03-08 | Tohoku Univ | High-reflectance visible-light reflector member, liquid-crystal display backlight unit employing the same and manufacturing method of the high-reflectance visible-light reflector member |
| JP4688674B2 (en) * | 2005-10-20 | 2011-05-25 | 京セラ株式会社 | Light emitting element storage package and light emitting device |
| JP4367457B2 (en) * | 2006-07-06 | 2009-11-18 | パナソニック電工株式会社 | Silver film, silver film manufacturing method, LED mounting substrate, and LED mounting substrate manufacturing method |
| WO2010071182A1 (en) * | 2008-12-19 | 2010-06-24 | 古河電気工業株式会社 | Optical semiconductor device lead frame and manufacturing method thereof |
| JP4897981B2 (en) * | 2008-12-26 | 2012-03-14 | 古河電気工業株式会社 | Lead frame for optical semiconductor device, manufacturing method thereof, and optical semiconductor device |
| JP5432863B2 (en) * | 2010-08-25 | 2014-03-05 | 住友電気工業株式会社 | Alignment substrate for film formation and superconducting wire |
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| JP5684431B2 (en) | 2015-03-11 |
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| JPWO2014054817A1 (en) | 2016-08-25 |
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| KR102088267B1 (en) | 2020-03-12 |
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