JP5472969B2 - Light reflecting material and light emitting diode device using the same - Google Patents
Light reflecting material and light emitting diode device using the same Download PDFInfo
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- JP5472969B2 JP5472969B2 JP2009097030A JP2009097030A JP5472969B2 JP 5472969 B2 JP5472969 B2 JP 5472969B2 JP 2009097030 A JP2009097030 A JP 2009097030A JP 2009097030 A JP2009097030 A JP 2009097030A JP 5472969 B2 JP5472969 B2 JP 5472969B2
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- 239000000463 material Substances 0.000 title claims description 40
- 229910052709 silver Inorganic materials 0.000 claims description 60
- 239000004332 silver Substances 0.000 claims description 60
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 59
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 35
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical group [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 11
- 239000002344 surface layer Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- -1 platinum group metals Chemical class 0.000 claims description 2
- 238000007747 plating Methods 0.000 description 40
- 238000001579 optical reflectometry Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 10
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 229910001252 Pd alloy Inorganic materials 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- 238000005275 alloying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- 239000006172 buffering agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
Description
本発明は、光反射性が優れた皮膜を最表面に有する光反射材、その光反射材を光反射部に用いた発光ダイオードデバイスに関する。 The present invention relates to a light reflecting material having a film having excellent light reflectivity on the outermost surface, and a light emitting diode device using the light reflecting material for a light reflecting portion.
発光ダイオード（ＬＥＤ）デバイスは、半導体のｐｎ接合に順方向電流を流し、接合領域で電子と正孔とを再結合させることにより発光させるダイオードであり、構造が単純で電気エネルギーを直接光エネルギーに変換するため、変換効率、信頼性が高く、すでに広く実用化されている。
また、近年、省エネルギー、延いては環境保全の観点からこれまでの白熱電球や蛍光灯に代わる新たな光源、照明器具として白色光発光ダイオードの利用が注目されている。
この発光ダイオードデバイスは、リードフレームの台座を加工し、反射部に囲まれた位置にＬＥＤチップを載置し、ＬＥＤチップの発光を反射部で効率的に取り出す設計となっている。また必要に応じて前記ＬＥＤチップをエポキシ樹脂等の樹脂により封止する構成となっている。
この発光ダイオードデバイスは、光源としても実用化されているが、種々改善すべき問題がある。その一つに、反射部の反射率を向上させる課題がある。
これまで光反射率の優れた材料としては銀やアルミニウム、あるいは金の皮膜が有用な材料として知られている（特許文献１、２）。中でも銀は光沢度、反射率が高く反射材として最も好適な材料として知られている。
A light emitting diode (LED) device is a diode that emits light by flowing a forward current through a semiconductor pn junction and recombining electrons and holes in the junction region, and has a simple structure and directly converts electrical energy into light energy. In order to convert, conversion efficiency and reliability are high and it has already been widely put into practical use.
In recent years, the use of white light-emitting diodes has attracted attention as a new light source and lighting fixture that can replace conventional incandescent bulbs and fluorescent lamps from the viewpoint of energy saving and environmental conservation.
This light-emitting diode device is designed such that a pedestal of a lead frame is processed, an LED chip is placed at a position surrounded by a reflective portion, and light emitted from the LED chip is efficiently extracted by the reflective portion. Further, the LED chip is sealed with a resin such as an epoxy resin as necessary.
This light-emitting diode device has been put into practical use as a light source, but has various problems to be improved. One of them is a problem of improving the reflectance of the reflecting portion.
To date, silver, aluminum, or gold films are known as useful materials having excellent light reflectance (
しかしながら、銀は活性であり、銀皮膜の表面は酸化などにより変色し易く、また銀皮膜の下地に銀以外の金属、金属酸化物、硫化物が存在する場合には銀皮膜中にこれらの物質が拡散し易く銀皮膜表面に移行して、いずれも銀皮膜の光反射性に影響し、その性能を低下させる。前記ＬＥＤデバイスの構成でいえば、リードフレームを形成する銅の上に光反射部として銀皮膜を形成すると、銅が銀皮膜中に拡散して銀皮膜の表面にまで達してその反射率の低下を招くこととなる。
前記銀皮膜中への拡散を防止するための技術については例えば、銀めっき皮膜の形成前に、白金族金属のパラジウム、ロジウム、白金、ルテニウム、イリジウムのいずれかまたはそれらの合金からなる拡散防止層を設けることが提案されている（特許文献３）。
しかし、銀皮膜の光反射性能の改善、あるいは酸化による変色、特に高温環境下での変色による光反射性能の低下に対する対策については、まだ有効な技術開発がなされておらず、特に前記白色光源としての利用促進に資する上でこうした改善が要望されている。
However, silver is active, and the surface of the silver film is likely to be discolored by oxidation or the like, and these substances are contained in the silver film when a metal, metal oxide, or sulfide other than silver is present on the base of the silver film. Easily diffuses to the surface of the silver coating, both of which affect the light reflectivity of the silver coating and reduce its performance. Speaking of the configuration of the LED device, when a silver film is formed as a light reflecting portion on the copper forming the lead frame, the copper diffuses into the silver film and reaches the surface of the silver film, and the reflectance decreases. Will be invited.
Regarding the technique for preventing diffusion into the silver film, for example, before the formation of the silver plating film, a diffusion prevention layer comprising any of the platinum group metals palladium, rhodium, platinum, ruthenium, iridium or an alloy thereof. Has been proposed (Patent Document 3).
However, effective technological development has not been made yet for measures to improve the light reflection performance of the silver film or to discoloration due to oxidation, particularly deterioration of light reflection performance due to discoloration in a high temperature environment. Such improvements are required to contribute to promoting the use of
ところで、銀皮膜の形成のためのめっき方法については、すでに各種の提案がされている。銀は電気抵抗が金属中最も小さく、はんだ付け性も良好なことから電子部品等に広く用いられている。しかし、その反面、銀は高活性であり大気中で酸化あるいは硫化されやすくその結果変色しやすい、耐摩耗性が劣るなどの欠点を有する。こうした問題点を改良することを目的とした、銀の合金めっき液についてもすでに多くの提案がある。
例えば、プリント配線板の銀めっき皮膜が酸化されやすく、はんだ付け性に劣ることとなる問題を、銀めっき皮膜を白金族金属のパラジウム、白金、金及びロジウムからなる群から選ばれた少なくとも一つの金属により合金化した銀合金めっき皮膜とすることによりこれらの特性を改善することを提案するもの（特許文献４）。
特定の緩衝剤を使用することによりｐＨを約６．５ないし９．５に維持してパラジウム又はパラジウム合金金属が浴から沈殿することを防止した水性めっき浴を提案するもの（特許文献５）。
耐酸化性、耐摩耗性の改善のため銀をパラジウムと合金化したメッキとすることを提案するもの（特許文献６）。
銀めっき皮膜の耐食性などを向上するための銀−パラジウムめっき皮膜を形成するめっき液浴が、パラジウムの組成比が高まるとめっき皮膜の表面状態や密着性が悪くなる問題点を改良しためっき浴組成を提案するもの（特許文献７）。
安定性が良好で、形成された合金皮膜の合金組成、膜厚などが均一で、良好な外観を有するめっき皮膜を得ることができる特定の組成の無電解めっき液を提案するもの（特許文献８）。
安定性が良好で、めっき浴組成が大きく変動することなく、目的とする合金組成のＡｇ−Ｐｄめっき皮膜を容易に形成できる電気めっき浴組成を提案するもの（特許文献９）。
安定性良好、密着性、外観良好なＡｇ−Ｐｄめっき皮膜を得る特定組成のめっき浴を提案するもの（特許文献１０）。
しかしながら、これら先行技術文献には、銀合金皮膜表面の光反射性、あるいは耐熱性に関しては、何らの開示もされていない。
By the way, various proposals have already been made regarding plating methods for forming a silver film. Silver is widely used in electronic parts and the like because it has the lowest electrical resistance among metals and has good solderability. On the other hand, however, silver is highly active and has the disadvantages that it is easily oxidized or sulfided in the atmosphere, resulting in discoloration and poor wear resistance. There have already been many proposals for silver alloy plating solutions aimed at improving these problems.
For example, at least one selected from the group consisting of palladium, platinum, gold and rhodium of the platinum group metal is used for the problem that the silver plating film of the printed wiring board is easily oxidized and has poor solderability. It proposes improving these characteristics by making it the silver alloy plating film alloyed with the metal (patent document 4).
An aqueous plating bath is proposed in which the pH is maintained at about 6.5 to 9.5 by using a specific buffering agent to prevent precipitation of palladium or palladium alloy metal from the bath (Patent Document 5).
It is proposed that silver is plated with palladium to improve oxidation resistance and wear resistance (Patent Document 6).
Plating bath composition that improves the surface condition and adhesion of the plating film when the palladium composition ratio increases as the plating solution bath forms a silver-palladium plating film to improve the corrosion resistance of the silver plating film. (Patent Document 7).
An electroless plating solution having a specific composition capable of obtaining a plating film having good stability, an alloy composition of the formed alloy film, a uniform film thickness, etc., and a good appearance is proposed (Patent Document 8). ).
Proposed is an electroplating bath composition that has good stability and can easily form an Ag-Pd plating film of an intended alloy composition without greatly changing the plating bath composition (Patent Document 9).
A plating bath having a specific composition for obtaining an Ag—Pd plating film with good stability, adhesion, and good appearance is proposed (Patent Document 10).
However, these prior art documents do not disclose anything about the light reflectivity or heat resistance of the silver alloy film surface.
本願発明は、こうした状況の下に、銀皮膜の光反射性、及びその耐熱性を向上させる最表面を有する光反射材、該光反射材を反射部に具備する発光ダイオードデバイスを提供することを目的とするものである。 Under such circumstances, the present invention provides a light reflecting material having an outermost surface that improves the light reflectivity and heat resistance of a silver film, and a light emitting diode device comprising the light reflecting material in a reflecting portion. It is the purpose.
本発明者は、銀皮膜の光反射性の向上について鋭意検討した結果、銀に白金族金属を合金化した皮膜が、驚くべきことに銀皮膜自体の光反射性より勝り、また該白金族金属を合金化した皮膜は特に耐熱性、耐食性に優れ、高温の環境の下で使用に供される場合においても、同様に銀皮膜自体の光反射性に勝る光反射性を発揮することを見出し、本発明を完成するに至った。 As a result of intensive investigations on the improvement of the light reflectivity of the silver film, the present inventors surprisingly found that the film obtained by alloying a platinum group metal with silver is superior to the light reflectivity of the silver film itself. The alloyed film is particularly excellent in heat resistance and corrosion resistance, and even when used in a high-temperature environment, the film is found to exhibit light reflectivity superior to the light reflectivity of the silver film itself, The present invention has been completed.
すなわち、本発明は、
[１] 銀と白金族金属との合金皮膜を最表面に有する光反射材であって、前記最表面皮膜の下層に銀皮膜を有し、かつ最表層と前記下層銀皮膜との間に、白金族金属品位が前記最表層の合金皮膜の品位より高い白金族金属の品位を有する銀−白金族金属の合金皮膜を設け、銀−白金族金属の合金皮膜が２層構造をなすことを特徴とする光反射材、
[２] 前記最表面皮膜が白金族金属を０．０１〜２０重量％含有する[１]記載の光反射材、
[３] 前記最表面皮膜と銀皮膜との間に白金族金属を２〜２０重量％含有する銀と白金族金属との合金皮膜を具備する[１] または[２]に記載の光反射材、
[４] 前記最表面皮膜の膜厚が３０ｎｍ〜１０００ｎｍである[１]〜[３]のいずれか一つに記載の光反射材、
[５] 前記銀皮膜の膜厚が０．５〜５μｍである[１]〜[４]のいずれか一つに記載の光反射材、
[６] 前記白金族金属がパラジウムである[１]〜[５]のいずれか一つに記載の光反射材、
[７] 少なくとも発光ダイオード素子及びそれを囲む反射部からなる発光ダイオードデバイスにおいて、前記光反射部が前記[１]〜[６]のいずれか一つに記載の光反射材を具備する発光ダイオードデバイス、
[８] 銅又は銅合金からなる台座、該台座上に形成した銀皮膜、該銀皮膜の上に載置した発光ダイオード素子、及び該素子を囲むように設けた光反射部からなり、前記光反射部が前記[１]〜[６]のいずれか一つに記載の光反射材を具備する発光ダイオードデバイス、
に関する。
That is, the present invention
[1] A light reflecting material having an alloy film of silver and a platinum group metal on the outermost surface, having a silver film on the lower layer of the outermost surface film, and between the outermost layer and the lower layer silver film, Provided is a silver-platinum group metal alloy film having a platinum group metal grade that is higher than that of the outermost layer alloy film, and the silver-platinum group metal alloy film has a two-layer structure. A light reflector ,
[ 2 ] The light reflecting material according to [1], wherein the outermost film contains 0.01 to 20% by weight of a platinum group metal,
[ 3 ] The light reflecting material according to [ 1 ] or [ 2 ], comprising an alloy film of silver and a platinum group metal containing 2 to 20% by weight of a platinum group metal between the outermost surface film and the silver film. ,
[ 4 ] The light reflecting material according to any one of [1] to [ 3 ], wherein the film thickness of the outermost surface film is 30 nm to 1000 nm.
[ 5 ] The light reflecting material according to any one of [1] to [ 4 ], wherein the film thickness of the silver film is 0.5 to 5 μm.
[ 6 ] The light reflecting material according to any one of [1] to [ 5 ], wherein the platinum group metal is palladium,
[ 7 ] A light-emitting diode device comprising at least a light-emitting diode element and a reflective portion surrounding the light-emitting diode element, wherein the light-reflecting portion comprises the light-reflecting material according to any one of [1] to [ 6 ]. ,
[ 8 ] A base made of copper or a copper alloy, a silver film formed on the base, a light-emitting diode element placed on the silver film, and a light reflecting portion provided so as to surround the element, A light emitting diode device having a light reflecting material according to any one of [1] to [ 6 ],
About.
本発明の光反射材は、その反射部の最表面に特定組成の白金族金属を合金化した銀−白金族金属皮膜を有することにより、その光反射性を銀皮膜自体の光反射性よりも向上することができる。特に白金族金属との合金化により銀皮膜はその耐熱性を向上することができ高温環境下での使用、例えば発光ダイオードデバイスの反射材として有用である。また、該最表面の下層に白金族金属組成のより高い銀−白金族金属合金皮膜を形成することにより、フレームを構成する銅などの金属の拡散を防止することができ、該拡散金属の最表面への移行による光反射率の低下を防止することができる。 The light reflecting material of the present invention has a silver-platinum group metal film obtained by alloying a platinum group metal having a specific composition on the outermost surface of the reflecting part, so that the light reflectivity is higher than the light reflectivity of the silver film itself. Can be improved. In particular, the silver film can improve its heat resistance by alloying with a platinum group metal, and is useful as a reflector for use in a high temperature environment, for example, a light emitting diode device. Further, by forming a silver-platinum group metal alloy film having a higher platinum group metal composition in the lower layer of the outermost surface, diffusion of a metal such as copper constituting the frame can be prevented. It is possible to prevent a decrease in light reflectance due to the transition to the surface.
以下、本願発明について具体的に説明する。
本発明の光反射材は、その最表面において銀−白金族金属合金皮膜を有することが重要である。銀と合金化する白金族金属はいずれも用いることができる。すなわちルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金のいずれでも良い。中でも、パラジウムが特に好ましい。
前記最表面皮膜は、反射材の製造後の保存、流通過程中、あるいは応用品への組立加工時においてその保護のために、保護膜を設けることもできる。
光反射材のベース材は、基本的には金属、セラミックス、ガラスなどが使用でき、特に制限されるものではない。
Hereinafter, the present invention will be specifically described.
It is important that the light reflecting material of the present invention has a silver-platinum group metal alloy film on its outermost surface. Any platinum group metal alloying with silver can be used. That is, any of ruthenium, rhodium, palladium, osmium, iridium, and platinum may be used. Of these, palladium is particularly preferable.
The outermost surface film may be provided with a protective film for protection after the reflection material is manufactured, during the distribution process, or during assembly into an applied product.
The base material of the light reflecting material can be basically made of metal, ceramics, glass or the like, and is not particularly limited.
しかし、発光ダイオードデバイスの反射材として利用する場合には、リードフレームをＬＥＤ素子が載置できるように加工した台座をベース材とすることが好ましい。このリードフレームは一般に銅又は銅合金から構成されており、この銅又は銅合金の上に銀皮膜を形成し、この銀皮膜にＬＥＤ素子への給電を担わせる。また、反射部においては、その下地銀皮膜の上に最表面層となる銀−白金族金属合金皮膜を形成する。より好ましくは、該下地銀皮膜と銀−白金族金属合金皮膜の間に、より白金族金属品位の高い銀−白金族金属合金皮膜を挟むように形成することである。このように白金族金属品位のより低い最表面皮膜と同高い皮膜で銀−白金族金属皮膜の２層構造とすることにより、前者により高い光反射率を維持して、後者により銅などの拡散を防止して、拡散により銅などが最表面へ移行することを防止して、また耐熱性を向上させ、最表面の光反射性の低下を防止することができる。また、前記銀下地皮膜は、素材の銅からの拡散を抑制すると共に、電導性、放熱性伝導、ＬＥＤ発光素子の搭載接着、ワイヤーボンディング性等のために使用されており、本発明においてもこうした点から有効である。
なお、ＬＥＤ素子は、反射材を含め透明な樹脂で封止することが好ましい。封止樹脂としてはエポキシ樹脂が好ましい。
However, when used as a reflective material for a light-emitting diode device, it is preferable to use a pedestal that has been processed so that the LED element can be placed thereon as a base material. This lead frame is generally composed of copper or a copper alloy, and a silver film is formed on the copper or copper alloy, and this silver film is responsible for supplying power to the LED element. Moreover, in a reflection part, the silver-platinum group metal alloy membrane | film | coat used as the outermost surface layer is formed on the foundation | substrate silver membrane | film | coat. More preferably, a silver-platinum group metal alloy film having a higher platinum group metal quality is sandwiched between the underlying silver film and the silver-platinum group metal alloy film. In this way, the silver-platinum group metal coating has a two-layer structure of the same level as the outermost surface coating with a lower platinum group metal quality, so that the former maintains a higher light reflectivity and the latter diffuses copper and the like. It is possible to prevent copper and the like from migrating to the outermost surface by diffusion, to improve heat resistance, and to prevent a decrease in light reflectivity of the outermost surface. In addition, the silver undercoat is used for suppressing the diffusion of copper from the material, as well as for electrical conductivity, heat dissipation conductivity, LED light-emitting element mounting adhesion, wire bonding properties, and the like in the present invention. It is effective from the point of view.
The LED element is preferably sealed with a transparent resin including a reflective material. An epoxy resin is preferable as the sealing resin.
前記最表面層の銀−白金族金属合金皮膜における白金族金属の含有量は、０．０１〜２０重量％、好ましくは０．１〜１５重量％、更に好ましくは０．１〜５重量％である。白金族金属の含有量が０．０１重量％未満では、白金族金属合金化による最表面皮膜の光反射性向上への効果が実質的に見られず、また２０重量％を超えるとコスト的に不利である上に光反射性向上への効果が低下する。また、最表面層の下に拡散防止のために設ける銀−白金族金属合金皮膜の白金族金属含有量は、最表面層の白金族金属含有量よりも高く、２重量％以上、２０重量％以下であり、好ましくは、４重量％〜１５重量％以下である。 The platinum group metal content in the silver-platinum group metal alloy film of the outermost surface layer is 0.01 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.1 to 5% by weight. is there. When the platinum group metal content is less than 0.01% by weight, the effect of improving the light reflectivity of the outermost surface film by the platinum group metal alloying is not substantially seen. In addition to being disadvantageous, the effect of improving light reflectivity is reduced. In addition, the platinum group metal content of the silver-platinum group metal alloy film provided to prevent diffusion under the outermost surface layer is higher than the platinum group metal content of the outermost surface layer, and is 2% by weight or more and 20% by weight. Or less, preferably 4 to 15% by weight or less.
本発明における前記光反射性向上効果は、銀皮膜を基準として、これよりも光反射性能が向上することを示すものである。更にこの光反射性向上効果は、常温時及び高温雰囲気での使用を想定して、いずれかの状態において銀皮膜よりも勝る光反射性能を示すことを意味する。
最表面層の銀−白金族金属合金皮膜の膜厚は、好ましくは３０ｎｍ〜１０００ｎｍであり、より好ましくは４０〜３００ｎｍである。
最表面層の下層として拡散防止のために設ける銀−白金族金属合金皮膜の膜厚は、４０〜１０００ｎｍが好ましくは、より好ましくは５０〜５００ｎｍである。
また、本発明において下地銀皮膜の膜厚は、０．５〜５μｍ、好ましくは２〜４μｍである。
The light reflectivity improvement effect in the present invention indicates that the light reflection performance is improved more than the silver film as a reference. Furthermore, this light reflectivity improvement effect means that the light reflection performance is superior to the silver film in any state, assuming use at normal temperature and in a high temperature atmosphere.
The film thickness of the silver-platinum group metal alloy film of the outermost surface layer is preferably 30 nm to 1000 nm, more preferably 40 to 300 nm.
The film thickness of the silver-platinum group metal alloy film provided as a lower layer of the outermost surface layer for preventing diffusion is preferably 40 to 1000 nm, more preferably 50 to 500 nm.
In the present invention, the film thickness of the underlying silver film is 0.5 to 5 μm, preferably 2 to 4 μm.
本発明の各皮膜は、その形成方法については特に制限はなく公知技術を利用することができる。例えば無電解めっき、電気めっき、ＣＶＤ、ＰＶＤ、ＡＬＤ（原子層堆積法）、ＡＬＥいずれの方法によるものであってもかまわないが、電気めっき法が簡便で好ましい。
電気めっき方法に使用する、めっき液はＡｇと白金族金属との合金皮膜を形成できるものであればいずれでも良くこれも公知技術を利用することができる。
以下の実施例では、白金族金属としてパラジウムを使用した場合について示すが、他の白金族金属を合金化した場合においても同様な傾向を示す。
銀−パラジウム合金皮膜は、例えば、特開昭５６−１５６７９０号公報に記載のめっき液、めっき方法を使用することができる。また、前記公報記載の方法では高シアン浴を使用するが、低シアン浴、例えば、日鉱商事株式会社製ＨＳ−Ｍ４００なども使用することができる。
Each film of the present invention is not particularly limited with respect to its formation method, and a known technique can be used. For example, any of electroless plating, electroplating, CVD, PVD, ALD (atomic layer deposition method), and ALE may be used, but electroplating is simple and preferable.
Any plating solution may be used for the electroplating method as long as it can form an alloy film of Ag and a platinum group metal.
In the following examples, although the case where palladium is used as the platinum group metal is shown, the same tendency is shown when other platinum group metals are alloyed.
For the silver-palladium alloy film, for example, a plating solution and a plating method described in JP-A-56-156790 can be used. In the method described in the above publication, a high cyan bath is used, but a low cyan bath such as HS-M400 manufactured by Nikko Shoji Co., Ltd. can also be used.
実施例１
銀−パラジウム合金皮膜の形成は、以下のめっき浴及びめっき条件を使用した。
Ａｇ：２．５ｇ／Ｌ
Ｐｄ：５ｇ／Ｌ
ＫＣＮ：１００ｇ／Ｌ
浴量：０．３Ｌ
めっき温度：２５℃
めっき面積：０．１ｄｍ２（２５×２０ｍｍ）
被めっき材：銅板への直接めっき
なお、前記Ａｇとしてはシアン化銀カリウムを、またＰｄとしてはシアン化パラジウムカリウムを使用した。
めっき後のめっき皮膜の膜厚、Ｐｄ品位（Ｐｄ重量％）を以下の表に示す。
また、この測定値から電流密度とめっき膜厚の関係及び電流密度とＰｄ品位との関係を図２に示す。表中ＤＫは電流密度Ａ／ｄｍ２を示す。
Example 1
The following plating bath and plating conditions were used for forming the silver-palladium alloy film.
Ag: 2.5 g / L
Pd: 5 g / L
KCN: 100g / L
Bath volume: 0.3L
Plating temperature: 25 ° C
Plating area: 0.1 dm 2 (25 × 20 mm)
Material to be plated: direct plating on copper plate In addition, potassium cyanide was used as Ag, and palladium potassium cyanide was used as Pd.
The following table shows the film thickness and Pd quality (Pd wt%) of the plated film after plating.
Further, the relationship between the current density and the plating film thickness and the relationship between the current density and the Pd quality are shown in FIG. Table in DK shows the current density A / dm 2.
実施例２
めっき温度を４０℃とする以外は実施例１と同様にして銀−パラジウム合金皮膜を形成した。
その結果を以下の表に示す。また、この測定値から電流密度とめっき膜厚及び電流密度とＰｄ品位との関係を図３に示す。
Example 2
A silver-palladium alloy film was formed in the same manner as in Example 1 except that the plating temperature was 40 ° C.
The results are shown in the following table. Moreover, the relationship between the current density, the plating film thickness, the current density, and the Pd quality is shown in FIG.
実施例３
めっき温度を５０℃とする以外は実施例１と同様にして銀−パラジウム合金皮膜を形成した。
その結果を以下の表に示す。また、この測定値から電流密度とめっき膜厚の関係及び電流密度とＰｄ品位との関係を図４に示す。
Example 3
A silver-palladium alloy film was formed in the same manner as in Example 1 except that the plating temperature was 50 ° C.
The results are shown in the following table. Moreover, the relationship between the current density and the plating film thickness and the relationship between the current density and the Pd quality are shown in FIG.
実施例４
めっき温度を６０℃とする以外は実施例１と同様にして銀−パラジウム合金皮膜を形成した。
その結果を以下の表に示す。また、この測定値から電流密度とめっき膜厚の関係及び電流密度とＰｄ品位との関係を図５に示す。
Example 4
A silver-palladium alloy film was formed in the same manner as in Example 1 except that the plating temperature was 60 ° C.
The results are shown in the following table. Moreover, the relationship between the current density and the plating film thickness and the relationship between the current density and the Pd quality are shown in FIG.
以上のように、銀−パラジウム合金皮膜の膜厚、及びパラジウム品位（Ｐｄ重量％）は、めっき条件を選ぶことにより、それぞれ容易に調整することができる。 As described above, the film thickness and palladium quality (Pd wt%) of the silver-palladium alloy film can be easily adjusted by selecting the plating conditions.
実施例５
パラジウム品位の異なる銀−パラジウム合金皮膜の光反射性能を、加熱処理試験前と加熱処理試験後においてそれぞれ光反射率を測定することにより評価した。
各試料は、銅基材に銀めっき下地２μｍをつけ、その上に所定の銀−パラジウムめっきを１００ｎｍ施した。対照試料は下地銀めっきのみとした。
加熱処理試験は、めっきした試料を３００℃のホットプレート上に２時間置いて行った。光反射率の測定には島津製作所製「ＵＶ−２２００シリーズ用積分球付属装置ＩＳＲ−２２００（Ｐ／Ｎ２０６−６１６００）」を使用した。
その結果を図６（加熱処理試験前）、７（加熱処理試験後）に示す。
図６は、銀皮膜に対して０．４重量％のパラジウムを合金化した皮膜は可視領域において銀皮膜を超える光反射率を示している。常温下ではパラジウムの品位が高まると光反射率は銀皮膜より低下する。しかし、高温雰囲気下では耐熱性が劣る銀皮膜の光反射率は著しく低下するのに対して銀−パラジウム合金化皮膜では、可視光領域の光反射率はむしろ向上している。こうした驚くべき現象を図７は明確に示している。
Example 5
The light reflection performance of silver-palladium alloy films having different palladium qualities was evaluated by measuring the light reflectance before and after the heat treatment test.
Each sample was obtained by applying a silver plating base of 2 μm to a copper base material and applying predetermined silver-palladium plating thereon to 100 nm. The control sample was only the base silver plating.
In the heat treatment test, the plated sample was placed on a hot plate at 300 ° C. for 2 hours. For the measurement of the light reflectance, “Integrated sphere attachment device ISR-2200 (P / N206-61600) for UV-2200 series” manufactured by Shimadzu Corporation was used.
The results are shown in FIGS. 6 (before the heat treatment test) and 7 (after the heat treatment test).
FIG. 6 shows that the film obtained by alloying 0.4% by weight of palladium with respect to the silver film has a light reflectance exceeding the silver film in the visible region. At room temperature, the light reflectivity is lower than that of the silver film when the quality of palladium increases. However, the light reflectance of a silver film having poor heat resistance under a high temperature atmosphere is remarkably lowered, whereas the light reflectance in the visible light region is rather improved in a silver-palladium alloyed film. FIG. 7 clearly shows such a surprising phenomenon.
このように本発明の光反射材は、その最表面に銀−白金族金属合金化皮膜を有することにより、光反射性能を向上することができ、特に高機能化、小型化での高温の環境下ではその向上効果は著しく、実用上極めて有用である。
したがって、発光ダイオードデバイスの反射材として、あるいは従来の白熱電球や蛍光灯に代わる照明器具用の反射材として、またその他の広い分野で有用である。例えば、ａ）携帯電話、ｂ）ＬＣＤバックライト、ｃ）自動車用メーター、ルームライト、ヘッドライト、フォグライト、ｄ）信号機、ｅ）住宅用、オフィス、商業施設などの照明、ｆ）街路灯，ｇ）大型映像表示機、ｈ）アミューズメント、ｉ）ビルボード、ｊ）可視光光通信、ｋ）樹脂硬化、ｌ）光触媒励起用光源、ｍ）コネクター、リードスィッチの市場などにおいて有用である。
As described above, the light reflecting material of the present invention has a silver-platinum group metal alloyed coating on the outermost surface thereof, so that the light reflecting performance can be improved. The improvement effect is remarkable below, and it is extremely useful in practice.
Therefore, it is useful as a reflective material for light-emitting diode devices, as a reflective material for lighting fixtures replacing conventional incandescent bulbs and fluorescent lamps, and in other wide fields. For example, a) mobile phones, b) LCD backlights, c) automobile meters, room lights, headlights, fog lights, d) traffic lights, e) lighting for residential, office, commercial facilities, etc., f) street lights, g) Large-sized video display, h) amusement, i) billboard, j) visible light communication, k) resin curing, 1) photocatalyst excitation light source, m) connector, reed switch market, etc.
Claims (8)
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