CN106573307A - 制造具有氧化银表面的银烧结件的方法及其在通过加压烧结将元件接合的方法中的用途 - Google Patents

制造具有氧化银表面的银烧结件的方法及其在通过加压烧结将元件接合的方法中的用途 Download PDF

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CN106573307A
CN106573307A CN201580040033.1A CN201580040033A CN106573307A CN 106573307 A CN106573307 A CN 106573307A CN 201580040033 A CN201580040033 A CN 201580040033A CN 106573307 A CN106573307 A CN 106573307A
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silver
metal
sintering
silver oxide
purposes
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CN106573307B (zh
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M.舍费尔
W.施密特
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Heraeus Deutschland GmbH and Co KG
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Heraeus Precious Metals GmbH and Co KG
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
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    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
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Abstract

制造具有氧化银表面的层状银烧结体形式的银烧结件的方法及其用途。

Description

制造具有氧化银表面的银烧结件的方法及其在通过加压烧结 将元件接合的方法中的用途
本发明涉及制造具有氧化银表面的银烧结件的方法及其在通过加压烧结将元件接合的方法中的用途。
其中提及的金属氧化物-和氧化银表面或金属氧化物-和氧化银层分别是外部或朝外的金属氧化物-和氧化银表面或金属氧化物-和氧化银层。关于银烧结件，也可以特别是覆盖其整个外表面和因此朝外的氧化银表面或氧化银层。
US 2010/0195292 A1公开了具有银电极的电子元件，其配备有外部的氧化银层。该氧化银层可用于电子元件在待与其接合的表面上的直接烧结接合，其中将氧化银还原成银。
US 2008/160183 A1公开了一种烧结接合方法，其中能够烧结成导电层且包含经有机涂覆的银颗粒和氧化银颗粒的组合物用于在待接合的表面之间制造烧结接合。该还能烧结的组合物可具有油墨、糊料或层状压制品形式的烧结预成型体（Vorform）的使用形式。
EP 0 579 911 A2公开了制造浆料浇铸（schlickergegossen）且各向同性的铜基复合材料的方法。在此，将混合浆料浇铸到合适的基材上、烧灼、烧结并通过冷轧-和回火步骤加工成实心带。该复合材料可用于制造电子元件。
在电子工业中，已知将金属-和/或银烧结糊料或由其通过施加和干燥所制成的还能够烧结（可烧结）的烧结预成型体（所谓的烧结预成型体）用于固定和电接触电子元件例如半导体芯片并从中散热。例如，此类金属-和/或银烧结糊料和烧结预成型体例如于2014年1月17日描述在在线出版物“Are Sintered Silver Joints Ready for Use asInterconnect Material in Microelectronic Packaging”，作者KIM S. SIOW，Journalof ELECTRONIC MATERIALS（DOI:10.1007/s11664-013-2967-3）。关于金属-和/或银烧结糊料的专利文献的实例是WO2011/026623A1、EP2425920A1、EP2428293A1和EP2572814A1。通常，此类金属-和/或银烧结糊料通过印刷例如丝网印刷或模板印刷施加到载体基材上，任选地干燥，配备有电子元件并然后经受烧结操作。不经过液体状态，该金属-和/或银粒子在烧结过程中通过扩散而接合并在载体和电子元件之间形成固体的导电和导热的金属和/或银接合。
然而，如由申请人所发现的，元件之间的通过形成烧结接合的固定也可以在不使用或不直接使用金属-和/或银烧结糊料的情况下实现。代替金属-和/或银烧结糊料，令人惊奇地可以使用根据下面更详细阐述的本发明方法制成的具有氧化银表面的层状银烧结体形式的银烧结件。
根据本发明方法制成的银烧结件是具有氧化银表面，即整个表面或多个不连续表面各自以氧化银层形式的层状银烧结体。所述银烧结件还是不连续的，即独立和/或作为单个分开的零件存在的层状银烧结体，即具有所述氧化银表面的不连续和/或独立烧结的银层。该层状银烧结体的厚度或层厚度例如为10至300 µm。
所述银烧结件的银可为纯银或银合金。该合金例如具有> 50重量%的银含量。
如已所述，根据本发明方法制成的银烧结件是层状银烧结体，即层形式的烧结的银结构，换句话说，是本身不再能烧结的银结构。此类烧结的银结构除了已提及的外部氧化银表面外特别地不包含氧化银，即在本体中没有氧化银。此类层状银烧结体不能与一开始提及的还能烧结的烧结预成型体混淆。
具有氧化银表面的层状银烧结体形式的银烧结件（以下也简称为“银烧结件”或“层状银烧结件”）可根据本发明的方法通过如下方式制造：(1)例如借助丝网印刷、模板印刷或喷涂由银烧结制剂施加到具有不能形成烧结接合的表面的载体基材上，(2)随后使用或优选不使用机械压力烧结所施加的银烧结制剂，然后(3)将如此形成的层状银烧结体从该载体基材的表面上脱离。如果在该制造顺序之后，在所述层状银烧结体的表面上例如通过空气氧化不形成或仅形成不够的氧化银层，可以接着进行(4)随后的氧化步骤以制造或增强在该层状银烧结体的整个或部分外表面上的氧化银层。在此，可使用如以下还将阐述的氧化方法。
据此，根据本发明制造具有氧化银表面的层状银烧结体形式的银烧结件的方法包括下列步骤：
(1)将银烧结制剂施加到具有不能形成烧结接合的表面的载体基材上，
(2)烧结如此施加的银烧结制剂，
(3) 将在步骤(2)中形成的层状银烧结体从该载体基材的表面脱离，以及
(4)任选地在步骤(3)之后的氧化步骤过程中制造或增强所述层状银烧结体的整个或部分外表面上的氧化银层。
可在制造此类层状银烧结体中使用的银烧结制剂的实例是一开始已提及的银烧结糊料。
作为可在制造该层状银烧结体中使用的具有不能形成烧结接合的表面的载体基材，例如合适的是氧化铝陶瓷、镍片、聚酰亚胺薄膜、聚四氟乙烯薄膜和硅酮薄膜。对于本领域技术人员而言在此理所当然的是，不依赖于材料的选择，选择具有非多孔且足够光滑的表面的平整载体基材。
银烧结制剂的施加例如丝网印刷、模板印刷或喷涂，以及烧结的实施是本领域技术人员已知的，不存在方法特别点，因此可以免除详细描述并例如参阅一开始已提及的文献。具有不能形成烧结接合的表面的载体基材的脱离也不困难，因为在烧结操作过程中实际上导致所形成的层状银烧结体的脱落。
可以将所述银烧结件以使用者例如通过加压烧结接合元件的方法的操作者所希望的形式制造，以使得对于使用者不产生边角料形式的废物。同样，可能适宜的是，将所述银烧结件作为连续产品（Endlosware）制造，并且例如以还存在于载体基材上或已经从其脱离的形式提供给使用者。在连续产品的情况中，其本身可配备有预定断裂点例如穿孔，以对于使用者而言可以容易且如规定那样使用。在连续产品的情况中，卷材产品是优选的供货形式。
在每种情况中，银烧结件具有所述的氧化银表面，其可以与元件的金属接触表面各自形成共同的接触面。在此，能够与元件的金属接触表面形成共同的接触面的氧化银表面可以以不连续的，即彼此隔开的氧化银表面存在。
但是，它们也可以以覆盖所述银烧结件的部分或整个表面的连续氧化银层的形式存在。
该银烧结件的氧化银表面优选存在于其前侧和后侧上，以使得在用于通过加压烧结接合元件的方法中所制造的组合件（Anordnung）具有夹层结构，即由元件与设置在其之间的银烧结件构成的组合件的元件此时存在于所述银烧结件的彼此对立侧上。
所述银烧结件的外部或朝外的氧化银层牢固地与位于其下的银接合。该氧化银层例如可为0.02至6 µm厚。其可通过在空气接触下的氧化形成、或通过化学方式借助氧化剂、或通过不、尚未、少许或者或多或少程度氧化的银表面的阳极氧化来制造或增强。如在上句中已表明，已存在的氧化银薄层可例如借助阳极氧化产生或增强。例如，不、部分或开始氧化的银表面可阳极氧化直至形成例如0.03至5 µm的氧化银层厚度。在银表面的情况中，具有例如0.05至1 µm层厚度的氧化银层可通过阳极氧化形成。
所述阳极氧化可例如通过将作为阳极接通且在表面处或上待氧化的银烧结件浸入合适的电解质水溶液中来进行。作为电解质水溶液，合适的例如是5至10重量%的碳酸钠、碳酸氢钠、氢氧化钾或氢氧化钠水溶液。该阳极氧化可例如在5至20伏的直流电压下进行5至30秒。
本发明还涉及根据本发明的方法制造的银烧结件在接合元件的方法中的用途，在该方法中提供由至少两个各自具有金属接触表面的元件和设置在这些元件之间的银烧结件制成的组合件并将该组合件进行加压烧结，其中该银烧结件的氧化银表面与所述元件的金属接触表面各自形成共同的接触面，且其中(I)加压烧结在含有至少一种可氧化的化合物的气氛中进行，和/或(II)氧化银表面在形成各自共同的接触面之前配备有至少一种可氧化的有机化合物。
在此使用的措辞“其中该银烧结件的氧化银表面与所述元件的金属接触表面各自形成共同的接触面”应明确地也包括如下情况，其中该银烧结件的氧化银表面的仅一部分面与所述元件的金属接触表面形成共同的接触面。
据此，实施方案(I)中的方法包括下列步骤：
(i)提供至少两个各自具有金属接触表面的元件和具有氧化银表面的层状银烧结体形式的银烧结件，
(ii)提供由至少两个元件和设置在其之间的银烧结件制成的组合件以形成该银烧结件的各个氧化银表面和各个元件的金属接触表面的各自共同的接触面，和
(iii)在含至少一种可氧化的化合物的气氛中加压烧结该组合件。
相反，实施方案(II)中的方法包括下列步骤：
(i)提供至少两个各自具有金属接触表面的元件和具有氧化银表面的层状银烧结体形式的银烧结件，
(ii)对该氧化银表面配备至少一种可氧化的有机化合物；
(iii)提供由至少两个元件和设置在其之间的银烧结件制成的组合件以形成该银烧结件的各个配备有至少一种可氧化的有机化合物的氧化银表面和各个元件的金属接触表面的各自共同的接触面，和
(iv)加压烧结该组合件。
可以将实施方案(I)和(II)组合。
在所述方法的两个实施方案(I)和(II)中，将至少两个元件接合。在此，提供由至少两个各自具有金属接触表面的元件和设置在这些元件之间的具有氧化银表面的层状银烧结体形式的银烧结件制成的组合件，并将该组合件以本领域技术人员已知的常见方式使用机械压力和提高的温度进行烧结。
至少两个元件的接合理解为是指第一元件在第二元件上的固定。在本发明中，“在……上”仅仅表示第一元件的金属接触表面与第二元件的金属接触表面通过银烧结件接合，其中这些元件或包含这些元件的组合件的相对位置不那么重要。
在本发明中，术语元件应优选包括单件。这些单件优选是不能再拆分的。
根据特别的实施方案，元件表示用于电子业中的零件。据此，元件可以是例如有效元件（例如半导体芯片如LED、二极管、IGBT、晶闸管、MOSFET、晶体管、IC）、无源元件（例如DCB、引线框、电阻器、电容器、线圈、感应器、忆阻器、芯片、冷却体）、压电陶瓷和珀尔帖元件。
待接合的元件可以是同类或不同类的元件。
所述元件各自具有金属接触表面，其中该金属接触表面的金属可以是纯金属或金属合金。该合金例如具有> 50重量%含量的所涉金属。
待接合的元件的金属接触表面的金属可相同或不同。优选地，其选自银、铜、钯和这些金属的合金。银和银合金作为该金属接触表面的金属是特别优选的。
所述一个或多个元件可由金属构成或其金属接触表面可例如以金属化的形式存在。例如，可以是通过蒸镀、化学电镀、电镀或通过金属烧结制剂的施加与随后的烧结而制造的金属化。金属烧结制剂的实例是一开始已提及的金属-或银烧结糊料。
在不总是由金属构成的元件的情况下，所述金属接触表面可例如为100 nm至200µm厚。
如同银烧结件，待接合的元件之一或所有待接合的元件的金属接触表面也可以具有金属氧化物层。这样的金属氧化物层的金属氧化物可以特别是所涉金属接触表面的金属的氧化物。
所述元件通过加压烧结借助设置在其之间的银烧结件相互接合，即这些元件和位于其间的银烧结件通过加热和使用机械压力相互接合，而这些元件的金属接触表面的金属以及银烧结件的银金属没有达到液相。
在所述方法的实施方案(I)中，加压烧结在含有至少一种可氧化化合物的气氛中进行。合适的可氧化化合物的实例是一氧化碳、氢气和甲酸。该气氛可由至少一种可氧化且气态存在的化合物构成或含有后者与惰性气体如特别是氮气和/或氩气的组合。优选地，可氧化化合物在该气氛中的含量为1至30体积%。
在所述方法的实施方案(II)中，银烧结件的氧化银表面和——如果至少两个元件中至少之一的金属接触表面具有金属氧化物层——优选还有后者，在形成共同的接触面之前配备有至少一种可氧化的有机化合物，即一种可氧化的有机化合物或者两种或更多种可氧化有机化合物的混合物。
所述可氧化的有机化合物优选具有1至50，更优选2至24，还更优选6至24，还更优选8至20个碳原子并具有至少一个官能团。
优选地使用游离的脂肪酸、脂肪酸盐或脂肪酸酯作为可氧化的有机化合物。该游离的脂肪酸、脂肪酸盐和脂肪酸酯优选是非支化的。此外，该游离的脂肪酸、脂肪酸盐或脂肪酸酯优选为饱和的。
优选的脂肪酸盐是铵、单烷基铵、二烷基铵、三烷基铵、铝、铜、锂、钠和钾的盐。
优选的酯是烷基酯，特别是甲酯、乙酯、丙酯和丁酯。
根据一个优选的实施方案，所述游离的脂肪酸、脂肪酸盐或脂肪酸酯是具有8至24，更优选8至18个碳原子的化合物。
优选的可氧化的有机化合物是羊脂酸（辛酸）、羊蜡酸（癸酸）、月桂酸（十二烷酸）、肉豆蔻酸（十四烷酸）、棕榈酸（十六烷酸）、珠光脂酸（十七烷酸）、硬脂酸（十八烷酸）、花生酸（二十烷酸/二十酸）、山嵛酸（二十二烷酸）、木蜡酸（二十四烷酸）以及相应的酯和盐。
特别优选的可氧化的有机化合物是十二烷酸、十八烷酸、硬脂酸铝、硬脂酸铜、硬脂酸钠、硬脂酸钾、棕榈酸钠和棕榈酸钾。
为了将各个金属氧化物-和/或氧化银层配备至少一种可氧化的有机化合物，后者可例如不经稀释地作为有效物质或由含水制剂或由有机溶剂中的制剂施涂到金属氧化物-和/或氧化银层的表面上，然后例如在15至50℃的目标温度下干燥10至60分钟的干燥时间。关于施涂类型，原则上没有限制；例如可将金属氧化物-和/或氧化银层浸入至少一种可氧化的有机化合物的制剂中，或可将至少一种可氧化的有机化合物的制剂喷洒或刷涂到金属氧化物-和/或氧化银层上。含水制剂或基于有机溶剂的制剂可以是至少一种可氧化的有机化合物的例如1至20重量%的溶液、分散液或悬浮液。
所述至少一种可氧化的有机化合物的质量与待配备或配备该至少一种可氧化的有机化合物的氧化银层的面积的比例为例如0.0005至10 g该至少一种可氧化的有机化合物/平方米氧化银面积。本领域技术人员根据氧化银层厚度来选择这一比例，即氧化银层厚度越大，他所选择的该至少一种可氧化的有机化合物的质量与待配备该至少一种可氧化的有机化合物的氧化银层的面积的比例越大。
为了制造共同的接触面，将元件各自以其金属接触表面放置到银烧结件的配备有所述至少一种可氧化的有机化合物的所涉氧化银表面上。金属接触表面的重叠区域或其与所涉氧化银表面的面积部分在此定义共同的接触面。
最后，由至少两个元件与位于其间的具有配备有至少一种可氧化有机化合物的氧化银表面的银烧结件制成的组合件经受加压烧结过程。
实际的加压烧结在例如200至280℃的目标温度和例如1至小于40 MPa，优选5至20MPa的工艺压力下进行。烧结时间为例如1至5分钟。
如果仅根据所述方法的实施方案(II)操作，加压烧结可在没有特别限制的气氛中进行，但除了其不同于在实施方案(I)中主导的气氛之外。例如，在实施方案(II)中，可以主导的是含氧气的气氛，或者是不含氧气的气氛。不含氧气的气氛在本发明中被理解为是指气氛，特别是惰性气体气氛，其例如由氮气和/或氩气构成，其氧气含量不大于500 ppm，优选不大于10 ppm，还更优选不大于1 ppm。
所述加压烧结在适合于加压烧结的传统装置中进行，其中可设定上述工艺参数。
实施例和应用实例1
在聚四氟乙烯薄膜形式的载体基材上，以100 µm的湿层厚度借助模板印刷施加银烧结糊料（Heraeus Materials Technology的ASP 043-04P2）的10 x 10 mm2大的层，然后在循环空气干燥箱中在250℃的目标温度下烧结30分钟。
将经烧结的产品小心地借助抽吸吸管从载体基材上脱离，获得独立的层状银烧结体。
在不锈钢容器中预先放置10重量%的碳酸钠水溶液，将该不锈钢容器与10 V 直流电压源的阴极相连。该电压源的阳极与独立的层状银烧结体相连，将后者浸入碳酸钠溶液中30秒。
在取出后，将该独立的层状银烧结体的由于阳极氧化而变黑的表面用去离子水冲洗并干燥。随后，将一滴2重量% 在ExxsolTM D60中的月桂酸溶液添加到氧化银表面的前侧和后侧上，均匀分散并在70℃下在循环空气干燥箱中干燥。此后，将由此配备有月桂酸的银烧结体接合在相应的DCB基材的金表面和10 x 10 mm2 大的IGBT的银接触面之间，并将由此获得的夹层组合件在250℃的目标温度下和20 MPa的机械压力下在烧结压机中烧结120秒。
在烧结后，通过剪切强度测定粘附性。在此，将元件用剪切凿以0.3 mm/s的速度在20℃下剪断（abgeschert）。借助测力传感器记录所述力（DAGE, 德国公司的DAGE 2000仪器）。表1展示了通过实施例1获得的结果。
表1
实施例 1
剪切强度（N/mm2） 31

Claims (16)

1.制造具有氧化银表面的层状银烧结体形式的银烧结件的方法，其包括下列步骤：
(1) 将银烧结制剂施加到具有不能形成烧结接合的表面的载体基材上，
(2) 烧结如此施加的银烧结制剂，
(3) 将在步骤(2)中形成的层状银烧结体从所述载体基材的表面脱离，以及
(4) 任选地在步骤(3)之后的氧化步骤过程中制造或增强所述层状银烧结体的整个或部分外表面上的氧化银层。
2.根据权利要求1的方法，其中所述层状银烧结体的层厚度为10至300 µm。
3.根据权利要求1或2的方法，其中所述具有不能形成烧结接合的表面的载体基材选自氧化铝陶瓷、镍片、聚酰亚胺薄膜、聚四氟乙烯薄膜和硅酮薄膜。
4.根据前述权利要求任一项的方法，其中所述银烧结件作为连续产品存在。
5.根据前述权利要求任一项的方法，其中所述银烧结件具有前侧和后侧，它们分别具有氧化银表面。
6.根据前述权利要求任一项的方法，其中所述氧化银层或氧化银表面通过空气接触形成或通过化学方式借助氧化剂或通过阳极氧化制造或增强。
7.根据前述权利要求任一项的方法制成的银烧结件在用于接合元件的方法中的用途，在所述方法中提供由至少两个各自具有金属接触表面的元件和设置在这些元件之间的银烧结件制成的组合件并将该组合件进行加压烧结，其中所述银烧结件的氧化银表面与所述元件的金属接触表面各自形成共同的接触面，且其中(I)所述加压烧结在含有至少一种可氧化的化合物的气氛中进行，和/或(II)所述氧化银表面在形成各自共同的接触面之前配备有至少一种可氧化的有机化合物。
8.根据权利要求7的用途，其中所述元件是用于电子业中的零件。
9.根据权利要求7或8的用途，其中所述待接合的元件的金属接触表面的金属相同或不同，并选自银、铜、钯和这些金属的合金。
10.根据权利要求7至9任一项的用途，其中所述至少两个元件中至少之一的金属接触表面具有金属氧化物层。
11.根据权利要求10的用途，其中所述至少两个元件中至少之一的金属氧化物层在形成共同的接触面之前配备有至少一种可氧化的有机化合物。
12.根据权利要求7至11任一项的用途，其中所述至少一种可氧化的有机化合物具有1至50个碳原子并具有至少一个官能团。
13.根据权利要求7至10或12任一项的用途，其中所述至少一种可氧化的有机化合物的质量与所涉氧化银层的面积的比例为0.0005至10 g/平方米氧化银面积。
14.根据权利要求7至13任一项的用途，其中所述至少一种可氧化的有机化合物选自游离的脂肪酸、脂肪酸盐和脂肪酸酯。
15.根据权利要求7至14任一项的用途，其中所述至少一种可氧化的有机化合物由含水制剂或由有机溶剂中的制剂施加到所述氧化银层上。
16.根据权利要求15的用途，其中所述制剂是溶液、分散液或悬浮液。
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