470734 經濟部智慧財產局員工消費合作社印製 A7 B7 _五、發明説明（1 ) ' 發明背景 1 .發明範疇 本發明有關一種於陶瓷基材上塗覆銅膜之方法，尤其 有關一種於銅膜和陶瓷基材表面間提供改善之粘著性之方 法，該基材於銅膜形成前不進行任何糙化處理。 2 .先前技藝揭示 曰本專利早期公告〔1(01(0〇〕第63 — 4 336及 3 — 6 9 1 9 1號提出一種不於形成銅膜前於基材表面上 進行糙化處理而於陶瓷基材上形成銅膜之方法。 前一種先前技藝（第6 3 — 4 3 3 6號）中，於陶瓷 基材表面上施用包含至少一種選自銅、鋅、鎘、鉍及鉛中 者之漿液，形成底塗層。於介於3 5 0°C及9 0 0 °C間之 溫度下非氧化氣氛中加熱塗底塗層之基材沈澱底塗層之金 屬或合金顆粒後，藉包含鈀及/或鈉離子之溶液處理，以 鈀及/或鉑置換金屬或合金顆粒表面。之後，藉無電電鍍 於陶瓷基材上經處理之底塗層上形成鎳、鈷或銅之金屬膜 。但是，先前技藝說明書顯示其實例所確定之銅膜最佳粘 合強度僅有 2. 75kg/5mm<^，良P，0. 56kg/4 m m 2 。需進一步改善銅膜之粘著強度。 後一種先前技藝（No. 3-6919 1)中，藉無 電電鍍於諸如氧化鋁等陶瓷基材上形成厚度介於0 . 5 及2 間之銅底塗層。經底層塗覆之基材於介於 3 0 0 X及9 0 0 °C間之溫度下氧化氣氛中加熱，於陶瓷 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 ： ---------裝 I —訂— — — —I,線 (請先閲讀背面之注意事項再填寫本頁) -4 - 470734 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（2 ) 基材上形成氧化銅層。氧化銅層於介於2 0 0。(：及9 0 0 °C間之溫度下於還原氣氛中加熱；將氧化銅層還原成金屬 銅層。藉無電電銨於金屬銅層上形成厚度介於〇. 5//m 及2 Aim間之銅膜’亦藉電鍍於銅膜上形成額外銅膜，得 到所需厚度。但是，此法中，金屬銅層與銅膜間之粘著強 度無法充分改善’因爲金屬銅層對無電電鍍所用之電鍍液 之潤溼性差。此外，因爲需於高溫下控制還原氣氛，形成-金屬銅層，故需昂貴且特殊之爐具。 發明概述 本發明有關一種於陶瓷基材上形成銅膜之方法。即， 於陶瓷基材上形成包含銅之底塗層，於氧化氣氛中熱處理 得到氧化銅層。具有氧化銅層之基材浸入還原溶液浴中， 將氧化銅層還原成金屬銅層。之後，藉（例如）無電電鍰 於金屬銅層上形成銅膜，得到所需厚度。較佳於介於2 0 °c及1 〇 〇 °c間之溫度下，藉諸如氫化硼鹽，二甲胺硼烷 ，次磷酸鹽等還原溶液還原氧化銅層。因爲以還原溶液還 原氧化銅層所形成之金屬銅層對無電電鍍所用之電鍍溶液 顯示良好潤溼性，故銅膜與金屬銅層間之粘著性較於高溫 ，例如介於2 0 0 °C及9 0 0 °C間之溫度，下還原氣氛中 還原氧化銅層形成金屬銅層者高。此外，應注意不需使用 於高溫下控制還原氣氛之昂貴特殊爐具，即可使用充填於 浴中之還原溶液輕易且均勻地於陶瓷基材上還原整體氧化 銅層。 因此，本發明主要目的是提供一種形成對陶瓷基材具 (請先閱讀背面之注意事項再填寫本頁) 裝. -s 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐·） -5 - 470734 經濟·部智慧財產局員工消費合作社印製 A7 B7五、發明説明（3 ) 有優越粘著性之銅膜。 本發明較佳實例中’底塗層包含於陶瓷基材表面形成 之銅和祕其中之一者之第一層底塗層，及於第一層底塗層 上形成另一種銅和鉍之第二底塗層。尤其，藉無電電鍍於 陶瓷基材上形成第一層銅底塗層較佳。當底塗層包含鉍時 ，金屬銅層與陶瓷基材間之粘著性較佳，可降低熱處理之 溫度範圍。較佳賓例可使甩釩取代鉍。 另外較佳者係使用經乙二胺螯合劑處理之銅粉形成底 塗層。螯合劑處理於銅粉表面中顯示銅之螯合化合物。因 爲螯合化合物防止於底塗層氧化時形成過量氧化銅（ C u 0 )，故可以還原溶液有效均勻地還原氧化銅層。 熟習此技藝者可由以下列發明詳述及發明較佳實例明 瞭本發明上述及其他特色及優點。 附圖簡述 圖1 A至1. F爲明瞭本發明於陶瓷基材上形成銅電路 圖型之方法之示意圖； 圖2 A至2 F爲說明另一種本發明於陶瓷基材上形成 銅電路圖型之方法的示意圖；且 圖3爲說明於陶瓷上形成之銅膜之粘著性試驗的示意 圖。. 元件符號之說明 1，1A:陶瓷基材 20:第二層鉍之底塗層 2，2A:銅膜（銅電路圖型）2 0A:第二層銅之底塗層 _3 :塗錫銅線 2 1 :氧化鉍層 本纸張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐) ' ---------- 裝-------訂------線 (請先閲讀背面之注意事項再填寫本頁) 470734 經濟/部智慧財產局員工消費合作社印製 A7 __ B7 _ 五、發明説明（4 ) 10，10A:第一層銅底塗層 21A:氧化銅層 1 1 :氧化銅層 22A:金屬銅層 11A:氧化鉍層 30，30A:額外銅層 1 2 :金屬銅層 F :拉拔方向 發明詳述 本發明於陶瓷基材上形成銅膜之方法可分成下列四個 步驟，以製造步驟之順序說明。 〔1〕於陶瓷基材上形成包含銅之底塗層 例如，諸如氧化銅、氧化锆、鈦酸鋇，或堇青石（ cordierite)等氧化物陶瓷，諸如氮化砂或氮化鋁等氮化 物陶瓷，或諸如碳化矽等碳化物陶瓷可於本發明中充作陶 瓷基材。可藉施加樹脂酸銅漿液於陶瓷基材上，藉濺射銅 ，或藉銅之無電電鍍形成僅含銅金屬元素之底塗層。尤其 採用無電電鍍較佳。或者，可於陶瓷基材上形成含有鉍、 釩及其混合物中之一.者之底塗層。含銅和鉍之底塗層可藉 於陶瓷基材上施加銅及鉍之樹脂酸鹽漿液之混合物，或藉 於陶瓷基材上施加銅及鉍其中之一之第一種樹脂酸鹽漿液 形成第一層底塗層，並於_第一層底塗層上施加另一者之第 二種樹脂酸鹽漿液得到第二層底塗層。本發明方法所用之 金屬之樹脂酸鹽漿液定義爲包含金屬之.有機金屬化合物之 漿液。例如，銅之樹脂酸鹽漿液爲包含銅之有機金屬化合 物之漿液。可藉濺射或無電電鍍形成第一及第二層底塗層 。尤其藉無電電鍍於陶瓷基材上形成第一層銅底塗層爲佳 。若使用樹脂酸鉍漿液，則樹脂酸鹽漿液中鉍含量較佳爲 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X 297公釐') ~ ----------裝------訂------^ (請先閲讀背面之注意事項再填寫本頁) 470734 A7 B7 經濟·部智慧財產局員工消費合作社印製 五、發明説明（5 ) I 〇w t%或更高》底塗層厚度較佳介於〇 . 0 5至 〇. 3 //m間。樹脂酸釩漿液可用於取代樹脂酸鉍漿液形 成含銅及釩之底塗層。 〔2〕底塗層之氧化 上述步驟〔1〕所形成之底塗層於氧化氣氛中熱處理 ，氧化底塗層。例如，於介於8 5 0 °C及1 1 0 0°C間之 氧化溫度下於空氣中氧化銅之底塗層，於陶瓷基材上形成-氧化銅層。當氧化溫度低於8 5 0 °C時，無法於氧化期間 於氧化銅和陶瓷基材間形成反應層。當氧化溫度高於 II 0 0°C時，底塗層之銅蒸發或擴散至陶瓷基材內，故 陶瓷基材表面上無法形成足量氧化銅。若使用含有釩、鉍 及其混合物其中之一者之底塗層，則可降低氧化溫度。例 如，銅及鉍之底塗層可於介於6 0 0 °C及1 1 0 0°C間之 氧化溫度下於空氣中氧化，得到銅及鉍氧化物。即使形成 底塗層之方式係將第一層銅底塗層排列於陶瓷基材與第二 層鉍底塗層間，但因第二層底塗層之鉍於氧化時向陶瓷基 材擴散，故於底塗層表面中形成氧化銅層。當氧化溫度低 於6 0 0 °C時，無法於氧化期間充分形成介於氧化鉍與陶 瓷基材間之反應層。氧化溫度高於1 1 0 0 °C時，氧化鉍 蒸發，故無法使足量氧化鉍與陶瓷基材反應。若使用銅及 釩之底塗層，則較佳於介於4 5 0 °C及6 2 Ο Λ：間之氧化 溫度下於空氣中氧化底塗層。 〔3〕氧化銅層之還原 步驟〔2〕所得之氧化銅層於還原溶液浴中還原得到 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐) -----------^-------,玎------^ (請先閲讀背面之注意事項再填寫本頁) -8 - 470734 A7 B7 經濟'部智慧財產局員工消費合作社印製470734 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 _V. Description of the Invention (1) 'Background of the Invention 1. Field of the Invention The present invention relates to a method for coating a copper film on a ceramic substrate, and more particularly to a method for coating a copper film and A method for providing improved adhesion between the surfaces of ceramic substrates, which is not subjected to any roughening treatment before the copper film is formed. 2. The prior art reveals that the early publication of this patent [1 (01 (0〇) No. 63-4336 and 3-6119 1 No. 1 proposes a method of roughening the surface of a substrate before forming a copper film. A method for forming a copper film on a ceramic substrate. In the former prior art (No. 6 3-4 3 3 6), the surface of the ceramic substrate is applied with at least one selected from the group consisting of copper, zinc, cadmium, bismuth and lead. To form an undercoat layer. After heating the basecoat substrate to deposit the metal or alloy particles in the non-oxidizing atmosphere at a temperature between 350 ° C and 900 ° C, Treatment with a solution containing palladium and / or sodium ions, replacing the surface of metal or alloy particles with palladium and / or platinum. Afterwards, electroless plating is used to form a metal of nickel, cobalt or copper on the treated undercoat on a ceramic substrate However, the prior art specification shows that the optimum adhesion strength of the copper film determined by its examples is only 2.75kg / 5mm < ^, good P, 0.56kg / 4 mm2. The adhesion strength of the copper film needs to be further improved In the latter prior art (No. 3-6919 1), electroless plating is applied to a ceramic substrate such as alumina Into a copper base coating with a thickness between 0.5 and 2. The base coated substrate is heated in an oxidizing atmosphere at a temperature between 300 X and 900 ° C, at the ceramic paper size Applicable to China National Standard (CNS) A4 specification (210X297mm>: --------- install I — order — — — — I, line (please read the precautions on the back before filling this page) -4 -470734 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (2) A copper oxide layer is formed on the substrate. The copper oxide layer is between 200 and 200 ° C (and 90 ° C). Heating in a reducing atmosphere; reducing the copper oxide layer to a metal copper layer. Forming a copper film with a thickness between 0.5 // m and 2 Aim on the metal copper layer by means of electroless ammonium; An additional copper film is formed on the substrate to obtain the desired thickness. However, in this method, the adhesion strength between the metal copper layer and the copper film cannot be improved sufficiently because the metal copper layer has poor wettability to the plating solution used for electroless plating. In addition, Because the reducing atmosphere needs to be controlled at a high temperature to form a metallic copper layer, an expensive and special stove is required. The invention relates to a method for forming a copper film on a ceramic substrate. That is, an undercoat layer containing copper is formed on the ceramic substrate, and the copper oxide layer is obtained by heat treatment in an oxidizing atmosphere. The substrate with the copper oxide layer is immersed in a reducing solution bath. The copper oxide layer is reduced to a metal copper layer. After that, a copper film is formed on the metal copper layer by, for example, electroless electricity to obtain a desired thickness. It is preferably between 20 ° c and 100 ° c. At intermediate temperatures, the copper oxide layer is reduced by a reducing solution such as a borohydride salt, dimethylamine borane, hypophosphite and the like. Because the metal copper layer formed by reducing the copper oxide layer with a reducing solution shows good wettability to the electroplating solution used for electroless plating, the adhesion between the copper film and the metal copper layer is higher than high temperature, such as between 20 ° C And a temperature between 9 0 ° C, the reduction of the copper oxide layer in the lower reducing atmosphere to form a metal copper layer is higher. In addition, it should be noted that instead of using expensive special stoves that control the reducing atmosphere at high temperature, the entire copper oxide layer can be easily and uniformly reduced on the ceramic substrate using the reducing solution filled in the bath. Therefore, the main object of the present invention is to provide a ceramic substrate (please read the precautions on the back before filling this page). -S The size of this paper is applicable to Chinese National Standard (CNS) A4 (210 X 297) ··) -5-470734 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and Ministry of Economic Affairs 5. Description of the invention (3) Copper film with superior adhesion. In the preferred embodiment of the present invention, the 'undercoat layer' includes a first layer of copper and one of the first layer of copper formed on the surface of the ceramic substrate, and another layer of copper and bismuth formed on the first layer of the bottom layer. Second base coating. In particular, it is preferred to form a first copper undercoat layer on a ceramic substrate by electroless plating. When the priming layer contains bismuth, the adhesion between the metallic copper layer and the ceramic substrate is better, which can reduce the temperature range of the heat treatment. A preferred example is to replace vanadium with vanadium. It is also preferable to use copper powder treated with an ethylenediamine chelator to form an undercoat layer. Chelating agents show copper chelating compounds on the surface of copper powder. Since the chelate compound prevents excessive copper oxide (Cu 0) from being formed when the undercoat layer is oxidized, the reducing solution can effectively and uniformly reduce the copper oxide layer. Those skilled in the art can clarify the above and other features and advantages of the present invention with the following detailed description and preferred embodiments of the invention. Brief Description of the Drawings Figures 1 A to 1. F are schematic diagrams illustrating a method for forming a copper circuit pattern on a ceramic substrate according to the present invention; Figures 2 A to 2 F are diagrams illustrating another method for forming a copper circuit pattern on a ceramic substrate according to the present invention A schematic diagram of the method; and FIG. 3 is a schematic diagram illustrating an adhesion test of a copper film formed on a ceramic. Explanation of component symbols 1, 1A: ceramic substrate 20: second layer of bismuth undercoat layer 2, 2A: copper film (copper circuit pattern) 2 0A: second layer of copper undercoat layer _3: tin-coated copper Line 2 1: Bismuth oxide layer The paper size is applicable to China National Standard (CNS) A4 specification (2 丨 0X297 mm) '---------- installed ------- order --- --- line (Please read the precautions on the back before filling this page) 470734 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy / Ministry A7 __ B7 _ V. Description of Invention (4) 10, 10A: The first layer of copper primer Layer 21A: copper oxide layer 1 1: copper oxide layer 22A: metal copper layer 11A: bismuth oxide layer 30, 30A: additional copper layer 1 2: metal copper layer F: drawing direction Detailed description of the invention The invention is on a ceramic substrate The method of forming a copper film can be divided into the following four steps, which will be explained in the order of manufacturing steps. [1] An undercoat layer containing copper is formed on a ceramic substrate, for example, an oxide ceramic such as copper oxide, zirconia, barium titanate, or cordierite, and a nitride such as sand nitride or aluminum nitride Ceramics, or carbide ceramics such as silicon carbide, can be used as a ceramic substrate in the present invention. An undercoat containing only copper metal elements can be formed by applying a resin acid copper slurry on a ceramic substrate, by sputtering copper, or by electroless plating of copper. Especially, electroless plating is preferred. Alternatively, an undercoat layer containing one of bismuth, vanadium, and mixtures thereof may be formed on the ceramic substrate. The base coating containing copper and bismuth can be formed by applying a mixture of copper and bismuth resinate slurry on a ceramic substrate, or by applying a first resinate slurry of copper and bismuth on a ceramic substrate. The first layer of the undercoat layer is applied to the first layer of the undercoat layer to obtain a second layer of the undercoat layer. A resinate slurry of a metal used in the method of the present invention is defined as a slurry of a metal. Organometallic compound. For example, a copper resinate slurry is a slurry of an organometallic compound containing copper. The first and second undercoat layers can be formed by sputtering or electroless plating. In particular, it is better to form the first copper undercoat layer on the ceramic substrate by electroless plating. If a resin acid bismuth slurry is used, the bismuth content in the resin acid salt slurry is preferably suitable for the paper size. National National Standard (CNS) A4 Specification (210X 297 mm ') ~ ---------- Packing ------ Order ------ ^ (Please read the notes on the back before filling out this page) 470734 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy and Economy 〇wt% or higher》 The thickness of the undercoat layer is preferably between 0.05 to 0.3 // m. The vanadium resin acid slurry can be used to replace the bismuth resin acid slurry to form a base coating containing copper and vanadium. [2] Oxidation of the undercoat layer The undercoat layer formed in the above step [1] is heat-treated in an oxidizing atmosphere to oxidize the undercoat layer. For example, an undercoat layer of copper oxide in the air at an oxidation temperature between 850 ° C and 110 ° C forms a copper oxide layer on a ceramic substrate. When the oxidation temperature is lower than 850 ° C, a reaction layer cannot be formed between the copper oxide and the ceramic substrate during the oxidation. When the oxidation temperature is higher than II 0 0 ° C, the copper of the undercoat layer evaporates or diffuses into the ceramic substrate, so a sufficient amount of copper oxide cannot be formed on the surface of the ceramic substrate. If an undercoat containing one of vanadium, bismuth and mixtures is used, the oxidation temperature can be reduced. For example, the base coating of copper and bismuth can be oxidized in air at an oxidation temperature between 600 ° C and 110 ° C to obtain copper and bismuth oxides. Even though the way to form the undercoat layer is to arrange the first copper undercoat layer between the ceramic substrate and the second bismuth undercoat layer, since the bismuth of the second undercoat layer diffuses to the ceramic substrate during oxidation, Therefore, a copper oxide layer is formed in the surface of the undercoat layer. When the oxidation temperature is lower than 600 ° C, a reaction layer between bismuth oxide and a ceramic substrate cannot be sufficiently formed during the oxidation. When the oxidation temperature is higher than 110 ° C, bismuth oxide evaporates, so a sufficient amount of bismuth oxide cannot react with the ceramic substrate. If a base coat of copper and vanadium is used, it is better to oxidize the base coat in air at a temperature between 450 ° C and 6 2 0 Λ :. [3] The reduction step of the copper oxide layer [2] The copper oxide layer obtained in the reduction solution bath is reduced to obtain the paper size applicable to Chinese national standards (CNS> A4 specification (210X297 mm) --------- -^ -------, 玎 ------ ^ (Please read the notes on the back before filling out this page) -8-470734 A7 B7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy
五、發明説明（6 ) 金屬銅層。較佳於介於2 0。(：及1 0 0°C間之還原溫度下 進行還原。因爲所得之金屬銅層對無電電鍍使用之電鍍溶 液之潤溼性良好’可於無電電鍍期間提供更多之銅成核部 位。因此’本發明方法中，不需於銅無電電鍍前以包含鈀 及/或鉑離子之溶液處理具有金屬銅層之陶瓷基材。至於 還原溶液’可使用氫化硼鹽 '次磷酸鹽、二甲胺硼烷等溶 液。尤其當還原溶液係二甲胺硼烷時，可於介於3 0°(：及-5 0°C間之還原溫度下進行還原。當還原溶液爲氫化硼鹽 時’可於介於5 0°C及8 0°C間之還原溫度下進行還原。 〔.4〕於金屬銅層上之銅塗層 於金屬銅層上塗覆銅，而於陶瓷基材上得到具所需厚 度之金屬銅層。塗覆銅之方法實例可應用無電電鍍、電鍍 或濺射銅。 根據上述步驟〔1〕至〔4〕，於陶瓷基材上形成銅 電路圖型2之方法說明如下。.例如，如圖1 A及1 B所示 ，於陶瓷基材上沿電路圖型形成第一層銅底塗層1 0，之 後於第一層底塗層.10.之電路圖型及未形成第一層底塗層 1 0之陶瓷基材曝露區上形成第二層鉍之底塗層2 0。氧 化步驟（2 )中，第一層底塗層1 〇之銅氧化，於電路圖 形表面中形成氧化銅層11 ，如圖1C所示。另一方面’ 亦氧化第二層底塗層2 0之鉍，而於陶瓷基材1上及氧化 銅層1 1與陶瓷基材1之間形成氧化鉍層2 1。氧化鉍層 21可用於改善氧化銅層11與陶瓷基材1間之粘著性。 氧化銅層1 1以還原液還原成金屬銅層1 2後’如圖1 D nn· I, 111 I I n .1....- !、1TI— n n» 踩 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐) 470734 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（7 ) 所示，藉無電電銨於金屬銅層1 2上形成額外銅層3 〇。 氧化鉍層2 1不被還原步驟〔3〕所還原。因爲該額外銅 層3 0非於無電電鍍期間澱積於氧化鉍層2 1上’如圖 1 E所示，陶瓷基材1之曝露區上之氧化鉍層2 1可充作 無電電鍍之遮蔽圖型。氧化鉍層2 1可藉酸溶液触刻而輕 易去除，得到於陶瓷基材1上之銅電路2，如圖1F所示。 或者，可依下述方法於陶瓷基材1 A上形成銅電路圖-型2 A。即，如圖2 A及2 B所示，於陶瓷基材1 A之表 面上形成第1層鉍之底塗層1 0 A，之後沿電路圖型於第 一層底塗層1 Ο A上形成第二層銅之底塗層2 Ο A。氧化 步驟〔2〕中，於第二層底塗層2 0A中形成氧化銅層 2 1 A，於陶瓷基材1 A上及氧化銅層2 1 A與陶瓷基材 1A間形成氧化鉍層1 1A，如圖2C所示。氧化銅層· 2 1 A以還原液還原成金屬銅層2 2 A後，如圖2 D所示 ，藉無電電鍍於金屬銅層2 2A上形成額外銅層3 0A， 如圖2 E所示。額外銅層3 Ο A不澱積於未形成金屬銅層 2 2 A之電路圖型之氧化鉍層1 1 A曝露區上。曝露區之 氧化鉍層1 1 A可藉酸溶液蝕刻而輕易移除，得到位於陶 瓷基材1A上之銅電路圖型2A，如圖2F所示。 另一方面，於陶瓷基材上沿電路圖型形成銅之底塗層 時，較佳於氧化步驟〔2〕前，於未形成銅底塗層之陶瓷 基材曝露區上施加或噴灑包含燒結溫度高於1 1 〇 〇°c之 無機粉末之遮掩塗料。例如，可於曝露區上噴灑包含氧化 鋁或氧化鉻粉末之無機粉末及甲基纖維素粘合劑之遮掩塗 I------- t------、玎------0 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中.國國家標準（CNS ) A4規格（210'/297公釐.） -10 - 470734 A7 B7 經濟/部智慧財產局員工消費合作社印製 五、發明説明（8 ) 料。或者’可藉篩印印刷該遮掩塗料於曝露區上。結果， 其可於氧化步驟〔2〕中防止由底塗層蒸發之銅澱積於曝 露區上。氧化步驟後，可藉超音波清潔法由陶瓷基材之曝 露區移除遮掩塗料β 使用銅漿液形成第一或第二層底塗層時，銅漿液較佳 使用經乙二胺螯合劑處理之銅粉。此情況下，於銅粉表面 中形成銅之螯合物。因爲銅螯合物於氧化步驟〔2〕中防-止形成過量C u 0形式之氧化銅，故可藉還原步驟〔3〕 輕易且均勻地提供金屬銅層。可採用乙二胺四乙酸，乙二 胺二乙酸’乙二銨四乙酸鈉等充作螯合劑。以螯合劑處理 銅粉時’銅粉可浸入螯合劑浴中，或螯合劑可噴灑於銅粉 上。尤其》較佳銅之第一層底塗層藉無電電鍍由含螯合劑 之銅電鍍液澱積於陶瓷基材上，或使用包含由銅電銨液澱 積之銅粉之漿液形成第一層或第二層底塗層。 實施例1 — 5 如表1所示，製備氧化鋁、氮化鋁、鈦酸鋇、碳化矽 ，及氧化锆之陶瓷基材。基本上由2重量份數樹脂酸鉍漿 液（B i含量：2 0 % )及8重量份數樹脂酸銅漿液（ C u含量：6 % )所組成之混合樹脂酸鹽槳液藉篩印法印 刷於個別陶瓷基材表面上，得到混合漿液之電路圖型及陶 瓷基材曝露區。陶瓷基材於篩印前皆未進行任何糙化處理 。經印刷之基材於1 2 5 °C乾燥1 〇分鐘後，於8 5 0 °C 溫度下之空氣中熱處理1小時，於電路圖型表面中形成氧 化銅層。氧化銅層藉將具有氧化銅層之陶瓷基材浸於溫度 ^ I I I 訂 I¼ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐） ~ 11 - 470734 A7 B7 五、發明説明（9 ) 8 0°C之硼氫化鈉水溶液浴中5分鐘而還原成金屬銅層。 水溶液p Η爲12.5。藉無電電鍍於金屬銅層上形成額外銅 層，沿陶瓷基材上之電路圖型得到厚約1 0 //m之銅膜。 進行粘著性試驗測量銅膜與陶瓷基材間之粘著強度。 即’如圖3所示，直徑0· 7mm之塗鍚銅線3焊接於陶 瓷基材1上所形成之具有2 m X 2 mm正方面積之銅膜2 上。沿如圖1箭頭F所示方向拉拔銅線3時，藉由陶瓷基-材1去除銅膜2所需之力決定粘著強度。實例1至5之粘 著性試驗結果列於表1。 表 1 (請先閱讀背面之注意事項存填寫本貫〕 装· 經濟部智慧財產局員工消費合作社印製 陶瓷基材 粘著強度 (/ 4mm2 ) 實例1 氧化鋁 4. 5 實例2 氮化鋁 4. 3 實例3 鈦酸鋇 4.6 實例4 碳化矽 4. 2 實例5 氧化鉻 4. 4 訂 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐'） 470734 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（ίο ) 實施例6—14 表2所列之陶瓷基材各浸於包含鈀離子之溶液浴中。 藉無電電鍍於陶瓷基材表面上形成第一層銅底塗層。實例 6 - 1 0中，於氧化鋁陶瓷基材上形成具不同厚度之第一 層底塗層。陶瓷基材表面於以鈀溶液處理前不進行任何糙 化處理。第一層底塗層沿預定圖型蝕刻得到其電路圖型及 陶瓷基材曝露區。樹脂酸鉍漿液（B i含量：20%)藉-篩印印刷於第一層底塗層之電路圖型及陶瓷基材曝露區上 ，形成第二層鉍底塗層。經印刷之基材於約1 2 5 °C乾燥 1. 0分鐘，於8 5 0 °C溫度之空氣中熱處理1小時，於第 二層底塗層表面中沿電路圖型形成氧化銅層。同時，第二 層底塗層之鉍氧化形成氧化鉍層。氧化銅層藉浸漬具氧化 銅層之陶瓷基材於溫度8 0°C之硼氫化鈉以溶液浴中5分 鐘而還原成金屬銅層。以溶液PHI 2. 5。藉無電電鍍 於金屬銅層上形成額外銅層，得到沿陶瓷基材上電路圖型 之厚約1 〇 # m之銅膜。於陶瓷基材曝露區上氧化鉍層上 不形成額外銅層。結果,顯示陶瓷基材曝露區上形成之第二 層鉍之底塗層可影響無電電鍍之遮蔽圖型。無電電鍍後， 曝露區上之氧化鉍層藉酸液蝕刻。 實例6至1 4中，依實例1之粘著性試驗測量銅膜與 陶瓷基材間之粘著強度。粘著性試驗之結果列於表2中。 ----_---n I 裝 n —-訂 線 (請先閱讀背面之注意事項再填寫本頁) 本紙浪尺度適用中國國家標準（CNS ) A4規格（210 X 297公嫠） -13 - 470734 A7 B7 五、發明説明（11 ) 表 2 經濟'部智慧財產局員工消費合作社印製 陶瓷基材 第一層底塗層 粘著強度 厚度（// m ) (kg / 4mm2) 實例6 氧化銘 0.05 5. 2 實例7 氧化鋁 0.5 5. 5 實例8 氧化鋁 1 . 0 5. 0 實例9 氧化銘 2.0 4. 8 實例10 氧化鋁 3. 0 4. 5 實例11 氮化鋁 0. 5 5. 5 實例1 2 鈦酸鋇 0.5 5.7 實例13 碳化砂 0.5 4. 9 實例14 氧化锆 0. 5 5.1 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐·） -14 - 470734 A7 _ B7五、發明説明（12 ) 實施例1 5 - 2 4 於表3所列之各陶瓷基材表面上形成第一層鉍之底塗 層。實例1 5 — 1 9中，藉篩印於陶瓷基材表面印上樹脂 酸鉍漿液（B i含量：2 0%)形成第一層底塗層。實例 2 0 — 2 4中，陶瓷基材浸入包含鈀離子之溶液浴中後， 於陶瓷基材表面上進行鉍之無電電鍍，形成第一層底塗層 。陶瓷基材表面於篩印或以鈀溶液處理前未進行任何糙化_ 處理。於第一層底塗層上沿預定電路圖型印上樹脂酸銅漿 液（Cu含量：6%)，於第一層底塗層上得到第二層銅 底塗層。印刷基材於8 5 0 °C空氣中熱處理1小時於第二 層底塗層表面中形成氧化銅層。同時，第一層底塗層之鉍 氧化形成氧化鉍層。藉浸漬具氧化銅層之陶瓷基材於溫度 8 0°C之硼氫化鈉以溶液浴中5分鐘而將氧化銅層還原成 金屬銅層，水溶液P Η爲1 2 · 5。 丨.------^---裝------訂 银 (請先閲讀背面之注意事項再填寫本頁) 經濟/部智慧財產局員工消費合作社印製 本紙張尺度適用中.國國家標準（CNS ) Α4規格（210 X 297公釐) 470734 A7 B7 五、發明説明（l3 ) 表 3 經濟部智慧財產局員工消費合作社印製 陶瓷基材 形成第一層底 塗層方法 粘著強度 (kg / 4mm2 ) 實例1 5 氧化鋁 樹脂酸鹽漿液 5.0 實例16 氧化鋁 樹脂酸鹽漿液 4.9 實例17 鈦酸鋇 樹脂酸鹽漿液 5. 3 實例18 碳化矽 樹脂酸鹽漿液 4.8 實例19 氧化锆 樹脂酸鹽漿液 5. 2 實例20 氮化鋁 電鍍 4. 4 實例21 氧化1呂 電鍍 4.3 實例22 鈦酸鋇 電鍍 4. 6 實例23 碳化砂 電鍍 4.2 實例2 4 氧化锆 電鍍 4.9 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐’） -16 470734 A7 B7 _____五、發明説明（14 ) /藉無電電鍍於金屬銅層上形成額外銅層’沿陶瓷基材 上之電路得到厚約1 0 之銅膜。未形成第二層底塗層 之氧化鉍層曝露區上不形成額外銅層。事實顯示第一層鉍 底塗層可充作無電電鍍之遮蔽圖型。無電電鍍後，曝露區 之氧化鉍層藉酸液蝕刻。 依實例1之粘著性試驗方式測量實例1 5至2 4之銅 膜與陶瓷基材間之粘著強度。粘著性試驗結果列於表3中-〇 實例2 5至2 8 依基本上同於實例7之方法於氧化鋁陶瓷基材上形成 實例2 5至2 8之約1 0 /zm厚度之銅膜，不同處係使用 具不同鉍含量之樹脂酸鉍漿液形成第二層鉍之底塗層’如 表4所列。 ---------裝------訂 故 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐’） _ 17 _ 470734 A7 B7 五、發明説明（is ) 表 4 陶瓷基材 第二層底塗層 中之B i含量 (w t % ) _ -----^ 粘著強度 (kg /4mm2) 實例25 氧化鋁 15 5. 4 實例26 氧化鋁 12 4.8 實例27 氧化鋁 1 0 2. 5 實例28 氧化鋁 5 1. 5 H. ---- - If j H - - ..... I — IT n ! -- »1 I I—- - - -1 - -.11 I I ---- - HI _ (請先閱讀背面之注意事項再填寫本頁) 經濟·部智慧財產局員工消費合作社印製 依實例1之粘著性試驗方式測量實例2 5至2 8之銅 膜與陶瓷基材間之粘著強度。粘著性試驗結果列於表4上 。由該粘著性試驗之結果得知樹脂酸鹽漿液中鉍含量較佳 1 0 w t %或更高，以得到更佳之粘著強度。 實施例29-32 依實質上同於實例15之方法於氧化鋁陶瓷基材上形 成實例29 — 3 2之約1 Oem厚之銅膜，不同處係於表 5所列之不同溫度及時間條件下進行於空氣中之熱處理。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐·) 470734 A7 B7 五、發明説明（ie ) 依實例1之粘著性試驗方式測量實例2 9至3 2之銅 膜與陶瓷基材間之粘著強度。粘著性試驗結果列於表5中 經濟 +部智慧財產局員工消費合作社印製 表 5 陶瓷基材 熱處理之條件 溫度.時間 (°C ) (min) 粘著強度 (kg /4mm2) 實例29 氧化鋁 600 60 4.0 實例30 氧化銘 700 60 4. 6 實例31 氧化銘 95 0 15 5.1 實例32 氧化鋁 1100 5 4.0 實施例3 3及3 4 . 實例3 3中，平均粒徑1 之銅粉於攙拌乙二胺四 乙酸二鈉鹼飽和溶液下浸於該飽和浴中後，過濾由飽和溶 液取出銅粉，乾燥得到第一種銅粉。1 · 0 5重量份數第 一種銅粉與2重量份數之樹脂酸鉍漿液（B i含量：2, 〇 本紙張尺度適用中.國國家榇準（CNS ) A4規格（210 X 297公釐) — « , I 裝 I ――訂— —~~ n . .線 (請先閲讀背面之注意事項再填寫本頁) 470734 A7 B7 五、發明説明（17 ) % )混合得到鉍及銅之混合漿液。依基本上同於實例1之 方法，於氧化鋁陶瓷基材上形成實例3 3之約1 0 am厚 之銅膜，不同處係使用實例3 3所製之混合漿液。 實例3 4中，由包含乙二胺四乙酸二鈉之銅電鍍液藉 添加硼氫化鈉於電鍍液中而澱積第二種銅粉。1. 0 5重 量份數第二種銅粉與2重量份數樹脂酸鉍漿液（B i含量 =2 0%)混合得到鉍及銅之混合漿液。依基本上同於實-例1之方法於氧化鋁陶瓷基材上形成實例3 4約1 0 /zm 厚度之銅膜，不同處係使用實例3 4所製之混合漿液。 依實例1之粘著性試驗方式測量實例3 3及3 4之銅 膜與陶瓷基材間之粘著強度。粘著性試驗結果列於表6 » (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表 6 陶瓷基材 粘著強度 (kg /4mm2 ) 實例33 氧化鋁 4.8 實例34 氮化鋁 5.2 比較實例1銅膜與實例3 3或3 4之銅膜之粘著強度 時，已知使用本發明方法之第一或第二種銅粉時，可進一 本纸張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） -20 - 470734 A7 B7 五、發明説明（18 ) 步改善粘著性強度。實施例35 — 39 如表7所不’製備氧化銘、氮化銘、欽酸鋇、碳化砂 ’及氧化銷之陶瓷基材。基本上由5重量份數樹脂酸釩漿 液（V含：3 . 9%)及5重量份數樹脂酸銅漿液（c u 量·· 6 . 4 % )所組成之混合樹脂酸鹽漿液藉篩印法印刷_ 於個別陶瓷基材表面上’得到混合漿液之電路圖型及陶瓷 基材曝露區。陶瓷基材於篩印前皆未進行任何糙化處理。 經印刷之基材於約1 2 5 °C乾燥1 〇分鐘後，於5 5 0 °C 溫度下之空氣中熱處理1小時，於電路圖型表面中形成氧 化銅層。藉將具有氧化銅層之陶瓷基材浸於溫度8 0°C之 硼氫化鈉水溶液浴中5分鐘而將氧化銅層還原成金屬銅層 ，水溶液pH爲12. 5。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格< 210X297公釐） -21 ~ 470734 ki B7 五、發明説明（19 ) 表 7 陶瓷基材 粘著強度 .(kg / 4mm2) 實例35 氧化鋁 4.2 實例36 氮化鋁 4. 1 實例37 鈦酸鋇 4.5 實例3 8 碳化矽 4.0 實例3 9 氧化锆 4.1 I Ί 裝 I 訂 線 (請先閱讀背面之注意事項再填寫本頁) 經廣部智慧財產局員工消費合作社印製 藉無電電鍍於金屬銅層上形成額外銅層，沿陶瓷基材上之 電路圖型得到厚約1 0 /zm之銅膜。額外銅層中銅含量高 於 9 9 w t %。 進行粘著性試驗測量實例3 5至3 9之銅膜與陶瓷基 材間之粘著強度。粘著性試驗結果列於表7。 實施例4 0 — 4 8 表8所列之陶瓷基材各藉包含鈀離子之溶液處理後， 本紙張尺度適用中圈國家標準（CNS ) A4規格（2I0X297公釐·） -Ti 470734 A7 B7 五、發明説明（20 ) 藉無電電鍍於陶瓷基材表面上形成第一層銅底塗層。陶瓷 基材表面於以鈀溶液處理前不進行任何糙化處理實例4 0 一 4 4中，於氧化鋁陶瓷基材上形成具不同厚度之第一層 底塗層。樹脂酸釩漿液（V含量：3 . 9 % )藉篩印印刷 於第一層底塗層上，形成第二層釩底塗層。經印刷之基材 於約1 2 5°C乾燥1 0分鐘，於5 5 0 °C溫度之空氣中熱 處理1小時，於第二層底塗層表面中形成氧化銅層。藉浸-漬具氧化銅層之陶瓷基材於溫度8 0 °C之硼氫化鈉水溶液 浴中5分鐘而將氧化銅層還原成金屬銅層，水溶液p H 12. 5。藉無電電鑛於金屬銅層上形成額外銅層，得到 於陶瓷基材上厚約10之銅膜。 實例4 0至48中，依實例1之牯著性試驗測量銅膜 與陶瓷基材間之粘著強度。粘著性試驗之結果列於表8中 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格_( 210X297公釐’） -23 - 470734 A7 B7 五、發明説明（2i ) 表 8 經濟部智慧財產局員工消費合作社印製 陶瓷基材 第一層底塗層 粘著強度 厚度（V m ) (kg / 4mm2) 實例40 氧化銘 0.05 4. 8 實例4 1 氧化鋁 0. 5 5. 0 實例42 氧化鋁 1.0 5. 2 實例43 '氧化鋁 2.0 4.8 實例44 氧化銘_ 3. 0 4. 5 實例45 氮化鋁 0. 5 5. 5 實例46 鈦酸鋇 0.5 5. 7 實例47 碳化矽 0. 5 4. 9 實例48 氧化鉻 0. 5 5.1 (請先閱讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS ) A4規格（210X：297公釐') 470734 A7 B7 五、發明説明（22) 實施例49-53 於表9所列之各陶瓷基材表面上，藉篩印於陶瓷基材 表面印上樹脂酸釩漿液（V含量：3. 9%)並於12 5 °C乾燥1 〇分鐘形成第一層釩底塗層。陶瓷基材表面於篩 印前未進行任何糙化處理。於第一層底塗層上篩印上樹脂 酸銅漿液（Cu含量：6%)，於125 °C乾燥10分鐘 後得到第二層銅底塗層。印刷陶瓷基材於5 5 0 °C空氣中-熱處理1小時於第二層底塗層表面中形成氧化銅層。氧化 銅層藉浸漬具氧化銅層之陶瓷基材於溫度8 0°C之硼.氫化 鈉水溶液浴中5分鐘而還原成金屬銅層。水溶液p Η爲 12. 5。藉無電電鍍於金屬銅層上形成額外銅層，得到 厚約1 0〆m之銅膜。 依實例1之粘著性試驗方式測量實例4 9至5 3之銅 膜與陶瓷基材間之粘著強度。粘著性試驗結果列於表9中 (請先閱讀背面之注意事項再填寫本頁) 裝. 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中.國國家標準（CNS > A4規格（21〇χ297公釐) _ 25 - 470734 A7 B7 五、發明説明（23 ) 表9 陶瓷基材 粘著強度 (kg /4mm2 ) 實例49 氧化鋁 5. 1 實例50 氮化鋁 5.3 實例51 鈦酸鋇 5. 5 實例5 2 碳化砍 4. 9 實例53 氧化锆 4. 7 .......!'-- !. 1 ---1 Hr ------ . _ ......- I ........ I . - I (請先閱讀背面之注意事項再填寫本頁) 經濟'部智慧財產局員工消費合作社印製 實例5 4至5 5 依基本上同於實例49之方法於氧化鋁陶瓷基材上形 成實例5 4至5 5之約1 0 μηι厚度之銅膜，不同處係於 表.1 0所列之不同溫度下進行於空氣中.之熱處理。 依實例1之粘著性試驗方式測量實例5 4至5 5之銅 膜與陶瓷基材間之粘著強度。粘著性試驗結果列於表1 〇 中。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐-) 470734 A7 B7 五、發明説明（24 ) 表1 〇 陶瓷基材 氧化溫度 粘著強度 (V ) (kg / 4mm2) 實例54 氧化鋁 500 4.0 實例5 5 氧化鋁 60 0 5.0 經濟/部智慧財產局員工消費合作社印製 實施例56及57 實例33中，平均粒徑1 /zm之銅粉浸於攪拌的乙二 胺四乙酸二鈉鹼飽和溶液，過濾該飽和溶液取出銅粉，乾 燥得到第一種銅粉。3重量份數第一種銅粉與7重量份數 之樹脂酸釩漿液（V含量：3 . 9 % )混合得到釩及銅之 混合漿液。依基本上同於實例3 5之方法，形成實例5 6 之約1 0 /zm厚之銅膜，不同處係使用實例5 6所製之混 合槳液。 實例5 7中，由包含乙二胺四乙酸二鈉之銅電鍍液藉 添加硼氫化鈉於電鍍液中而澱積第二種銅粉。3重量份數 第二種銅粉與7重量份數樹脂酸釩漿液（V含量=3. 9 %)混合得到釩及銅之混合漿液。依基本上同於實例3 5 之方法形成實例5 7約1 0 //m厚度之銅膜，不同處係使 用實例.5 7所製之混合漿液。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐·) ~ -27 - I---,------裝-------訂------線 (請先閲讀背面之注意事項再填寫本頁) 470734 A7 B7 五、發明説明（25 ) 依實例1之粘著性試驗方式測量實例5 6及5 7之銅 膜與陶瓷基材間之粘著強度。粘著性試驗結果列於表1 1 表1 1 陶瓷基材 粘著強度 (kg / 4nim2 ) 實例56 氧化鋁 4.8 實例5 7 氧化銘 5. 2 n- fl ^^—^1 ml·* (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 比較實例1銅膜與實例5 6或5 7之銅膜之粘著強度 時，已知使用本發明方法之第一或第二種銅粉時，可進一 步改善粘著性強度。 實施例58及59 依實質上同於實例4 9之方法形成實例5 8及5 9之 約1 0 jt/m厚度之銅膜’不同處係藉電鍍或蜜用濺射法於 金屬銅層上形成額外銅層。額外銅層中之銅含量高於9 9 w t. %。 . 依同於實例1粘著試驗之方式測量實例5 8及5 9銅 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公董） -28 - 470734 A7 B7 經濟/部智慧財產局員工消費合作社印製 五、發明説明（26 ) 膜舆陶瓷基材間之粘著強度。粘著性試驗結果列於表1 2 中0 表1 2 陶瓷基材 粘著強度 (kg / 4mm2) 實例58 氧化鋁 5. 1 實例59 氧化鋁 5. 05. Description of the invention (6) Metal copper layer. Better than 20. (: And reduction at a reduction temperature between 100 ° C. Because the obtained metal copper layer has good wettability to the plating solution used for electroless plating, 'more copper nucleation sites can be provided during electroless plating. Therefore 'In the method of the present invention, it is not necessary to treat a ceramic substrate having a metallic copper layer with a solution containing palladium and / or platinum ions before the electroless copper electroplating. As for the reducing solution,' boron hydride salts' hypophosphite, dimethylamine Solutions such as borane. Especially when the reduction solution is dimethylamine borane, reduction can be performed at a reduction temperature between 30 ° (: and -50 ° C. When the reduction solution is a borohydride salt, it may be The reduction is performed at a reduction temperature between 50 ° C and 80 ° C. [.4] Copper coating on the metal copper layer The copper is coated on the metal copper layer, and the ceramic substrate is obtained with a unique A metal copper layer with a desired thickness. Examples of the method for coating copper can be electroless plating, electroplating, or sputtered copper. According to the above steps [1] to [4], a method for forming a copper circuit pattern 2 on a ceramic substrate is described below. For example, as shown in Figures 1 A and 1 B, a circuit is formed on a ceramic substrate. The first layer of copper undercoat layer 10 is formed, and then a second layer of bismuth is formed on the circuit pattern of the first layer of undercoat layer 10. and on the exposed area of the ceramic substrate without the first layer of undercoat layer 10. Undercoat layer 20. In the oxidation step (2), the copper of the first undercoat layer 10 is oxidized to form a copper oxide layer 11 on the surface of the circuit pattern, as shown in FIG. 1C. On the other hand, the second layer is also oxidized. Layer of bismuth layer 20, and a bismuth oxide layer 21 is formed on the ceramic substrate 1 and between the copper oxide layer 11 and the ceramic substrate 1. The bismuth oxide layer 21 can be used to improve the copper oxide layer 11 and the ceramic substrate. Adhesiveness between materials 1. Copper oxide layer 11 is reduced to metal copper layer 12 by reducing solution as shown in Figure 1 D nn · I, 111 II n .1 ....- !, 1TI— nn » (Please read the precautions on the back before filling out this page) The paper size is applicable. National National Standard (CNS) A4 size (210X297 mm) 470734 A7 B7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 7) As shown in the figure, an additional copper layer 3 is formed on the metal copper layer 12 by the electroless ammonium. The bismuth oxide layer 21 is not reduced by the reduction step [3]. The copper layer 30 is not deposited on the bismuth oxide layer 21 during electroless plating. As shown in FIG. 1E, the bismuth oxide layer 21 on the exposed area of the ceramic substrate 1 can be used as a shielding pattern for electroless plating. The bismuth oxide layer 21 can be easily removed by etching with an acid solution, and a copper circuit 2 on the ceramic substrate 1 is obtained, as shown in FIG. 1F. Alternatively, a copper circuit diagram can be formed on the ceramic substrate 1 A according to the following method. -Type 2 A. That is, as shown in Figures 2 A and 2 B, a first layer of bismuth undercoat layer 10 A is formed on the surface of ceramic substrate 1 A, and then the first layer of undercoat layer is formed along the circuit pattern. A second copper undercoat layer of 2 OA is formed on 1 OA. In the oxidation step [2], a copper oxide layer 2 1 A is formed in the second undercoat layer 20A, and a bismuth oxide layer 1 is formed on the ceramic substrate 1 A and between the copper oxide layer 2 1 A and the ceramic substrate 1A. 1A, as shown in Figure 2C. After the copper oxide layer 2 1 A is reduced to a metallic copper layer 2 2 A with a reducing solution, as shown in FIG. 2 D, an extra copper layer 3 0A is formed on the metallic copper layer 2 2A by electroless plating, as shown in FIG. 2 E . The additional copper layer 3 0 A is not deposited on the exposed area of the 1 1 A bismuth oxide layer 1 2 A in the circuit pattern of the metal copper layer 2 2 A. The bismuth oxide layer 1 1 A in the exposed area can be easily removed by etching with an acid solution, and a copper circuit pattern 2A on the ceramic substrate 1A is obtained, as shown in FIG. 2F. On the other hand, when a copper undercoat layer is formed on the ceramic substrate along the circuit pattern, it is preferable to apply or spray the sintering temperature on the exposed area of the ceramic substrate without the copper undercoat layer before the oxidation step [2]. Masking coating for inorganic powders above 1 100 ° c. For example, the exposed area can be sprayed with an inorganic powder containing alumina or chromium oxide powder and a masking coating of methyl cellulose binder I ------- t ------, 玎 ---- --0 (Please read the precautions on the back before filling out this page) The paper size is applicable. National Standard (CNS) A4 (210 '/ 297 mm.) -10-470734 A7 B7 Economy / Ministry Intellectual Property Printed by the Bureau's Consumer Cooperatives V. Invention Description (8). Alternatively, the masking coating can be printed on the exposed area by screen printing. As a result, it can prevent the copper evaporated from the undercoat layer from being deposited on the exposed area in the oxidation step [2]. After the oxidation step, the masking coating can be removed from the exposed area of the ceramic substrate by ultrasonic cleaning. Β When the copper slurry is used to form the first or second primer layer, the copper slurry is preferably treated with ethylenediamine chelating agent. Copper powder. In this case, a chelate of copper is formed on the surface of the copper powder. Because the copper chelate prevents the formation of excess Cu oxide in the form of Cu 0 in the oxidation step [2], the metal copper layer can be easily and uniformly provided by the reduction step [3]. As the chelating agent, ethylenediaminetetraacetic acid, ethylenediaminediacetic acid 'sodium diammoniumtetraacetate and the like can be used. When the copper powder is treated with a chelating agent, the copper powder may be immersed in the chelating agent bath, or the chelating agent may be sprayed on the copper powder. In particular, the first layer of the base layer of the preferred copper is deposited by electroless plating on a ceramic substrate from a copper plating solution containing a chelating agent, or the first layer is formed by using a slurry containing copper powder deposited by a copper electrolytic ammonium solution. Or a second base coat. Examples 1 to 5 As shown in Table 1, ceramic substrates of alumina, aluminum nitride, barium titanate, silicon carbide, and zirconia were prepared. Basically, a mixed resinate paddle liquid consisting of 2 parts by weight of bismuth resin acid slurry (Bi content: 20%) and 8 parts by weight of resin acid copper slurry (Cu content: 6%) is sieved. Printed on the surface of individual ceramic substrates to obtain the circuit pattern of the mixed slurry and the exposed area of the ceramic substrate. The ceramic substrate was not subjected to any roughening treatment before screen printing. The printed substrate was dried for 10 minutes at 125 ° C, and then heat-treated in air at 850 ° C for 1 hour to form a copper oxide layer on the circuit pattern surface. The copper oxide layer is immersed in a ceramic substrate with a copper oxide layer at a temperature of ^ III Order I¼ (please read the precautions on the back before filling out this page) This paper size is applicable. National Standard (CNS) A4 Specification (210X297) (Centi) ~ 11-470734 A7 B7 V. Description of the invention (9) The sodium borohydride aqueous solution at 80 ° C for 5 minutes was reduced to a metallic copper layer. The aqueous solution p Η was 12.5. An extra copper layer is formed on the metal copper layer by electroless plating, and a copper film with a thickness of about 10 // m is obtained along the circuit pattern on the ceramic substrate. An adhesion test was performed to measure the adhesion strength between the copper film and the ceramic substrate. That is, as shown in FIG. 3, a copper-coated copper wire 3 having a diameter of 0.7 mm is welded to a copper film 2 having a positive surface area of 2 m × 2 mm formed on a ceramic base material 1. When the copper wire 3 is drawn in the direction shown by arrow F in FIG. 1, the force required to remove the copper film 2 by the ceramic base material 1 determines the adhesive strength. The results of the adhesion tests of Examples 1 to 5 are shown in Table 1. Table 1 (Please read the precautions on the back and fill in the original contents) Adhesion strength of ceramic substrates printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (/ 4mm2) Example 1 Aluminum oxide 4.5 Example 2 Aluminum nitride 4 3 Example 3 Barium Titanate 4.6 Example 4 Silicon Carbide 4.2 2 Example 5 Chromium Oxide 4. 4 The size of the revised paper applies to the Chinese National Standard (CNS) A4 (210x297 mm ') 470734 A7 B7 Employees of the Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperatives 5. Description of the Invention (ίο) Examples 6-14 The ceramic substrates listed in Table 2 are each immersed in a solution bath containing palladium ions. The first layer of copper bottom is formed on the surface of the ceramic substrate by electroless plating Coating. In Example 6-10, a first undercoat layer with different thickness was formed on an alumina ceramic substrate. The surface of the ceramic substrate was not subjected to any roughening treatment before being treated with a palladium solution. The coating is etched along the predetermined pattern to obtain its circuit pattern and exposed area of the ceramic substrate. The bismuth resin slurry (Bi content: 20%) is-screen printed and printed on the first layer of the primer layer and the ceramic substrate is exposed. Area, a second bismuth undercoat layer is formed The printed substrate was dried for about 1.0 minute at about 12.5 ° C, and then heat-treated in air at a temperature of 850 ° C for 1 hour, and a copper oxide layer was formed along the circuit pattern on the surface of the second primer layer. At the same time The second layer of bismuth is oxidized to form a bismuth oxide layer. The copper oxide layer is reduced to a metallic copper layer by dipping a ceramic substrate with a copper oxide layer at a temperature of 80 ° C in sodium borohydride in a solution bath for 5 minutes. With solution PHI 2. 5. An extra copper layer was formed on the metal copper layer by electroless plating to obtain a copper film with a thickness of about 10 mm along the circuit pattern on the ceramic substrate. A bismuth oxide layer was exposed on the exposed area of the ceramic substrate. No additional copper layer was formed on the surface. As a result, it was shown that the second bismuth undercoat layer formed on the exposed area of the ceramic substrate can affect the masking pattern of electroless plating. After electroless plating, the bismuth oxide layer on the exposed area was etched by acid In Examples 6 to 14, the adhesion strength between the copper film and the ceramic substrate was measured according to the adhesion test of Example 1. The results of the adhesion test are listed in Table 2. ----_--- n I installed n --- order (please read the precautions on the back before filling this page) This paper wave scale is applicable to China Standard (CNS) A4 (210 X 297 Gong) -13-470734 A7 B7 V. Description of Invention (11) Table 2 The first layer of the base coat of the ceramic substrate printed by the Consumer Cooperative of the Ministry of Economic Affairs' Intellectual Property Bureau Strength Thickness (// m) (kg / 4mm2) Example 6 Oxidation 0.05 0.05 5 2 Example 7 Alumina 0.5 5. 5 Example 8 Alumina 1. 0 5. 0 Example 9 Oxidation 2.0 4. 8 Example 10 Alumina 3. 0 4. 5 Example 11 Aluminum Nitride 0.5 5 5. 5 Example 1 2 Barium Titanate 0.5 5.7 Example 13 Carbide 0.5 4. 9 Example 14 Zirconia 0.5 5 5.1 (Please read the precautions on the back first (Fill in this page) This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm ·) -14-470734 A7 _ B7 V. Description of the invention (12) Example 1 5-2 4 Each of the items listed in Table 3 A first bismuth undercoat layer is formed on the surface of the ceramic substrate. In Examples 15-19, the first base coat was formed by printing a resin bismuth acid slurry (Bi content: 20%) on the surface of the ceramic substrate by screen printing. In Examples 20 to 24, the ceramic substrate was immersed in a solution bath containing palladium ions, and electroless plating of bismuth was performed on the surface of the ceramic substrate to form a first undercoat layer. The surface of the ceramic substrate was not subjected to any roughening treatment before being screen-printed or treated with a palladium solution. A copper resinate slurry (Cu content: 6%) was printed on the first base coat layer along a predetermined circuit pattern, and a second copper base coat layer was obtained on the first base coat layer. The printed substrate was heat treated in air at 850 ° C for 1 hour to form a copper oxide layer on the surface of the second undercoat layer. At the same time, the first layer of bismuth is oxidized to form a bismuth oxide layer. The copper oxide layer was reduced to a metallic copper layer by impregnating a ceramic substrate with a copper oxide layer at a temperature of 80 ° C in sodium borohydride in a solution bath for 5 minutes, and the aqueous solution PΗ was 1 2 · 5.丨 .------ ^ --- install ------ order silver (please read the notes on the back before filling out this page) China National Standard (CNS) A4 specification (210 X 297 mm) 470734 A7 B7 V. Description of invention (l3) Table 3 The ceramic substrate printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to form the first base coat method Impact strength (kg / 4mm2) Example 1 5 Alumina resin salt slurry 5.0 Example 16 Alumina resin salt slurry 4.9 Example 17 Barium titanate resin salt slurry 5. 3 Example 18 Silicon carbide resin slurry 4.8 Example 19 Oxidation Zirconate resin slurry 5. 2 Example 20 Aluminum nitride plating 4. 4 Example 21 Oxidation 1 Lu plating 4.3 Example 22 Barium titanate plating 4. 6 Example 23 Carbide plating 4.2 Example 2 4 Zirconium oxide plating 4.9 (Please read first Note on the back, please fill in this page again.) This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm ') -16 470734 A7 B7 _____ V. Description of the invention (14) / By electroless plating on the copper metal layer Additional copper layer is formed on the 'Tao The circuit on the porcelain substrate obtained a copper film with a thickness of about 10. No additional copper layer was formed on the exposed area of the bismuth oxide layer without the second undercoat layer. The fact shows that the first bismuth undercoat layer can be used as electroless plating The masking pattern. After electroless plating, the bismuth oxide layer in the exposed area was etched with an acid solution. The adhesion strength between the copper film and the ceramic substrate of Examples 15 to 24 was measured according to the adhesion test method of Example 1. Adhesion The results of the adhesion tests are listed in Table 3-Examples 2 to 2 8 A copper film having a thickness of about 10 / zm of Examples 2 5 to 28 was formed on an alumina ceramic substrate in substantially the same manner as in Example 7. In different places, a bismuth resin acid slurry with different bismuth content is used to form a second layer of bismuth undercoating 'as listed in Table 4. --------- Installation ------ Order (Please (Please read the notes on the back before filling in this page) The paper size printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (210X297 mm') _ 17 _ 470734 A7 B7 V. Description of the invention (Is) Table 4 B i content (wt%) in the second primer layer of ceramic substrate _ ----- ^ Adhesive strength (kg / 4mm2) Example 25 Alumina 15 5. 4 Example 26 Alumina 12 4.8 Example 27 Alumina 1 0 2. 5 Example 28 Alumina 5 1. 5 H. -----If j H--..... I — IT n!-»1 II—-----1--.11 II -----HI _ (Please read the precautions on the back before filling out this page) The adhesion test method of Example 1 measures the adhesion strength between the copper films of Examples 25 to 28 and the ceramic substrate. The results of the adhesion test are listed in Table 4. It is known from the results of the adhesion test that the bismuth content in the resinate slurry is preferably 10 wt% or higher to obtain better adhesion strength. Examples 29-32 A copper film of about 1 Oem thickness of Examples 29-3 2 was formed on an alumina ceramic substrate in substantially the same manner as in Example 15. The differences are in the different temperature and time conditions listed in Table 5. The heat treatment in air is performed next. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297mm ·) 470734 A7 B7 V. Description of the invention (ie) According to the adhesion test method of Example 1, the copper film and ceramic substrate of Examples 2 9 to 32 were measured Adhesive strength between materials. The results of the adhesion test are listed in Table 5. Printed by the Consumers' Cooperative of the Ministry of Economy + Ministry of Intellectual Property, Table 5. Conditions for heat treatment of ceramic substrates. Time (° C) (min) Adhesive strength (kg / 4mm2) Example 29 Oxidation Aluminum 600 60 4.0 Example 30 Oxide Ming 700 60 4. 6 Example 31 Oxide Ming 95 0 15 5.1 Example 32 Alumina 1100 5 4.0 Examples 3 3 and 3 4. In Example 3 3, the copper powder with an average particle diameter of 1 was After immersing in a saturated solution of ethylenediaminetetraacetic acid disodium alkali in the saturated bath, the copper powder was taken out from the saturated solution by filtration and dried to obtain the first copper powder. 1 · 0 5 parts by weight of the first copper powder and 2 parts by weight of bismuth resin acid slurry (B i content: 2, 〇 This paper size is applicable. CNS) A4 size (210 X 297) (%) — «, I installed I —— ordered — — ~~ n.. (Please read the precautions on the back before filling out this page) 470734 A7 B7 V. Description of the invention (17)%) Mixed to obtain bismuth and copper Mix the slurry. A copper film having a thickness of about 10 am of Example 33 was formed on an alumina ceramic substrate in substantially the same manner as in Example 1, except that the mixed slurry prepared in Example 33 was used. In Example 34, a second copper powder was deposited from a copper plating solution containing disodium ethylenediamine tetraacetate by adding sodium borohydride to the plating solution. 1.05 parts by weight of the second copper powder was mixed with 2 parts by weight of bismuth resin acid slurry (Bi content = 20%) to obtain a mixed slurry of bismuth and copper. A copper film with a thickness of about 10 / zm in Example 3 4 was formed on an alumina ceramic substrate in substantially the same manner as in Example 1. The difference was that the mixed slurry prepared in Example 3 4 was used. The adhesion strength between the copper films of Examples 3 3 and 34 and the ceramic substrate was measured according to the adhesion test method of Example 1. The results of the adhesion test are listed in Table 6 »(Please read the precautions on the back before filling out this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 6 Adhesive strength of ceramic substrates (kg / 4mm2) Example 33 Alumina 4.8 Example 34 Aluminum nitride 5.2 When comparing the adhesion strength between the copper film of Example 1 and the copper film of Examples 3 3 or 34, it is known that when using the first or second copper powder of the method of the present invention, a paper can be fed. The scale is applicable to Chinese national standard (CNS> A4 specification (210X297mm) -20-470734 A7 B7 V. Description of the invention (18) Step to improve the adhesive strength. Examples 35-39 As shown in Table 7 Ceramic substrates with nitride, barium acetate, sand carbide, and oxide pins. Basically it consists of 5 parts by weight of vanadium resin acid slurry (V: 3.9%) and 5 parts by weight of copper resin acid slurry (cu The amount of the mixed resinate slurry composed of 6.4%) is printed by screen printing method _ on the surface of individual ceramic substrates to get the circuit pattern of the mixed slurry and the exposed area of the ceramic substrate. The ceramic substrate is before the screen printing. No roughening has been performed. The printed substrate is at approximately 1 2 5 ° C After drying for 10 minutes, heat treatment in air at 5 50 ° C for 1 hour to form a copper oxide layer on the surface of the circuit pattern. By immersing the ceramic substrate with the copper oxide layer in boron at 80 ° C The copper oxide layer was reduced to a metallic copper layer in a sodium hydride aqueous solution bath for 5 minutes, and the pH of the aqueous solution was 12. 5. (Please read the precautions on the back before filling this page.) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The scale is applicable to Chinese National Standard (CNS) A4 specifications < 210X297 mm) -21 ~ 470734 ki B7 V. Description of the invention (19) Table 7 Adhesive strength of ceramic substrate. (Kg / 4mm2) Example 35 Alumina 4.2 Example 36 Aluminum Nitride 4.1 Example 37 Barium Titanate 4.5 Example 3 8 Silicon Carbide 4.0 Example 3 9 Zirconium Oxide 4.1 I Assembled I Thread (please read the precautions on the back before filling this page) Employees of Bureau of Intellectual Property of Guangxi The consumer cooperative prints an extra copper layer on the metal copper layer by electroless plating, and obtains a copper film with a thickness of about 10 / zm along the circuit pattern on the ceramic substrate. The copper content in the extra copper layer is higher than 9 9 w t%. An adhesion test was performed to measure the adhesion strength between the copper film and the ceramic substrate of Examples 35 to 39. The results of the adhesion test are shown in Table 7. Example 4 0 — 4 8 After the ceramic substrates listed in Table 8 are each treated with a solution containing palladium ions, the paper size is applicable to the National Standard (CNS) A4 specification (2I0X297 mm ·) -Ti 470734 A7 B7 5 2. Description of the invention (20) A first copper undercoat layer is formed on the surface of the ceramic substrate by electroless plating. The surface of the ceramic substrate was not subjected to any roughening treatment before being treated with a palladium solution. In Examples 40 to 4, a first undercoat layer having different thicknesses was formed on an alumina ceramic substrate. The vanadium resin acid slurry (V content: 3.9%) is printed on the first undercoat layer by screen printing to form a second vanadium undercoat layer. The printed substrate is dried at about 125 ° C for 10 minutes, and heat-treated in air at a temperature of 550 ° C for 1 hour to form a copper oxide layer on the surface of the second primer layer. The copper oxide layer was reduced to a metallic copper layer by dipping-staining a ceramic substrate with a copper oxide layer in a sodium borohydride aqueous solution at a temperature of 80 ° C for 5 minutes. The aqueous solution was p H 12.5. An extra copper layer was formed on the metal copper layer by using electroless ore to obtain a copper film with a thickness of about 10 on the ceramic substrate. In Examples 40 to 48, the adhesion strength between the copper film and the ceramic substrate was measured according to the adhesion test of Example 1. The results of the adhesion test are listed in Table 8. (Please read the precautions on the back before filling this page.) Printed on the paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to China National Standard (CNS) A4 specifications_ (210X297) Centi ') -23-470734 A7 B7 V. Description of Invention (2i) Table 8 Adhesive Thickness (V m) (kg / 4mm2) of the first base coat of the ceramic substrate printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 40 oxide name 0.05 4. 8 example 4 1 alumina 0.5 5 5. 0 example 42 alumina 1.0 5. 2 example 43 'alumina 2.0 4.8 example 44 oxide name _ 3. 0 4. 5 example 45 aluminum nitride 0. 5 5. 5 Example 46 Barium Titanate 0.5 5. 7 Example 47 Silicon Carbide 0.5 5 4. 9 Example 48 Chromium Oxide 0.5 5 5.1 (Please read the precautions on the back before filling this page) Size of this paper Applicable to China National Standard (CNS) A4 specification (210X: 297 mm ') 470734 A7 B7 V. Description of the invention (22) Examples 49-53 On the surface of each ceramic substrate listed in Table 9, printed on the ceramic by sieve The surface of the substrate was printed with vanadium resin acid slurry (V content: 3.9%) and dried at 12 5 ° C for 10 minutes. The first undercoat layer vanadium. The surface of the ceramic substrate was not roughened before screen printing. A resin acid copper slurry (Cu content: 6%) was screen-printed on the first undercoat layer, and dried at 125 ° C for 10 minutes to obtain a second copper undercoat layer. The printed ceramic substrate was heat-treated in air at 55 ° C for 1 hour to form a copper oxide layer on the surface of the second undercoat layer. The copper oxide layer is reduced to a metallic copper layer by impregnating a ceramic substrate with a copper oxide layer in a boron. Sodium hydride aqueous solution at a temperature of 80 ° C for 5 minutes. The aqueous solution pΗ is 12.5. An extra copper layer was formed on the metal copper layer by electroless plating to obtain a copper film having a thickness of about 10 μm. The adhesion strength between the copper films of Examples 4 9 to 53 and the ceramic substrate was measured according to the adhesion test method of Example 1. The results of the adhesion test are listed in Table 9 (please read the precautions on the back before filling in this page). Packing. Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, and the paper size is applicable. National Standards (CNS > A4 Specification (21 × 297 mm) _ 25-470734 A7 B7 V. Description of the invention (23) Table 9 Adhesive strength of ceramic substrate (kg / 4mm2) Example 49 Alumina 5.1 Example 50 Aluminum nitride 5.3 Example 51 Titanium Barium acid 5. 5 Example 5 2 Carbide 4. 9 Example 53 Zirconia 4. 7 .......! '-!. 1 --- 1 Hr ------. _ ... ...- I ........ I.-I (Please read the notes on the back before filling out this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economy 5 4 to 5 5 According to the basic The same method as in Example 49 was used to form a copper film with a thickness of about 10 μηι on the alumina ceramic substrate of Examples 5 4 to 55, except that the difference was performed in air at different temperatures listed in Table .10. Heat treatment. Measure the adhesion strength between the copper film and the ceramic substrate of Examples 5 4 to 5 5 according to the adhesion test method of Example 1. The results of the adhesion test are listed in Table 10. This paper scale applies to China Domestic Standard (CNS) A4 Specification (210 × 297 mm-) 470734 A7 B7 V. Description of Invention (24) Table 1 〇 Ceramic substrate oxidation temperature adhesive strength (V) (kg / 4mm2) Example 54 Alumina 500 4.0 Example 5 5 Alumina 60 0 5.0 Printed by the Consumers' Cooperatives of the Ministry of Economy / Ministry of Intellectual Property, Examples 56 and 57 In Example 33, copper powder with an average particle size of 1 / zm was immersed in a stirred saturated solution of ethylenediamine tetraacetic acid disodium alkali, The saturated solution was filtered, and the copper powder was taken out and dried to obtain the first copper powder. 3 parts by weight of the first copper powder was mixed with 7 parts by weight of the vanadium resin acid slurry (V content: 3.9%) to obtain vanadium and copper. The mixed slurry was formed in the same manner as in Example 3 5 to form a copper film having a thickness of about 10 / zm in Example 5 6 except that the mixed paddle liquid prepared in Example 5 6 was used. A copper plating solution of ethylenediaminetetraacetic acid disodium is deposited by adding sodium borohydride to the plating solution to deposit a second copper powder. 3 parts by weight of the second copper powder and 7 parts by weight of a vanadium resin acid slurry (V content = 3.9%) to obtain a mixed slurry of vanadium and copper. The shape is basically the same as that of Example 35. Example 5 7 The copper film with a thickness of about 10m / m is used in different places. The mixed slurry prepared by 5-7. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm ·) ~ -27- I ---, ------ install ------- order ------ line (please read the precautions on the back before filling this page) 470734 A7 B7 V. Description of the invention (25) The adhesion strength between the copper film and the ceramic substrate of Examples 56 and 57 was measured according to the adhesion test method of Example 1. The results of the adhesion test are listed in Table 1 1 Table 1 1 Adhesive strength of ceramic substrates (kg / 4nim2) Example 56 Alumina 4.8 Example 5 7 Oxide name 5. 2 n- fl ^^ — ^ 1 ml · * (Please (Read the precautions on the back before filling this page.) Order the adhesive strength of the copper film of Comparative Example 1 and the copper film of Example 5 6 or 57 7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. With the first or second copper powder, the adhesive strength can be further improved. Examples 58 and 59 A copper film having a thickness of about 10 jt / m of Examples 5 8 and 5 9 was formed in substantially the same manner as in Example 4 9. The difference was that the metal copper layer was sputtered by electroplating or honey. An additional copper layer is formed. The copper content in the extra copper layer is higher than 9 9 w t.%. . Measure examples 5 8 and 5 9 in accordance with the same adhesion test as in Example 1. The copper paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297). -28-470734 A7 B7 Employees ’consumption Printed by the cooperative V. Description of the invention (26) Adhesion strength between the ceramic substrates of the film. The results of the adhesion test are listed in Table 1 2 0 Table 1 2 Ceramic substrate Adhesive strength (kg / 4mm2) Example 58 Alumina 5. 1 Example 59 Alumina 5. 0
實施例6 0 - 6 3 陶瓷基材表面各以包含鈀離子之溶液處理後，藉無電 電鍍於陶瓷基材表面上形成第一層銅底塗層。第一層底塗 層厚度約0. 5vm。樹脂酸鉍漿液（Bi含量：1〇% )藉篩印印刷於第一層底塗層上，形成第二層鉍底塗層。 經印刷之基材於約1 2 5 °C乾燥1 0分鐘，於8 5 0 °C溫 度之空氣中熱處理1小時，於第二層底塗層表面中形成氧 化銅層。。實例60及61中，氧化銅層藉浸漬具氧化銅 層之陶瓷基材於溫度4 0或8 0°C之硼氨化鈉水溶液浴中 5分鐘而還原成金屬銅層。水溶液pH 1 2 . 5。實例 62及6 3中，藉浸漬具有氧化銅層之陶瓷基材於2 5 °C — Ί ^ .. J 裝 — 訂 I 111 ..線 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0 X 297公釐） -29 - 經濟·部智慧財產局員工消費合作社印製 470734 A7 B7 五、發明説明（27 ) 或4 0。(：二甲胺硼烷水溶液中5分鐘而將氧化銅層還原成 金屬銅層。水溶，液p Η 4 . 1。之後藉無電電鑛於金屬銅 層上形成額外銅層，得到厚約1 〇 之銅膜。 實例6 0至6 3中，依實例1之粘著性試驗測量銅膜 與陶瓷基材間之粘著強度。粘著性試驗之結果列於表1 3 中〇 表1 3 還原溶液. 還原溫度 粘著強度 (°C ) (kg / 4mm2 ) 實例60 硼氫化鈉 40 4.4 實例61 硼氫化鈉 80 4.5 實例62 二甲胺硼烷 25 4.6 實例63 二甲胺硼烷 40 4.6 實施例6 4 — 6 8 基本上由樹脂酸銅漿液（Cu含：3. 7 wt%)樹 脂酸鉍紫液（B i含量：1 〇 % .)及樹脂酸釩漿液（V含 本紙張尺度適用中國國家摞準（CNS ) A4規格（210X297公釐·) ~ " -30 - -----------私衣------~tr—-----m. (請先閲讀背面之注意事項再填寫本頁) 470734 A7 B7 五、發明説明（28 ) 量：1 . 9w t%)所組成之混合樹脂酸鹽漿液藉篩印法 印刷於表1 4所列之個別陶瓷基材表面上，得到混合漿液 之底塗層。底塗層於1 2 5 °C乾燥1 0分鐘後，於6 0 〇 °〇溫度下之空氣中熱處理1小時，於底塗層表面中形成氧 化銅層。氧化銅層藉將具有氧化銅層之陶瓷基材浸於溫度 8 0°C之硼氫化鈉水溶液浴中5分鐘而還原成金屬銅層。 水溶液pH爲12. 5。藉無電電鍍於金屬銅層上形成額- 外銅層，於陶瓷基材上得到厚約1 〇 // m之銅膜。 如實例1般進行粘著性試驗測量實例6 4至6 8之銅 膜與陶瓷基材間之粘著強度。粘著性試驗結果列於表1 4 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印^ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -31 - 470734 A7 B7五、發明説明（29 ) 表1 4 陶瓷基材 粘著強度 (kg / 4mm2) 實例64 氧化鋁 4.8 實例65 氮化鋁 4.5 實例66 鈦酸鋇 5.0 實例6 7 碳化矽 4.2 實例68 氧化锆 4.5 (請先閲讀背面之注意事項再填寫本頁) 經濟·部智慧財產局員工消費合作社印製 對照例1 一 5 表1 5所列之各陶瓷基材表面藉包含鈀離子之溶液處 理後，藉無電電鍍於陶瓷基材表面上形成銅底塗層。底塗 層厚度約1 Mm °具底塗層之陶瓷基材以水清洗，乾燥’ 並於5 0 0 °C溫度之空氣中熱處理30分鐘得到氧化銅層。 氧化銅層藉於具5 0 0 °C溫度之氫氣流中加熱具有氧化銅 層之陶瓷基材3 0分鐘而還原成金屬銅層。之後’藉無電 電鑛於金屬銅層上形成額外銅層.，於陶瓷基材上形成厚約. 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) ： -32 - 470734 Α7 Β7 五、發明説明（30 ) 1 0 // m之銅膜。 依實例1之粘著性試驗測量對照例1至5之銅膜與陶 瓷基材間之粘者強度。粘著性試驗結果列於表1 5中。粘 著性試驗中’發現金屬銅層與額外銅層間之界面，銅膜個 別剝落。 經濟/那智慧財產局員工消費合作社印製 表1 5 陶瓷基材 粘著強度· (kg /4mm2) '對照實例1 氧_化銘 0.2 對照實例2 氮化鋁 0. 3 對照實例3 鈦酸鋇 0.2 對照實例4 碳化矽 0. 2 對照實例5 氧化錯 0.3 ----------- 裝-------訂 故 (請先閲讀背面之注意事項再填寫本頁) 製備氧化鋁 實施例6 9 氮化鋁 7 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐.） 鈦酸鋇、碳化矽 33 - 及氧化鉻陶 470734 A7 B7 五、發明説明（31 ) 瓷塞材。藉無電電鍍 '濺射、或篩印表1 6所列之銅有機 金屬化合物之樹脂酸鹽漿液，而於各陶瓷基材表面上形成 銅底塗層。各陶瓷基材於形成底塗層前皆未於表面進行任 何糙化處理。然而，陶瓷基材表面於無電電銨前以包含鈀 離子之溶液處理。底塗層厚度約0 . 5 vm。塗有底塗層 之基材於1 0 0 0°C溫度之空氣中熱處理4 5分鐘形成氧 化銅層。氧化銅層藉浸漬具氧化銅層之陶瓷基材於溫度 -8 0 °C之硼氫化鈉水溶液浴.中，而還原成金屬銅層。水溶 液pH 12. 5。藉無電電鍍於金屬銅層上形成額外銅層 ，於陶瓷基材上得到厚約1 0 之銅膜。無電電鍍後， 藉感光印刷法於陶瓷基材上形成銅膜電路圖型。 依實例1之粘著性試驗法測量實例6 9至7 5之銅膜 與陶瓷基材間之粘著強度。粘著性試驗結果列於表1 6。 (請先閲讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -34 - 470734 A7 B7 五、發明説明（32 ) 表1 6 經濟部智慧財產局員工消費合作社印製 陶瓷基材 形成底塗層之 方法 粘著強度 (kg / 4mm2) 實例69 氧化鋁 無電電鑛 4.2 實例70 氮化鋁 無電電鍍 4.1 實例7 1 鈦酸鋇 無電電鍍 4.8 實例72 、碳化矽 無電電鍍 3.7 實例73 氧化锆 無電電鍍 4. 7 實例74 氮化銘 濺射 4,1 實例75 氧化鋁 篩印 3.8 實施例76及77 氧化鋁陶瓷基材表面各藉包含鈀離子之溶液處理後， 藉無電電鍍於陶瓷基材表面上形成銅底塗層。底塗層厚約 0 . 5 a m。藉感光印刷法進成底塗層之成型，得到底塗 本紙張尺度適用中屋1國家標準（CNS ) A4規格{ 210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂 -35 ~ 470734 A7 B7五、發明説明（33 ) 層圖型與陶瓷基材曝露區。陶瓷基材表面於形成底塗層前 皆未進行任何糙化處理。於陶瓷基材曝露區及底塗層電路 圖型上噴灑基本上由平均粒徑〇 . 1 // m之氧化锆粉及甲 基纖維素所組成之遮掩塗料。具有遮掩塗料之陶瓷基材於 表1 7所列之條件下之空氣中熱處理’於陶瓷基材上形成 氧化銅層電路圖型後，藉水超音波清洗去除遮掩塗料。之 後，藉浸漬具有氧化銅層之陶瓷基材於溫度8 0 °C硼氫化-鈉水溶液浴中，將氧化銅層還原成金屬銅層。水溶液P Η 12. 5。藉無電電鍍於金屬銅層上形成額外銅層，，沿陶 瓷基材電路圖型形成厚約1 0 之銅膜。陶瓷基材曝露 區上未形成額外銅層。 經濟'部智慧財產局員工消費合作社印製 表1 7 陶瓷基材 熱處理條件 溫度 時間 (°C ) (min) 粘著強度 (kg / 4mm2) 實例76 氧化鋁 1000 45 4. 0 實例77 氧化鋁 1100 10 4. Γ 依實例1之粘著性試驗方法測量實例7 6及7 7之銅 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐） ---------.裝 —II —訂— II 辣 (請先閲讀背面之注意事項再填寫本頁) -36, 470734 Α7 Β7 五、發明説明（34 ) 膜奥陶瓷基材間之粘著強度。粘著性試驗結果列於表1 7 中〇 實施例7 8 — 8 0 依實質同於實例7 6之方法，於氧化鋁陶瓷基材上形 成實例7 8至8 0之約1 0 μιη厚之銅膜，不同處係熱處 理前不噴灑遮掩塗料，於表1 8所列之不同溫度及時間條-件下進行於空氣中之熱處理。實例7 9及8 0中，因於 1 0 0 0 °C或更高溫度下進行熱處理，故於陶瓷基材上形 成之銅底塗層蒸發，澱積於未形成底塗層之陶瓷基材曝露 區上。銅澱積於曝露區時會使銅膜之電路圖型短路。結果 顯示於1 0 0 0°C或更高溫度下熱處理銅底塗層時，較佳 於熱處理前噴灑遮掩塗料於陶瓷基材曝露區上》 ----------.裝-------訂------级 (請先閲讀背面之注意事項再填寫本頁) 經濟/部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐） -37, 470734 A7 B7 五、發明説明（35 ) 表1 8 陶瓷基材 氧化條件 溫度 時間 (°C ) (min) 粘著強度 (kg /4mm2 ) 實例78 氧化鋁 850 360 3. 1 實例79 氧化鋁 1000 45 4.0 實例80 氧化鋁 1100 10 4.1 經濟'部智慈財產局員工消費合作社印製 依實例1粘著性試驗法測量實例7 8至8 0之銅膜用 陶瓷基材間之粘著強度。粘著性試驗結果列於表1 8中。 對上述實例銅膜所進行之粘著性試驗結果顯示，當藉 具有於還原溶液浴中將陶瓷基材上所形成之氧化銅層還原 成金屬銅層之步驟之本發明方法於陶瓷基材上形成銅膜時 ，可得到銅膜與陶瓷基材間高於4 kg / 4 mm2之高粘著強 度。尤其，比較實施例與對照例之結果時，發現使用還原 溶液而非於高溫（例如5 0 0 °C )加熱之還原氣體進行還 原步驟時，粘著強度有相當程度之增加。 ----------^---裝------訂 泳 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） -38，Example 6 0-6 3 After the surface of each ceramic substrate was treated with a solution containing palladium ions, a first copper undercoat layer was formed on the surface of the ceramic substrate by electroless plating. 5vm。 The thickness of the first base coat is about 0. 5vm. Bismuth resin acid slurry (Bi content: 10%) is printed on the first layer of undercoating by screen printing to form a second layer of bismuth undercoating. The printed substrate was dried at about 125 ° C for 10 minutes, and heat-treated in air at a temperature of 850 ° C for 1 hour to form a copper oxide layer on the surface of the second primer layer. . In Examples 60 and 61, the copper oxide layer was reduced to a metallic copper layer by impregnating a ceramic substrate having a copper oxide layer in a sodium boron ammonium hydroxide aqueous solution at a temperature of 40 or 80 ° C for 5 minutes. The aqueous solution has a pH of 1 2.5. In Examples 62 and 63, a ceramic substrate with a copper oxide layer was impregnated at 25 ° C — Ί ^ .. J Pack — Order I 111 .. (please read the precautions on the back before filling this page) The paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0 X 297 mm) -29-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy and Economy 470734 A7 B7 V. Description of Invention (27) or 40. (: Dimethylamine borane aqueous solution for 5 minutes to reduce the copper oxide layer to a metallic copper layer. Water-soluble, liquid p Η 4.1. Later, an extra copper layer is formed on the metallic copper layer by electroless electricity ore, and the thickness is about 1 〇 Copper film. In Examples 60 to 63, the adhesion strength between the copper film and the ceramic substrate was measured according to the adhesion test of Example 1. The results of the adhesion test are shown in Table 13 and Table 13. Reducing solution. Reducing temperature adhesive strength (° C) (kg / 4mm2) Example 60 Sodium borohydride 40 4.4 Example 61 Sodium borohydride 80 4.5 Example 62 Dimethylamine borane 25 4.6 Example 63 Dimethylamine borane 40 4.6 Implementation Example 6 4 — 6 8 Basically consist of copper resin acid slurry (Cu content: 3.7 wt%) bismuth resin acid purple solution (Bi content: 10%.) And vanadium resin acid slurry (V is applicable for this paper size) China National Standards (CNS) A4 specifications (210X297 mm ·) ~ -30------------ Private clothing ------ ~ tr ------- m. (Please read the precautions on the back before filling in this page) 470734 A7 B7 V. Description of the invention (28) Amount: 1. 9w t%) The mixed resin salt slurry composed of sieve printing method is listed in Table 1 4 Individual ceramics On the surface of the substrate, a base coat of the mixed slurry is obtained. After the base coat is dried at 125 ° C for 10 minutes, it is heat-treated in air at 600 ° C for 1 hour to form an oxide on the surface of the base coat. Copper layer. The copper oxide layer is reduced to a metallic copper layer by immersing a ceramic substrate having a copper oxide layer in a sodium borohydride aqueous bath at a temperature of 80 ° C. for 5 minutes. The aqueous solution has a pH of 12. 5. By electroless plating on A frontal-outer copper layer was formed on the metallic copper layer, and a copper film with a thickness of about 10 // m was obtained on the ceramic substrate. The adhesion test was performed as in Example 1. The copper films and ceramic substrates of Examples 6 4 to 68 were measured. The adhesion strength between materials. The results of the adhesion test are shown in Table 1 4 (Please read the precautions on the back before filling out this page) Duo Yin, employee cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ This paper size applies Chinese National Standard (CNS ) A4 specification (210X297 mm) -31-470734 A7 B7 V. Description of invention (29) Table 1 4 Adhesive strength of ceramic substrate (kg / 4mm2) Example 64 Alumina 4.8 Example 65 Aluminum nitride 4.5 Example 66 Titanic acid Barium 5.0 Example 6 7 Silicon Carbide 4.2 Example 68 Zirconia 4.5 (Please read the back first Please fill in this page again.) Printed by the Consumers and Cooperatives of the Ministry of Economy, Intellectual Property, and Consumers. Cooperative Examples 1-5 The surface of each ceramic substrate listed in Table 15 is treated with a solution containing palladium ions, and then electrolessly plated on the ceramic substrate A copper undercoat is formed on the surface. The thickness of the primer layer is about 1 Mm ° The ceramic substrate with the primer layer is washed with water, dried ', and heat treated in air at a temperature of 500 ° C for 30 minutes to obtain a copper oxide layer. The copper oxide layer is reduced to a metallic copper layer by heating a ceramic substrate having the copper oxide layer in a hydrogen stream at a temperature of 500 ° C for 30 minutes. Afterwards, an extra copper layer was formed on the metal copper layer by using non-electric power ore. The thickness of the paper was formed on the ceramic substrate. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm): -32-470734 Α7 Β7 V. Description of the invention (30) 1 0 // m copper film. The adhesion strength between the copper films of Comparative Examples 1 to 5 and the ceramic substrate was measured according to the adhesion test of Example 1. The results of the adhesion test are shown in Table 15. In the adhesion test ', it was found that at the interface between the metallic copper layer and the additional copper layer, the copper film was peeled off individually. Printed by Economic / That Intellectual Property Bureau Employees 'Cooperatives Table 15 Adhesive Strength of Ceramic Substrate · (kg / 4mm2)' Comparative Example 1 Oxygen_Chemical 0.2 Comparative Example 2 Aluminum Nitride 0.3 Comparative Example 3 Barium Titanate 0.2 Comparative Example 4 Silicon Carbide 0.2 Comparative Example 5 Oxidation Error 0.3 ----------- Install ------- Order (Please read the precautions on the back before filling this page) Preparation Alumina Example 6 9 Aluminum Nitride 7 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 × 297 mm.) Barium titanate, silicon carbide 33-and chromium oxide ceramic 470734 A7 B7 V. Description of the invention (31) Porcelain stopper. A copper undercoat layer is formed on the surface of each ceramic substrate by electroless plating 'sputtering, or screening a resinate slurry of the copper organometallic compound listed in Table 16 below. Each ceramic substrate was not subjected to any roughening treatment on the surface before the undercoat layer was formed. However, the surface of the ceramic substrate is treated with a solution containing palladium ions before electroless ammonium. The undercoat thickness is about 0.5 vm. The undercoating-coated substrate was heat-treated in air at 1000 ° C for 45 minutes to form a copper oxide layer. The copper oxide layer is reduced to a metallic copper layer by impregnating a ceramic substrate with a copper oxide layer in a sodium borohydride aqueous solution bath at a temperature of -8 0 ° C. Water solution pH 12.5. An extra copper layer is formed on the metal copper layer by electroless plating, and a copper film with a thickness of about 10 is obtained on the ceramic substrate. After electroless plating, a copper film circuit pattern is formed on a ceramic substrate by a photosensitive printing method. The adhesion strength between the copper film of Examples 69 to 75 and the ceramic substrate was measured according to the adhesion test method of Example 1. The results of the adhesion test are shown in Table 16. (Please read the precautions on the back before filling out this page} Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -34-470734 A7 B7 V. Description of the Invention (32) Table 16 6 Method for forming a primer layer by printing ceramic substrates for consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economy Adhesive strength (kg / 4mm2) Example 69 Alumina electroless ore 4.2 Example 70 Aluminum nitride electroless electroplating 4.1 Example 7 1 Barium Titanate Electroless Plating 4.8 Example 72, Silicon Carbide Electroless Plating 3.7 Example 73 Zirconia Electroless Plating 4. 7 Example 74 Nitriding Sputtering 4, 1 Example 75 Alumina Screen Printing 3.8 Examples 76 and 77 Alumina Ceramics After the substrate surface is treated with a solution containing palladium ions, a copper undercoat layer is formed on the surface of the ceramic substrate by electroless plating. The undercoat layer is about 0.5 am thick. The undercoat layer is formed by the photosensitive printing method. The paper size of the primer is applicable to the China House 1 National Standard (CNS) A4 specification {210X297 mm) (Please read the precautions on the back before filling this page) Order -35 ~ 470734 A7 B7 V. Description of the invention ( 33) Layer pattern and exposed area of ceramic substrate. The surface of the ceramic substrate was not subjected to any roughening treatment before forming the undercoat layer. A masking coating consisting of zirconia powder and methylcellulose with an average particle size of 0.1 / 1 m was sprayed on the exposed area of the ceramic substrate and the circuit pattern of the primer layer. The ceramic substrate with the masking coating is heat-treated in air under the conditions listed in Table 17 'to form a copper oxide layer circuit pattern on the ceramic substrate, and then the masking coating is removed by ultrasonic cleaning with water. Thereafter, the ceramic substrate having the copper oxide layer was immersed in a borohydride-sodium aqueous solution bath at a temperature of 80 ° C to reduce the copper oxide layer to a metallic copper layer. Aqueous solution P Η 12. 5. An extra copper layer is formed on the metal copper layer by electroless plating, and a copper film with a thickness of about 10 is formed along the circuit pattern of the ceramic substrate. No additional copper layer was formed on the exposed area of the ceramic substrate. Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 17 Thermal treatment conditions of ceramic substrates Temperature time (° C) (min) Adhesive strength (kg / 4mm2) Example 76 Alumina 1000 45 4. 0 Example 77 Alumina 1100 10 4. Γ The copper paper sizes of Examples 7 6 and 7 7 are measured according to the adhesion test method of Example 1. The Chinese national standard (CNS > A4 size (210X297 mm)) ---------. Packing — II — Order — II Spicy (Please read the precautions on the back before filling out this page) -36, 470734 Α7 Β7 V. Description of the invention (34) Adhesive strength between the film and alumina ceramic substrate. Results of the adhesion test It is listed in Table 17. Example 7 8 — 8 0 According to the method substantially the same as that of Example 76, a copper film of about 10 μm thick was formed on the alumina ceramic substrate of Examples 7 to 80, with the difference The coating is not sprayed before heat treatment. The heat treatment is performed in air at different temperature and time conditions listed in Table 18. In Examples 7 9 and 80, the temperature is 100 ° C or higher. The heat treatment is performed under the following conditions, so the copper base coating formed on the ceramic substrate evaporates and is deposited on the ceramic substrate without the base coating. On the exposed area of the material. When copper is deposited in the exposed area, the circuit pattern of the copper film will be short-circuited. The results show that when heat treating the copper base coating at 100 ° C or higher temperature, it is better to spray the masking coating before heat treatment On the exposed area of ceramic substrate》 ----------. Install ------- order ------ grade (Please read the precautions on the back before filling this page) Economy / The paper size printed by the Ministry of Intellectual Property Bureau ’s Consumer Cooperatives applies the Chinese national standard (CNS) A4 specification (210 × 297 mm) -37, 470734 A7 B7 V. Description of the invention (35) Table 1 8 Ceramic substrate oxidation conditions temperature time ( ° C) (min) Adhesive strength (kg / 4mm2) Example 78 Alumina 850 360 3. 1 Example 79 Alumina 1000 45 4.0 Example 80 Alumina 1100 10 4.1 Example 1 The adhesion test method measures the adhesion strength between the ceramic substrates for copper films of Examples 7 to 80. The results of the adhesion test are shown in Table 18. The adhesion of the copper film of the above example The test results show that when the copper oxide layer formed on the ceramic substrate is reduced to When the method of the present invention, which is a step of copper layer, forms a copper film on a ceramic substrate, a high adhesion strength between the copper film and the ceramic substrate of more than 4 kg / 4 mm2 can be obtained. In particular, the comparative examples and comparative examples are compared. As a result, it was found that when the reduction step was performed using a reducing solution instead of a reducing gas heated at a high temperature (for example, 500 ° C), the adhesion strength was increased to a considerable extent. ---------- ^ --- install ------ order swimming (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 Mm) -38,