JP2015203148A - Copper alloy material, ceramic wiring board and production method of ceramic wiring board - Google Patents
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Abstract
Description
本発明は、銅合金材、セラミック配線基板及びセラミック配線基板の製造方法に関する。 The present invention relates to a copper alloy material, a ceramic wiring board, and a method for manufacturing a ceramic wiring board.
半導体素子を実装する基板として、セラミック配線基板が用いられることがある（例えば特許文献１〜２参照）。セラミック配線基板は、セラミック基板と、セラミック基板上に設けられ、例えばエッチングにより所定箇所が除去されて配線パターン（銅配線）になる銅合金材と、を備えている。 A ceramic wiring substrate may be used as a substrate for mounting a semiconductor element (see, for example, Patent Documents 1 and 2). The ceramic wiring substrate includes a ceramic substrate and a copper alloy material that is provided on the ceramic substrate and becomes a wiring pattern (copper wiring) by removing a predetermined portion by, for example, etching.
セラミック配線基板では、銅合金材に電流が通電されたり、通電が停止されることで、銅合金材が昇温と降温とを繰り返し、銅合金材に反りが生じてしまうことがある。これにより、セラミック基板に割れ等が発生し、セラミック配線基板の信頼性が低下してしまうことがある。 In a ceramic wiring board, when a current is applied to a copper alloy material or the current supply is stopped, the copper alloy material repeatedly increases and decreases in temperature, and the copper alloy material may be warped. Thereby, a crack etc. may generate | occur | produce in a ceramic substrate and the reliability of a ceramic wiring board may fall.
本発明は、上記課題を解決し、昇温と降温とを繰り返した場合であっても、銅合金材の反りの発生を抑制することを目的とする。 An object of the present invention is to solve the above-mentioned problems and suppress the occurrence of warpage of a copper alloy material even when the temperature rise and the temperature fall are repeated.
上記課題を解決するために、本発明は次のように構成されている。
本発明の一態様によれば、圧延されることで平板状に形成された銅合金材であって、５００℃以上９００℃以下の条件下で１時間以上加熱した後、表面に存在する複数の結晶面の結晶方位をそれぞれ測定し、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を前記（１００）面とみなしたとき、前記表面の面積に対する前記表面に存在する前記（１００）面の合計面積の割合が８５％以上である銅合金材が提供される。
In order to solve the above problems, the present invention is configured as follows.
According to one aspect of the present invention, a copper alloy material formed into a flat plate shape by rolling, and after heating for 1 hour or more under a condition of 500 ° C. or higher and 900 ° C. or lower, When each crystal orientation of the crystal plane is measured and a crystal plane having a crystal orientation whose inclination from the crystal orientation of the (100) plane is within 10 ° is regarded as the (100) plane, the surface relative to the area of the surface The copper alloy material whose ratio of the total area of the said (100) surface which exists in 85 is 85% or more is provided.
本発明の他の態様によれば、セラミック基板と、前記セラミック基板のいずれかの主面上に設けられ、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を前記（１００）面とみなしたとき、前記表面の面積に対する前記表面に存在する前記（１００）面の合計面積の割合が８５％以上である銅合金材と、を備えるセラミック配線基板が提供される。 According to another aspect of the present invention, a ceramic substrate and a crystal plane that is provided on any main surface of the ceramic substrate and has a crystal orientation in which an inclination from a crystal orientation of the (100) plane is within 10 °. And a copper alloy material in which the ratio of the total area of the (100) plane existing on the surface to the area of the surface is 85% or more is provided. The
本発明のさらに他の態様によれば、セラミック基板と、前記セラミック基板のいずれかの主面上に配置される銅合金材と、を加熱処理によって貼り合わせる工程を有し、前記加熱処理によって、少なくとも前記銅合金材の表面で再結晶を生じさせ、前記銅合金材の表面に存在する複数の結晶面の結晶方位をそれぞれ測定し、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を前記（１００）面とみなしたとき、前記表面の面積に対する前記表面に存在する前記（１００）面の合計面積の割合が８５％以上にするセラミック配線基板の製造方法が提供される。 According to still another aspect of the present invention, the method includes a step of bonding a ceramic substrate and a copper alloy material disposed on any main surface of the ceramic substrate by heat treatment, and by the heat treatment, Recrystallization occurs at least on the surface of the copper alloy material, and the crystal orientations of a plurality of crystal planes existing on the surface of the copper alloy material are measured, and the inclination from the crystal orientation of the (100) plane is within 10 °. When a crystal plane having a certain crystal orientation is regarded as the (100) plane, a method of manufacturing a ceramic wiring board in which a ratio of a total area of the (100) plane existing on the surface to an area of the surface is 85% or more Is provided.
本発明によれば、昇温と降温とを繰り返した場合であっても、銅合金材の反りの発生を抑制できる。 According to this invention, even if it is a case where temperature rising and temperature falling are repeated, generation | occurrence | production of the curvature of a copper alloy material can be suppressed.
＜本発明の一実施形態＞
（１）銅合金材及びセラミック配線基板の構成
まず、本発明の一実施形態にかかる銅合金材、及びその銅合金材を備えるセラミック配線基板の構成について説明する。
<One Embodiment of the Present Invention>
(1) Configuration of Copper Alloy Material and Ceramic Wiring Board First, the configuration of a copper alloy material according to an embodiment of the present invention and a ceramic wiring board including the copper alloy material will be described.
本実施形態にかかる銅合金材は、圧延されることで平板状に形成されている。銅合金材は、例えば５００℃以上９００℃以下の条件下で１時間以上加熱した後、銅合金材の表面（例えば銅合金材のいずれかの主面）に存在する各結晶面の結晶方位をそれぞれ測定し、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を、（１００）面とみなしたとき、銅合金材の表面の面積（銅合金材のいずれかの主面の面積）に対する、銅合金材の表面に存在する（１００）面の合計面積の割合が例えば８５％以上（つまり８５％以上１００％以下）、好ましくは９０％以上となるように、形成されている。 The copper alloy material according to the present embodiment is formed into a flat plate shape by being rolled. The copper alloy material is heated for 1 hour or more under the condition of 500 ° C. or more and 900 ° C. or less, for example, and then the crystal orientation of each crystal plane existing on the surface of the copper alloy material (for example, any main surface of the copper alloy material) When each of the measured crystal planes having a crystal orientation whose inclination from the crystal orientation of the (100) plane is within 10 ° is regarded as the (100) plane, the surface area of the copper alloy material (any of the copper alloy materials) The ratio of the total area of the (100) plane existing on the surface of the copper alloy material to the area of the main surface is, for example, 85% or more (that is, 85% or more and 100% or less), preferably 90% or more. Is formed.
銅合金材の表面に存在する各結晶面（各結晶粒）の結晶方位は、ＳＥＭ／ＥＢＳＤ法により測定される。ＳＥＭ／ＥＢＳＤ法とは、走査型電子顕微鏡（ＳＥＭ：Scanning Electron Microscope）で、試料としての銅合金材に電子線を照射したときに生じる電子後方散乱回折（ＥＢＳＤ：Electron Backscattering Diffraction）により形成される回折パターンを利用して、試料である銅合金材の表面に存在する結晶面の結晶方位を解析する方法である。例えば、ＳＥＭに、ＳＥＭから照射される電子線の軸と直交する軸に対して約６０°〜７０°傾斜させて試料としての銅合金材を配置し、試料に電子線を照射する。これにより、試料（銅合金材）の表面から約５０ｎｍの深さまでの領域に存在する各結晶面で電子後方散乱回折が生じ、回折パターンが得られる。得られた回折パターンを解析し、試料（銅合金材）の表面に存在する複数の各結晶面の結晶方位をそれぞれ解析する。 The crystal orientation of each crystal plane (each crystal grain) existing on the surface of the copper alloy material is measured by the SEM / EBSD method. The SEM / EBSD method is formed by electron backscattering diffraction (EBSD) generated when a copper alloy material as a sample is irradiated with an electron beam by a scanning electron microscope (SEM). This is a method of analyzing the crystal orientation of a crystal plane existing on the surface of a copper alloy material as a sample using a diffraction pattern. For example, a copper alloy material as a sample is disposed in the SEM at an angle of about 60 ° to 70 ° with respect to an axis orthogonal to the axis of the electron beam irradiated from the SEM, and the sample is irradiated with the electron beam. Thereby, electron backscattering diffraction occurs in each crystal plane existing in a region from the surface of the sample (copper alloy material) to a depth of about 50 nm, and a diffraction pattern is obtained. The obtained diffraction pattern is analyzed, and the crystal orientations of a plurality of crystal planes existing on the surface of the sample (copper alloy material) are analyzed.
続いて、結晶方位によって結晶粒を色分けし、例えば図１に示すような結晶方位マップを得る。つまり、同一の結晶方位を有する結晶面には、同一の色を付して結晶方位マップを得る。このとき、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面は、（１００）面とみなすこととする。つまり、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面は、（１００）面に含めることとする。そして、得られた結晶方位マップから、銅合金材の表面の面積に対する、銅合金材の表面に存在する（１００）面の合計面積の割合を算出することで、銅合金材の表面の（１００）面の配向性を評価できる。 Subsequently, the crystal grains are color-coded according to the crystal orientation to obtain a crystal orientation map as shown in FIG. 1, for example. That is, crystal planes having the same crystal orientation are given the same color to obtain a crystal orientation map. At this time, a crystal plane having a crystal orientation whose inclination from the crystal orientation of the (100) plane is within 10 ° is regarded as a (100) plane. That is, a crystal plane having a crystal orientation whose inclination from the crystal orientation of the (100) plane is within 10 ° is included in the (100) plane. Then, by calculating the ratio of the total area of the (100) plane existing on the surface of the copper alloy material to the area of the surface of the copper alloy material from the obtained crystal orientation map, (100 ) The orientation of the surface can be evaluated.
銅合金材は、銀（Ａｇ）、スズ（Ｓｎ）、ジルコニウム（Ｚｒ）のいずれか一つのみを含み、残部が銅及び不可避不純物からなる銅合金で形成されている。 The copper alloy material includes only one of silver (Ag), tin (Sn), and zirconium (Zr), and the balance is formed of a copper alloy composed of copper and inevitable impurities.
銅合金中にＡｇが含有されている場合は、銅合金中のＡｇの含有量（濃度）は、０．００５重量％以上であるとよく、０．００５重量％以上０．２０重量％以下であるとよりよい。Ａｇの含有量が０．００５重量％未満であると、５００℃以上９００℃以下の条件下で１時間以上の加熱処理（以下では「所定の加熱処理」とも言う。）を行った後の銅合金材の表面に存在する（１００）面の割合が８５％未満になってしまうことがある。つまり、所定の加熱処理後の銅合金材の（１００）面の配向性が８５％未満になってしまうことがある。Ａｇの含有量を０．００５重量％以上とすることで、これを解決できる。つまり、所定の加熱処理後の銅合金材の（１００）面の配向性を８５％以上にできる。また、銅合金材の耐熱性を向上させることができる。しかしながら、Ａｇは高価な元素であるため、Ａｇの含有量が０．２０重量％を超えると、銅合金材の製造コストが高くなってしまい、費用対効果が低くなってしまうことがある。従って、Ａｇの含有量は０．２０重量％以下とするとよい。 When Ag is contained in the copper alloy, the content (concentration) of Ag in the copper alloy is preferably 0.005 wt% or more, and is 0.005 wt% or more and 0.20 wt% or less. It is better if there is. When the Ag content is less than 0.005% by weight, the copper after heat treatment (hereinafter also referred to as “predetermined heat treatment”) for 1 hour or more under conditions of 500 ° C. or more and 900 ° C. or less. The ratio of the (100) plane existing on the surface of the alloy material may be less than 85%. That is, the orientation of the (100) plane of the copper alloy material after the predetermined heat treatment may be less than 85%. This can be solved by setting the Ag content to 0.005% by weight or more. That is, the orientation of the (100) plane of the copper alloy material after the predetermined heat treatment can be 85% or more. Moreover, the heat resistance of the copper alloy material can be improved. However, since Ag is an expensive element, if the Ag content exceeds 0.20% by weight, the manufacturing cost of the copper alloy material becomes high, and the cost effectiveness may be low. Therefore, the Ag content is preferably 0.20% by weight or less.
銅合金中にＳｎが含有されている場合は、銅合金中のＳｎの含有量（濃度）は、０．００５重量％以上であるとよく、０．００５重量％以上０．１５重量％以下であるとよりよい。Ｓｎの含有量が０．００５重量％未満であると、所定の加熱処理後の銅合金材の（１００）面の配向性が８５％未満になってしまうことがある。Ｓｎの含有量を０．００５重量％以上とすることで、所定の加熱処理後の銅合金材の（１００）面の配向性を８５％以上にできる。また、銅合金材の耐熱性を向上させることができる。しかしながら、Ｓｎの含有量が０．１５重量％を超えると、銅合金材の導電率が低下してしまうことがある。例えば、銅合金材の導電率が９０％ＩＡＣＳ未満となってしまうことがある。従って、Ｓｎの含有量を０．１５重量％以下とするとよい。これにより、銅合金材の導電率の低下を抑制できる。例えば、９０％ＩＡＣＳ以上の導電率を維持できる。 When Sn is contained in the copper alloy, the content (concentration) of Sn in the copper alloy is preferably 0.005 wt% or more, and is 0.005 wt% or more and 0.15 wt% or less. It is better if there is. When the Sn content is less than 0.005% by weight, the orientation of the (100) plane of the copper alloy material after the predetermined heat treatment may be less than 85%. By making the Sn content 0.005% by weight or more, the orientation of the (100) plane of the copper alloy material after the predetermined heat treatment can be made 85% or more. Moreover, the heat resistance of the copper alloy material can be improved. However, if the Sn content exceeds 0.15% by weight, the conductivity of the copper alloy material may decrease. For example, the conductivity of the copper alloy material may be less than 90% IACS. Therefore, the Sn content is preferably 0.15% by weight or less. Thereby, the fall of the electrical conductivity of a copper alloy material can be suppressed. For example, a conductivity of 90% IACS or higher can be maintained.
銅合金中にＺｒが含有されている場合は、銅合金中のＺｒの含有量（濃度）は、０．００５重量％以上であるとよく、０．００５重量％以上０．０５重量％以下であるとよりよい。Ｚｒの含有量が０．００５重量％未満であると、所定の加熱処理後の銅合金材の（１００）面の配向性が８５％未満になってしまうことがある。Ｚｒの含有量を０．００５重量％以上とすることで、所定の加熱処理後の銅合金材の（１００）面の配向性を８５％以上にできる。また、銅合金材の耐熱性を向上させることができる。しかしながら、Ｚｒの含有量が０．０５重量％を超えると、銅合金材の導電率が低下してしまうことがある。例えば、銅合金材の導電率が９０％ＩＡＣＳ未満となってしまうことがある。従って、Ｚｒの含有量を０．０５重量％以下とするとよい。これにより、銅合金材の導電率の低下を抑制できる。例えば、９０％ＩＡＣＳ以上の導電率を維持できる。 When Zr is contained in the copper alloy, the content (concentration) of Zr in the copper alloy is preferably 0.005% by weight or more and 0.005% by weight or more and 0.05% by weight or less. It is better if there is. If the Zr content is less than 0.005% by weight, the orientation of the (100) plane of the copper alloy material after the predetermined heat treatment may be less than 85%. By setting the Zr content to 0.005% by weight or more, the orientation of the (100) plane of the copper alloy material after the predetermined heat treatment can be made 85% or more. Moreover, the heat resistance of the copper alloy material can be improved. However, if the content of Zr exceeds 0.05% by weight, the conductivity of the copper alloy material may decrease. For example, the conductivity of the copper alloy material may be less than 90% IACS. Therefore, the Zr content is preferably 0.05% by weight or less. Thereby, the fall of the electrical conductivity of a copper alloy material can be suppressed. For example, a conductivity of 90% IACS or higher can be maintained.
Ｃｕとしては、酸素含有量が少ない無酸素銅（ＯＦＣ：Oxygen Free Copper）を用いるとよい。これにより、銅合金材中に酸化物が生成されることを抑制できる。従って、銅合金材の耐熱性をより向上させることができる。 As Cu, oxygen-free copper (OFC: Oxygen Free Copper) having a low oxygen content is preferably used. Thereby, it can suppress that an oxide is produced | generated in a copper alloy material. Therefore, the heat resistance of the copper alloy material can be further improved.
上述したように、銅合金材は平板状に形成されている。銅合金材は、厚さが例えば１００μｍ以上となるように形成されているとよい。銅合金材が例えば後述のセラミック配線基板に用いられる場合、銅合金材の厚さは、例えば１００μｍ以上であってセラミック基板の厚さよりも薄い厚さであるとよい。具体的には、銅合金材の厚さは、例えば１００μｍ以上１ｍｍ以下であるとよい。これにより、銅合金材を用いて後述のセラミック配線基板が形成された際、銅合金材に大電流を流すことができる。 As described above, the copper alloy material is formed in a flat plate shape. The copper alloy material may be formed to have a thickness of, for example, 100 μm or more. When the copper alloy material is used for a ceramic wiring board, which will be described later, for example, the thickness of the copper alloy material is preferably 100 μm or more and thinner than the thickness of the ceramic substrate. Specifically, the thickness of the copper alloy material is preferably, for example, 100 μm or more and 1 mm or less. Thereby, when the below-mentioned ceramic wiring board is formed using a copper alloy material, a large current can be passed through the copper alloy material.
本実施形態にかかるセラミック配線基板は、上述の銅合金材と、所定厚さ（例えば０．５ｍｍ）のセラミック基板と、を備えている。セラミック配線基板は、銅合金材とセラミック基板とが、例えばロウ材を介して貼り合わされることで形成されている。セラミック配線基板では、セラミック基板と貼り合わされる際の加熱により銅合金材に再結晶が生じ、銅合金材の（１００）面の配向性が８５％以上となっている。セラミック基板として、例えば、窒化アルミニウム（ＡｌＮ）や窒化ケイ素（ＳｉＮ）等を主成分とするセラミック焼結体が用いられる。ロウ材は、銀（Ａｇ）、銅（Ｃｕ）、スズ（Ｓｎ）、インジウム（Ｉｎ）、チタン（Ｔｉ）、モリブデン（Ｍｏ）、炭素（Ｃ）等の金属、またはこれらの金属のうち少なくとも１つを含む金属合金で形成されているとよい。銅合金材の所定箇所が例えばエッチングにより除去されることで、配線パターン（銅配線）が形成されている。 The ceramic wiring board according to the present embodiment includes the above-described copper alloy material and a ceramic board having a predetermined thickness (for example, 0.5 mm). The ceramic wiring board is formed by bonding a copper alloy material and a ceramic substrate through, for example, a brazing material. In a ceramic wiring board, recrystallization occurs in the copper alloy material by heating when it is bonded to the ceramic substrate, and the orientation of the (100) plane of the copper alloy material is 85% or more. As the ceramic substrate, for example, a ceramic sintered body mainly composed of aluminum nitride (AlN), silicon nitride (SiN), or the like is used. The brazing material is a metal such as silver (Ag), copper (Cu), tin (Sn), indium (In), titanium (Ti), molybdenum (Mo), carbon (C), or at least one of these metals. It is good to form with the metal alloy containing one. A predetermined pattern of the copper alloy material is removed by, for example, etching to form a wiring pattern (copper wiring).
（２）銅合金材及びセラミック配線基板の製造方法
次に、本実施形態にかかる銅合金材及び銅合金材を用いたセラミック配線基板の製造方法について、図２を参照しながら説明する。図２は、本実施形態にかかる銅合金材及びセラミック配線基板の製造工程を示すフロー図である。
(2) Manufacturing Method of Copper Alloy Material and Ceramic Wiring Board Next, a manufacturing method of a ceramic wiring board using the copper alloy material and the copper alloy material according to the present embodiment will be described with reference to FIG. FIG. 2 is a flowchart showing a manufacturing process of the copper alloy material and the ceramic wiring board according to the present embodiment.
［銅合金材形成工程（Ｓ１０）］
（鋳造工程（Ｓ１１））
図２に示すように、まず、母材であるＣｕ（例えば無酸素銅）を、例えば高周波溶解炉等を用いて溶解して銅の溶湯を生成する。続いて、銅の溶湯中に、Ａｇ、Ｓｎ、Ｚｒのいずれか一つのみを添加（固溶）して混合し、銅合金の溶湯を生成する。Ａｇを添加する場合は、銅合金材中のＡｇの含有量（濃度）が０．００５重量％以上、好ましくは０．２０重量％以下となるようにＡｇを添加する。Ｓｎを添加する場合は、銅合金材中のＳｎの含有量（濃度）が０．００５重量％以上、好ましくは０．１５重量％以下となるようにＳｎを添加する。Ｚｒを添加する場合は、銅合金材中のＺｒの含有量（濃度）が０．００５重量％以上、好ましくは０．０５重量％以下となるようにＺｒを添加する。そして、この銅合金の溶湯を鋳型に注いで冷却し、所定形状の鋳塊を鋳造（溶製）する。
[Copper alloy material forming step (S10)]
(Casting process (S11))
As shown in FIG. 2, first, Cu (for example, oxygen-free copper) as a base material is melted by using, for example, a high-frequency melting furnace or the like to generate a molten copper. Subsequently, only one of Ag, Sn, and Zr is added (solid solution) to the molten copper and mixed to form a molten copper alloy. In the case of adding Ag, Ag is added so that the content (concentration) of Ag in the copper alloy material is 0.005% by weight or more, preferably 0.20% by weight or less. In the case of adding Sn, Sn is added so that the content (concentration) of Sn in the copper alloy material is 0.005% by weight or more, preferably 0.15% by weight or less. In the case of adding Zr, Zr is added so that the content (concentration) of Zr in the copper alloy material is 0.005 wt% or more, preferably 0.05 wt% or less. Then, the molten copper alloy is poured into a mold and cooled, and an ingot having a predetermined shape is cast (melted).
（熱間圧延工程（Ｓ１２））
鋳造工程（Ｓ１１）が終了した後、まず、鋳塊（鋳造組織）中に生じている偏析を均質化する前処理を行う。前処理として、鋳塊中の結晶組織が平衡状態で均質な固溶状態となる温度以上の温度域に、鋳塊を所定時間保持する加熱処理を行うとよい。例えば、鋳塊を８００℃以上９５０℃以下で３０分以上加熱するとよい。
(Hot rolling process (S12))
After the casting step (S11) is completed, first, pretreatment for homogenizing segregation occurring in the ingot (cast structure) is performed. As pre-processing, it is good to perform the heat processing which hold | maintains an ingot for a predetermined time in the temperature range more than the temperature from which the crystal structure in an ingot will be in a homogeneous solid solution state in an equilibrium state. For example, the ingot may be heated at 800 ° C. or higher and 950 ° C. or lower for 30 minutes or longer.
そして、前処理を行った鋳塊に対して熱間圧延処理を行う。具体的には、鋳塊を前処理で加熱した温度域（つまり８００℃以上９５０℃以下）に維持した状態で、熱間圧延処理を行い、所定厚さ（例えば１２ｍｍ）の熱間圧延材を形成する。 And the hot rolling process is performed with respect to the ingot which performed the pre-processing. Specifically, in a state where the ingot is maintained in a temperature range (800 ° C. or more and 950 ° C. or less) heated in the pretreatment, a hot rolling treatment is performed to obtain a hot rolled material having a predetermined thickness (for example, 12 mm). Form.
（第１の冷間圧延工程（Ｓ１３））
熱間圧延工程（Ｓ１２）が終了した後、熱間圧延材に対して、冷間圧延処理と、再結晶焼鈍処理と、を所定回数繰り返して行い、所定厚さ（例えば１．０ｍｍ以上）の再結晶焼鈍材を形成する。このとき、再結晶焼鈍処理は、焼鈍後（再結晶後）の結晶粒が所定の粒径（例えば数十μｍ）となるように行うとよい。例えば、再結晶焼鈍処理として、６００℃以上９００℃以下の条件下で、数秒間〜数時間の加熱処理を行うとよい。
(First cold rolling step (S13))
After the hot rolling step (S12) is completed, the hot rolled material is repeatedly subjected to a cold rolling process and a recrystallization annealing process a predetermined number of times to obtain a predetermined thickness (for example, 1.0 mm or more). Recrystallized annealed material is formed. At this time, the recrystallization annealing treatment is preferably performed so that the crystal grains after annealing (after recrystallization) have a predetermined grain size (for example, several tens of μm). For example, as the recrystallization annealing treatment, heat treatment may be performed for several seconds to several hours under conditions of 600 ° C. or higher and 900 ° C. or lower.
（第２の冷間圧延工程（Ｓ１４））
第１の冷間圧延工程（Ｓ１３）が終了した後、再結晶焼鈍材に所定の冷間圧延処理を複数回連続して行い、所定厚さ（例えば１００μｍ以上）の銅合金材を形成する。つまり、第２の冷間圧延工程（Ｓ１４）では、焼鈍処理を挟まずに、冷間圧延処理を複数回連続して行う。第２の冷間圧延工程（Ｓ１４）では、被圧延材（再結晶焼鈍材）に再結晶が生じないような冷間圧延処理を行う。具体的には、第２の冷間圧延工程（Ｓ１４）では、１回の加工度ｒが４０％未満である冷間圧延処理を、総加工度Ｒが９０％以上となるように複数回連続して行う。
(Second cold rolling step (S14))
After the first cold rolling step (S13) is completed, the recrystallized annealing material is continuously subjected to a predetermined cold rolling process a plurality of times to form a copper alloy material having a predetermined thickness (for example, 100 μm or more). That is, in the second cold rolling step (S14), the cold rolling process is continuously performed a plurality of times without sandwiching the annealing process. In the second cold rolling step (S14), a cold rolling process is performed so that recrystallization does not occur in the material to be rolled (recrystallized annealing material). Specifically, in the second cold rolling step (S14), the cold rolling process in which the degree of work r at one time is less than 40% is continuously performed a plurality of times so that the total degree of work R is 90% or more. And do it.
１回の冷間圧延処理（１回の圧延パス）の加工度ｒは、下記の（数１）から求められる。なお、（数１）中、ｔ０は、１回の冷間圧延処理前の被圧延材の厚さであり、ｔは１回の冷間圧延処理後の被圧延材の厚さである。
（数１）
加工度ｒ（％）＝｛（ｔ０−ｔ）／ｔ０｝×１００
The degree of processing r in one cold rolling process (one rolling pass) is obtained from the following (Equation 1). In (Equation 1), t 0 is the thickness of the material to be rolled before one cold rolling process, and t is the thickness of the material to be rolled after one cold rolling process.
(Equation 1)
Degree of processing r (%) = {(t 0 −t) / t 0 } × 100
１回の冷間圧延処理の加工度ｒを４０％未満とすることで、冷間圧延処理を行うことにより発生する加工熱の量を低減できる。従って、複数回の冷間圧延処理を行って銅合金材を形成している間に、被圧延材が、加工熱により、再結晶が生じるような温度に加熱されることを抑制できる。また、銅合金材中に、通常の圧延組織（圧延処理を行うことで生じる結晶組織）とは異なる結晶組織が生じることを抑制できる。例えば、銅合金材中にせん断帯が生じることを抑制できる。せん断帯とは、銅合金材の厚さ方向に斜めに横断する結晶組織である。 By setting the working degree r of one cold rolling process to less than 40%, the amount of processing heat generated by performing the cold rolling process can be reduced. Accordingly, it is possible to prevent the material to be rolled from being heated to a temperature at which recrystallization occurs due to processing heat while the copper alloy material is formed by performing the cold rolling process a plurality of times. Moreover, it can suppress that the crystal structure different from a normal rolling structure | tissue (crystal structure produced by performing a rolling process) arises in a copper alloy material. For example, it can suppress that a shear band arises in a copper alloy material. The shear band is a crystal structure that crosses obliquely in the thickness direction of the copper alloy material.
総加工度Ｒは、下記の（数２）から求められる。なお、（数２）中、Ｔ０は、第２の冷間圧延工程（Ｓ１４）を行う前の被圧延材（つまり第１の冷間圧延工程（Ｓ１３）後の再結晶焼鈍材）の厚さであり、Ｔは、第２の冷間圧延工程（Ｓ１４）が終了した後の被圧延材（つまり銅合金材）の厚さである。
（数２）
総加工度Ｒ（％）＝｛（Ｔ０−Ｔ）／Ｔ０｝×１００
The total processing degree R is obtained from the following (Equation 2). In (Expression 2), T 0 is the thickness of the material to be rolled before the second cold rolling step (S14) (that is, the recrystallized annealing material after the first cold rolling step (S13)). T is the thickness of the material to be rolled (that is, the copper alloy material) after the second cold rolling step (S14) is completed.
(Equation 2)
Total processing rate R (%) = {(T 0 −T) / T 0 } × 100
総加工度Ｒを高くすることで、銅合金材に導入されるひずみ量を多くできる。これにより、後述のセラミック配線基板形成工程で所定の加熱処理を行うことで、銅合金材の表面の（１００）面の配向性を高めることができる。具体的には、総加工度Ｒを９０％以上にすることで、所定の加熱処理後の銅合金材の（１００）面の配向性を８５％以上にできる。 By increasing the total workability R, the amount of strain introduced into the copper alloy material can be increased. Thereby, the orientation of the (100) plane of the surface of a copper alloy material can be improved by performing predetermined heat processing at the below-mentioned ceramic wiring board formation process. Specifically, by setting the total workability R to 90% or more, the orientation of the (100) plane of the copper alloy material after the predetermined heat treatment can be made 85% or more.
［セラミック配線基板形成工程（Ｓ２０）］
続いて、上述の銅合金材を用いてセラミック配線基板を形成する。例えば、上述の銅合金材と、例えばＡｌＮを主成分とするセラミック焼結体で形成されるセラミック基板のいずれかの主面と、を例えばロウ材を介して貼り合わせ、セラミック配線基板を形成する。
[Ceramic wiring board forming step (S20)]
Subsequently, a ceramic wiring board is formed using the above-described copper alloy material. For example, the above-described copper alloy material and any main surface of a ceramic substrate formed of a ceramic sintered body mainly composed of AlN, for example, are bonded together via a brazing material, for example, to form a ceramic wiring substrate. .
まず、セラミック基板の表面の清浄処理を行う。例えば、セラミック基板を所定温度（例えば８００℃〜９００℃）に加熱して、セラミック基板の表面に付着している有機物や残留炭素を除去する。そして、例えばスクリーン印刷法により、セラミック基板のいずれかの主面上にペースト状のロウ材を塗布する。 First, the surface of the ceramic substrate is cleaned. For example, the ceramic substrate is heated to a predetermined temperature (for example, 800 ° C. to 900 ° C.) to remove organic substances and residual carbon adhering to the surface of the ceramic substrate. Then, a paste-like brazing material is applied on any main surface of the ceramic substrate by, for example, screen printing.
続いて、ロウ材上に銅合金材を配置する。その後、所定温度（例えば５００℃以上９００℃以下）で所定時間（例えば１時間以上）、銅合金材とセラミック基板との積層体を加熱し、銅合金材とセラミック基板とを貼り合わせてセラミック配線基板を形成する。銅合金材とセラミック基板とを貼り合わせる際の加熱は、真空雰囲気中で行うとよい。例えば、真空引きした窒素ガス等の不活性ガス雰囲気中で行うとよい。 Subsequently, a copper alloy material is disposed on the brazing material. Thereafter, the laminated body of the copper alloy material and the ceramic substrate is heated at a predetermined temperature (for example, 500 ° C. or more and 900 ° C. or less) for a predetermined time (for example, 1 hour or more), and the copper alloy material and the ceramic substrate are bonded together. A substrate is formed. Heating when the copper alloy material and the ceramic substrate are bonded together is preferably performed in a vacuum atmosphere. For example, it may be performed in an inert gas atmosphere such as a vacuumed nitrogen gas.
銅合金材とセラミック基板とを貼り合わせる際の加熱によって、銅合金材が加熱される。これにより、少なくとも銅合金材の表面（表面近傍）で再結晶が生じ、銅合金材の表面に存在する（１００）面の割合が８５％以上となる。つまり、銅合金材の（１００）面の配向性が８５％以上となる。 The copper alloy material is heated by heating when the copper alloy material and the ceramic substrate are bonded together. As a result, recrystallization occurs at least on the surface of the copper alloy material (near the surface), and the ratio of the (100) plane existing on the surface of the copper alloy material becomes 85% or more. That is, the orientation of the (100) plane of the copper alloy material is 85% or more.
（３）本実施形態にかかる効果
本実施形態によれば、以下に示す１つまたは複数の効果を奏する。
(3) Effects According to the Present Embodiment According to the present embodiment, one or a plurality of effects described below are exhibited.
（ａ）本実施形態では、圧延により平板状に形成された銅合金材が、５００℃以上９００℃以下の条件下で１時間以上加熱した後、表面に存在する複数の結晶面の結晶方位をそれぞれ測定し、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を（１００）面とみなしたとき、銅合金材の表面の面積に対する、銅合金材の表面に存在する（１００）面の合計面積の割合が８５％以上となるように形成されている。これにより、例えば、銅合金材が昇温と降温とを交互に繰り返した場合であっても、銅合金材が反ってしまうことを抑制できる。 (A) In this embodiment, after the copper alloy material formed into a flat plate shape by rolling is heated for 1 hour or more under the condition of 500 ° C. or more and 900 ° C. or less, the crystal orientations of the plurality of crystal planes existing on the surface are changed. The surface of the copper alloy material with respect to the area of the surface of the copper alloy material when a crystal face having a crystal orientation whose inclination from the crystal orientation of the (100) face is within 10 ° is regarded as the (100) face. The ratio of the total area of the (100) plane existing in is set to 85% or more. Thereby, even if it is a case where copper alloy material repeats temperature rising and temperature falling alternately, it can control that a copper alloy material warps, for example.
（ｂ）本実施形態にかかる銅合金材とセラミック基板とを加熱して貼り合わせて、セラミック配線基板を形成することで、セラミック配線基板では、銅合金材の表面の面積に対する、銅合金材の表面に存在する（１００）面の合計面積の割合を８５％以上にできる。これにより、例えば、銅合金材から形成された銅配線（配線パターン）に電流が通電されたり、通電が停止されることで、銅合金材の昇温と降温とが繰り返された場合であっても、銅合金材が反ってしまうことを抑制できる。従って、セラミック基板が、銅合金材に生じた反りに追従して反ることを抑制できる。その結果、セラミック基板に割れ（クラック）が発生することを抑制でき、セラミック配線基板の信頼性を向上させることができる。 (B) The copper alloy material and the ceramic substrate according to the present embodiment are heated and bonded together to form a ceramic wiring substrate. In the ceramic wiring substrate, the copper alloy material has a surface area of the copper alloy material. The ratio of the total area of (100) planes existing on the surface can be 85% or more. Thereby, for example, when a current is applied to a copper wiring (wiring pattern) formed from a copper alloy material or when the current supply is stopped, the temperature increase and the temperature decrease of the copper alloy material are repeated. Moreover, it can suppress that a copper alloy material warps. Therefore, it is possible to suppress the ceramic substrate from warping following the warp generated in the copper alloy material. As a result, the generation of cracks (cracks) in the ceramic substrate can be suppressed, and the reliability of the ceramic wiring substrate can be improved.
（ｃ）本実施形態に係る銅合金材は、例えば大電流用半導体素子が搭載されるセラミック配線基板に用いられる場合に、特に有効である。つまり、本実施形態に係る銅合金材から形成された銅配線に大電流が流され、銅合金材が加熱される温度が高くなった場合であっても、銅合金材が反ってしまうことを抑制できる。 (C) The copper alloy material according to the present embodiment is particularly effective when used, for example, in a ceramic wiring board on which a high-current semiconductor element is mounted. That is, even when a large current flows through the copper wiring formed from the copper alloy material according to the present embodiment and the temperature at which the copper alloy material is heated increases, the copper alloy material warps. Can be suppressed.
（ｄ）銅合金材の反りの発生が抑制されることで、セラミック配線基板において、銅合金材がセラミック基板から剥離することを抑制できる。その結果、セラミック配線基板の信頼性をより向上させることができる。 (D) Since the warpage of the copper alloy material is suppressed, the copper alloy material can be prevented from peeling from the ceramic substrate in the ceramic wiring substrate. As a result, the reliability of the ceramic wiring board can be further improved.
（ｅ）銅合金材は、（１００）面の割合が増えることで、低耐力の特性を有するようになり、変形に対して柔軟となる。これにより、銅合金材の昇温及び降温に従ってセラミック基板も昇温と降温とを繰り返すことで、セラミック基板に膨張や収縮等の変形が生じた場合であっても、銅合金材は、セラミック基板の変形に容易に追従することができる。その結果、銅合金材がセラミック基板から剥離することをより抑制できる。 (E) The copper alloy material has a low proof stress characteristic by increasing the proportion of the (100) plane, and is flexible to deformation. Thereby, even if the ceramic substrate is repeatedly heated and lowered according to the temperature rise and fall of the copper alloy material, even if the ceramic substrate is deformed such as expansion or contraction, the copper alloy material is Can easily follow the deformation. As a result, it can suppress more that a copper alloy material peels from a ceramic substrate.
（ｆ）所定の加熱処理後の銅合金材の表面に存在する（１００）面の割合を８５％以上にすることで、銅合金材のエッチングレートを均一にできる。銅合金材のエッチングレートは銅合金材を形成する結晶の異方性によって変化する。例えば、結晶配向の近い結晶粒では、エッチングレートが近くなる。銅合金材の表面に存在する各結晶粒を粗大化させることなく、銅合金材の表面の結晶面の配向性を揃えることで、銅合金材のエッチングレートを均一にでき、エッチング処理の安定性を向上させることができる。これにより、高精細な配線パターンを備えるセラミック配線基板を形成できる。 (F) By making the ratio of the (100) plane existing on the surface of the copper alloy material after the predetermined heat treatment be 85% or more, the etching rate of the copper alloy material can be made uniform. The etching rate of the copper alloy material varies depending on the anisotropy of crystals forming the copper alloy material. For example, an etching rate is close in a crystal grain having a close crystal orientation. The etching rate of the copper alloy material can be made uniform by aligning the crystal plane orientation of the surface of the copper alloy material without coarsening each crystal grain present on the surface of the copper alloy material, and the stability of the etching process Can be improved. Thereby, a ceramic wiring board provided with a high-definition wiring pattern can be formed.
（ｇ）第２の冷間圧延工程（Ｓ１４）で行う１回の冷間圧延処理の加工度ｒを４０％未満にすることで、冷間圧延処理を行うことで発生する加工熱を低減できる。つまり、被圧延材（再結晶焼鈍材）が、加工熱により再結晶が生じるような温度に加熱されることを抑制できる。これにより、銅合金材の表面の結晶面の配向性を揃えることができる。具体的には、所定の加熱処理後（例えばセラミック配線基板を形成する際の加熱処理後）に、銅合金材の表面に存在する（１００）面の割合を８５％以上にできる。従って、上記（ａ）〜（ｆ）の効果をより得ることができる。 (G) By reducing the working degree r of one cold rolling process performed in the second cold rolling process (S14) to less than 40%, the processing heat generated by performing the cold rolling process can be reduced. . That is, it can suppress that a to-be-rolled material (recrystallization annealing material) is heated to the temperature which a recrystallization produces with processing heat. Thereby, the orientation of the crystal plane on the surface of the copper alloy material can be made uniform. Specifically, after a predetermined heat treatment (for example, after the heat treatment for forming the ceramic wiring substrate), the ratio of the (100) surface existing on the surface of the copper alloy material can be 85% or more. Therefore, the effects (a) to (f) can be obtained more.
（ｈ）第２の冷間圧延工程（Ｓ１４）で行う１回の冷間圧延処理の加工度ｒを４０％未満にすることで、銅合金材中に、結晶面の整列を阻害するせん断帯が生じることを抑制できる。これにより、銅合金材の結晶面の配向性をより高めることができる。従って、上記（ａ）〜（ｆ）の効果をより得ることができる。 (H) A shear band that inhibits the alignment of crystal planes in the copper alloy material by making the degree of processing r of one cold rolling process performed in the second cold rolling step (S14) less than 40%. Can be suppressed. Thereby, the orientation of the crystal plane of the copper alloy material can be further enhanced. Therefore, the effects (a) to (f) can be obtained more.
（ｉ）銅合金材を、０．００５重量％以上のＡｇ、０．００５重量％以上のＳｎ、０．００５重量％以上のＺｒのうちのいずれか一つのみを含有し、残部がＣｕ及び不可避的不純物からなる銅合金で形成することで、所定の加熱処理後の銅合金材の（１００）面の配向性をより高めることができる。つまり、所定の加熱処理後の銅合金材の表面に存在する（１００）面の割合を８５％以上に、より容易にできる。従って、上記（ａ）〜（ｆ）の効果をより容易に得ることができる。 (I) The copper alloy material contains only one of 0.005 wt% or more of Ag, 0.005 wt% or more of Sn, and 0.005 wt% or more of Zr, with the balance being Cu and By forming with the copper alloy which consists of an unavoidable impurity, the orientation of the (100) plane of the copper alloy material after predetermined heat processing can be improved more. That is, the ratio of the (100) plane existing on the surface of the copper alloy material after the predetermined heat treatment can be more easily set to 85% or more. Therefore, the effects (a) to (f) can be obtained more easily.
（ｊ）Ａｇ、Ｓｎ、Ｚｒのうちのいずれか一つのみが母材であるＣｕ中に添加された銅合金で銅合金材を形成することで、銅合金材の耐熱性を向上させることができる。従って、銅合金材が反ることをより抑制できる。 (J) To improve the heat resistance of a copper alloy material by forming a copper alloy material with a copper alloy in which only one of Ag, Sn, and Zr is added to Cu as a base material. it can. Therefore, it can suppress more that a copper alloy material warps.
（ｋ）銅合金材の厚さを１００μｍ以上とすることで、銅合金材に大電流を流すことができる。つまり、セラミック配線基板に、大電流用半導体素子を搭載できる。 (K) By setting the thickness of the copper alloy material to 100 μm or more, a large current can flow through the copper alloy material. That is, a large-current semiconductor element can be mounted on the ceramic wiring board.
（本発明の他の実施形態）
以上、本発明の一実施形態を具体的に説明したが、本発明は上述の実施形態に限定されるものではなく、その要旨を逸脱しない範囲で適宜変更可能である。
(Other embodiments of the present invention)
As mentioned above, although one Embodiment of this invention was described concretely, this invention is not limited to the above-mentioned embodiment, In the range which does not deviate from the summary, it can change suitably.
銅合金材は、Ａｇ、Ｓｎ、Ｚｒのうちの少なくとも２種以上を、合計含有量が０．１５重量％以下となるように含み、残部が銅及び不可避不純物からなる銅合金で形成されていてもよい。銅合金材をＡｇ、Ｓｎ、Ｚｒのうちの２種以上を含む銅合金で形成するときは、Ａｇ、Ｓｎ、Ｚｒの合計含有量が０．１５重量％を超えると、所定の加熱処理後の銅合金材の表面の面積に対する、銅合金材の表面に存在する（１００）面の合計面積の割合を８５％未満になってしまう。Ａｇ、Ｓｎ、Ｚｒの合計含有量を０．１５重量％以下とすることで、所定の加熱処理後の銅合金材の表面の面積に対する、銅合金材の表面に存在する（１００）面の合計面積の割合を８５％以上にできる。従って、上記（ａ）〜（ｆ）の効果を得ることができる。 The copper alloy material includes at least two of Ag, Sn, and Zr so that the total content is 0.15% by weight or less, and the balance is formed of a copper alloy composed of copper and inevitable impurities. Also good. When the copper alloy material is formed of a copper alloy containing two or more of Ag, Sn, and Zr, if the total content of Ag, Sn, and Zr exceeds 0.15% by weight, The ratio of the total area of the (100) plane existing on the surface of the copper alloy material to the surface area of the copper alloy material is less than 85%. By making the total content of Ag, Sn, and Zr 0.15% by weight or less, the total of (100) planes existing on the surface of the copper alloy material relative to the surface area of the copper alloy material after the predetermined heat treatment The area ratio can be 85% or more. Therefore, the effects (a) to (f) can be obtained.
Ａｇ、Ｓｎ、Ｚｒのうちの少なくとも２種以上を銅合金材中に含有するとき、銅合金中のＡｇの含有量（濃度）は、０．００５重量％以上であるとよく、０．００５重量％以上０．１５重量％未満であるとよりよい。また、銅合金中のＳｎの含有量（濃度）は、０．００５重量％以上であるとよく、０．００５重量％以上０．１５重量％未満であるとよりよい。また、銅合金中のＺｒの含有量（濃度）は、０．００５重量％以上であるとよく、０．００５重量％以上０．１５重量％以下であるとよりよい。Ａｇ、Ｓｎ、Ｚｒのうちの少なくとも２種以上を銅合金材中に含有する場合、Ａｇ、Ｓｎ、Ｚｒの合計含有量が０．１５重量％以下であっても、Ａｇ、Ｓｎ、Ｚｒのそれぞれの含有量が０．００５重量％未満であると、所定の加熱処理後の銅合金材の表面の面積に対する、銅合金材の表面に存在する（１００）面の合計面積の割合が８５％未満になってしまう。Ａｇ、Ｓｎ、Ｚｒのそれぞれの含有量を０．００５重量％以上とすることで、これを解決し、所定の加熱処理後の銅合金材の表面の面積に対する、銅合金材の表面に存在する（１００）面の合計面積の割合を８５％以上にできる。 When at least two of Ag, Sn, and Zr are contained in the copper alloy material, the content (concentration) of Ag in the copper alloy is preferably 0.005 wt% or more, and 0.005 wt. % Or more and less than 0.15% by weight. Further, the content (concentration) of Sn in the copper alloy is preferably 0.005% by weight or more, and more preferably 0.005% by weight or more and less than 0.15% by weight. Further, the content (concentration) of Zr in the copper alloy is preferably 0.005% by weight or more, and more preferably 0.005% by weight or more and 0.15% by weight or less. When at least two of Ag, Sn, and Zr are contained in the copper alloy material, each of Ag, Sn, and Zr, even if the total content of Ag, Sn, and Zr is 0.15% by weight or less If the content of is less than 0.005% by weight, the ratio of the total area of the (100) plane existing on the surface of the copper alloy material to the surface area of the copper alloy material after the predetermined heat treatment is less than 85% Become. This is solved by making each content of Ag, Sn, and Zr 0.005% by weight or more, and exists on the surface of the copper alloy material relative to the surface area of the copper alloy material after the predetermined heat treatment. The ratio of the total area of the (100) plane can be 85% or more.
上述の実施形態では、銅合金材の表面の（１００）面の配向性を、銅合金材の表面の面積（銅合金材のいずれかの主面の面積）に対する、銅合金材の表面に存在する（１００）面の面積の割合を算出することで評価したが、これに限定されない。例えば、銅合金材の表面に存在する結晶粒の大きさがほぼ同一である場合、銅合金材の表面の（１００）面の配向性を銅合金材の表面に存在する（１００）面の結晶方位を有する結晶粒の個数と、銅合金材の表面に存在する結晶粒の個数と、を算出することで評価してもよい。つまり、銅合金材の表面の（１００）面の配向性を、銅合金材の表面に存在する結晶粒の個数に対する銅合金材の表面に存在する（１００）面の結晶方位を有する結晶粒の個数の割合で評価してもよい。 In the above-described embodiment, the orientation of the (100) plane of the surface of the copper alloy material is present on the surface of the copper alloy material with respect to the surface area of the copper alloy material (the area of one of the main surfaces of the copper alloy material). Although it evaluated by calculating the ratio of the area of the (100) plane to do, it is not limited to this. For example, when the sizes of crystal grains existing on the surface of the copper alloy material are substantially the same, the orientation of the (100) plane on the surface of the copper alloy material is the crystal of the (100) plane existing on the surface of the copper alloy material. You may evaluate by calculating the number of the crystal grains which have an orientation, and the number of the crystal grains which exist in the surface of a copper alloy material. That is, the orientation of the (100) plane of the surface of the copper alloy material is determined by the crystal grains having the (100) plane crystal orientation existing on the surface of the copper alloy material with respect to the number of crystal grains existing on the surface of the copper alloy material. You may evaluate by the ratio of a number.
上述の実施形態では、セラミック配線基板形成工程（Ｓ２０）において、銅合金材とセラミック基板とを貼り合わせる際の加熱により、少なくとも銅合金材の表面（表面近傍）を再結晶させて、銅合金材の表面に存在する（１００）面の割合を８５％以上にしたが、これに限定されるものではない。例えば、第２の冷間圧延工程（Ｓ１４）が終了した後、銅合金材を所定温度で所定時間加熱して、銅合金材を再結晶させてもよい。 In the above-described embodiment, in the ceramic wiring substrate forming step (S20), at least the surface (near the surface) of the copper alloy material is recrystallized by heating when the copper alloy material and the ceramic substrate are bonded to each other. Although the ratio of the (100) plane existing on the surface of the film is 85% or more, it is not limited to this. For example, after the second cold rolling step (S14) is completed, the copper alloy material may be recrystallized by heating the copper alloy material at a predetermined temperature for a predetermined time.
上述の実施形態では、熱間圧延工程（Ｓ１２）として、前処理と熱間圧延処理とを行ったが、これに限定されない。例えば、前処理は行わなくてもよい。 In the above-described embodiment, the pretreatment and the hot rolling treatment are performed as the hot rolling step (S12), but the present invention is not limited to this. For example, pre-processing may not be performed.
上述の実施形態では、第１の冷間圧延工程（Ｓ１３）と、第２の冷間圧延工程（Ｓ１４）と、を行ったが、これに限定されない。条件によっては、例えば第１の冷間圧延工程（Ｓ１３）は省略してもよい。つまり、熱間圧延材に対して、焼鈍処理を挟むことなく、所定の冷間圧延処理を複数回連続して行い、所定厚さの銅合金材を形成してもよい。 In the above-described embodiment, the first cold rolling step (S13) and the second cold rolling step (S14) are performed, but the present invention is not limited to this. Depending on the conditions, for example, the first cold rolling step (S13) may be omitted. That is, a predetermined cold rolling process may be continuously performed a plurality of times without sandwiching the annealing process on the hot rolled material to form a copper alloy material having a predetermined thickness.
上述の実施形態では、セラミック配線基板形成工程で、清浄処理を行ったが、これに限定されない。例えば、清浄処理は行わなくてもよい。つまり、清浄処理は必要に応じて行えばよい。 In the above-described embodiment, the cleaning process is performed in the ceramic wiring substrate forming process, but the present invention is not limited to this. For example, the cleaning process may not be performed. That is, the cleaning process may be performed as necessary.
上述の実施形態では、ロウ材を介して銅合金材とセラミック基板とを貼り合わせてセラミック配線基板を形成したが、これに限定されない。つまり、銅合金材とセラミック基板とを、ロウ材を介さずに貼り合わせてもよい。例えば、銅合金材とセラミック基板とを直接貼り合わせてもよい。 In the above-described embodiment, the ceramic wiring substrate is formed by bonding the copper alloy material and the ceramic substrate via the brazing material. However, the present invention is not limited to this. That is, the copper alloy material and the ceramic substrate may be bonded together without using a brazing material. For example, a copper alloy material and a ceramic substrate may be bonded directly.
次に、本発明の実施例を説明するが、本発明はこれらに限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited thereto.
＜試料の作製＞
まず、実施例１〜２７及び比較例１〜７の各試料となる銅合金材を作製した。
<Preparation of sample>
First, the copper alloy material used as each sample of Examples 1-27 and Comparative Examples 1-7 was produced.
（実施例１）
実施例１では、母材として、無酸素銅を用いた。そして、例えば坩堝式溶解炉を用い、真空引きした不活性ガス（Ｎ２ガス）雰囲気中にて、母材を所定温度に加熱して溶解し、銅の溶湯を作製した。銅の溶湯の加熱を維持しつつ、Ａｇを銅の溶湯に添加して銅合金の溶湯を作製した。このとき、銅合金の溶湯中でのＡｇの含有量（濃度）が０．００５重量％となるように、Ａｇの添加量を調整した。銅合金の溶湯を鋳型に注いで冷却し、所定形状の銅合金の鋳塊（インゴット）を鋳造した。つまり、Ａｇの含有量が０．００５重量％であり、残部がＣｕ及び不可避不純物からなる銅合金のインゴットを鋳造した。なお、Ａｇの含有量（濃度）は、プラズマ発光分光法（ＩＣＰ−ＡＥＳ）により、鋳造したインゴット中のＡｇの濃度を分析した結果である。
(Example 1)
In Example 1, oxygen-free copper was used as a base material. Then, for example, using a crucible melting furnace, the base material was heated to a predetermined temperature and melted in an evacuated inert gas (N 2 gas) atmosphere to prepare a molten copper. While maintaining the heating of the molten copper, Ag was added to the molten copper to prepare a molten copper alloy. At this time, the addition amount of Ag was adjusted so that the content (concentration) of Ag in the molten copper alloy was 0.005 wt%. A molten copper alloy was poured into a mold and cooled to cast a copper alloy ingot having a predetermined shape. That is, a copper alloy ingot having an Ag content of 0.005% by weight and the balance of Cu and inevitable impurities was cast. The content (concentration) of Ag is a result of analyzing the concentration of Ag in the cast ingot by plasma emission spectroscopy (ICP-AES).
次に、インゴットに熱間圧延処理を行って熱間圧延材を形成した。そして、熱間圧延材に対して、冷間圧延処理と再結晶焼鈍処理とを所定回数繰り返して行い、所定厚さの再結晶焼鈍材を形成した。その後、再結晶焼鈍材に対して、１回の加工度が４０％未満である冷間圧延処理を、総加工度が９０％となるように所定回数連続して行い、厚さが０．３ｍｍの銅合金材を作製した。 Next, the ingot was hot-rolled to form a hot-rolled material. And the cold rolling process and the recrystallization annealing process were repeated with respect to the hot-rolled material by the predetermined number of times, and the recrystallization annealing material of the predetermined thickness was formed. Thereafter, the recrystallized annealed material is subjected to a cold rolling process in which the degree of work at one time is less than 40% continuously for a predetermined number of times so that the total degree of work is 90%, and the thickness is 0.3 mm. A copper alloy material was prepared.
続いて、セラミック基板として、ＡｌＮを主成分とし、厚さが０．５ｍｍであるセラミック焼結体を準備した。そして、セラミック基板を８００℃以上９００℃以下の条件で熱処理し、セラミック基板の表面に付着した有機物や残留炭素を除去する前処理を行った。 Subsequently, a ceramic sintered body having AlN as a main component and a thickness of 0.5 mm was prepared as a ceramic substrate. And the ceramic substrate was heat-processed on the conditions of 800 degreeC or more and 900 degrees C or less, and the pre-process which removes the organic substance and residual carbon which adhered to the surface of the ceramic substrate was performed.
その後、スクリーン印刷法により、セラミック基板のいずれかの主面上にペースト状のロウ材を、厚さが０．０３ｍｍとなるように塗布した。ロウ材として、Ａｇを５０重量％、Ｃｕを３０重量％、Ｓｎを９．５重量％、Ｉｎを９．５重量％、Ｃを１重量％含むロウ材を用いた。 Thereafter, a paste-like brazing material was applied on one of the main surfaces of the ceramic substrate by screen printing so as to have a thickness of 0.03 mm. As the brazing material, a brazing material containing 50% by weight of Ag, 30% by weight of Cu, 9.5% by weight of Sn, 9.5% by weight of In, and 1% by weight of C was used.
そして、ロウ材上に、作製した銅合金材を配置した後、真空雰囲気中（真空引きしたＮ２ガス雰囲気中）にて、銅合金材を配置したセラミック基板を５００℃の条件下で１時間以上加熱し、銅合金材とセラミック基板とを貼り合わせてセラミック配線基板をそれぞれ作製した。これを実施例１の試料とした。 Then, after arranging the produced copper alloy material on the brazing material, the ceramic substrate on which the copper alloy material is arranged is placed in a vacuum atmosphere (in a vacuumed N 2 gas atmosphere) at 500 ° C. for 1 hour. By heating as described above, the copper alloy material and the ceramic substrate were bonded to each other to produce a ceramic wiring board. This was used as the sample of Example 1.
（実施例２〜２７及び比較例１〜７）
実施例２〜２７及び比較例１〜７ではそれぞれ、Ａｇ、Ｓｎ、Ｚｒの含有量（濃度）と、銅合金材とセラミック基板とを貼り合わせる際の加熱温度と、を下記の表１に示す通りとした。その他は、実施例１と同様にしてセラミック配線基板を作製した。これらをそれぞれ、実施例２〜２７及び比較例１〜７の試料とした。
(Examples 2-27 and Comparative Examples 1-7)
In Examples 2 to 27 and Comparative Examples 1 to 7, the content (concentration) of Ag, Sn, and Zr, and the heating temperature when the copper alloy material and the ceramic substrate are bonded together are shown in Table 1 below. It was street. Otherwise, a ceramic wiring board was produced in the same manner as in Example 1. These were used as samples of Examples 2 to 27 and Comparative Examples 1 to 7, respectively.
＜評価結果＞
実施例１〜２７び比較例１〜７の各試料について、導電率と、所定の加熱処理後の（１００）面の配向性と、割れ・剥離評価と、寸法安定性と、を評価した。
<Evaluation results>
About each sample of Examples 1-27 and Comparative Examples 1-7, electrical conductivity, orientation of (100) plane after a predetermined heat treatment, crack / peeling evaluation, and dimensional stability were evaluated.
（導電率の評価）
実施例１〜２７及び比較例１〜７の各試料が備える銅合金材の導電率をそれぞれ測定した。導電率の測定は、四端子測定法により２０℃での電気抵抗を測定して行った。その結果を下記の表１に示す。
(Evaluation of conductivity)
The electrical conductivity of the copper alloy material with which each sample of Examples 1-27 and Comparative Examples 1-7 is equipped was measured, respectively. The conductivity was measured by measuring the electrical resistance at 20 ° C. by a four-terminal measurement method. The results are shown in Table 1 below.
（（１００）面の配向性の評価）
実施例１〜２７及び比較例１〜７の各試料が備える銅合金材について、銅合金材の表面（銅合金材のセラミック基板と対向する側とは反対側の面）の（１００）面の配向性について評価を行った。具体的には、ＳＥＭ／ＥＢＳＤ法により、銅合金材の表面に存在する各結晶面の結晶方位をそれぞれ測定し、結晶方位マップを作製した。このとき、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面は、（１００）面とみなした。そして、作製した結晶方位マップから、銅合金材の表面の面積に対する表面に存在する（１００）面の合計面積の割合を算出することで、銅合金材の（１００）面の配向性を評価した。その結果を下記の表１に示す。
(Evaluation of orientation of (100) plane)
About the copper alloy material with which each sample of Examples 1-27 and Comparative Examples 1-7 is equipped, (100) surface of the surface (the surface on the opposite side to the side which opposes the ceramic substrate of a copper alloy material) of a copper alloy material The orientation was evaluated. Specifically, the crystal orientation of each crystal plane existing on the surface of the copper alloy material was measured by the SEM / EBSD method, and a crystal orientation map was prepared. At this time, a crystal plane having a crystal orientation in which the inclination from the crystal orientation of the (100) plane was within 10 ° was regarded as a (100) plane. Then, the orientation of the (100) plane of the copper alloy material was evaluated by calculating the ratio of the total area of the (100) plane existing on the surface to the area of the surface of the copper alloy material from the produced crystal orientation map. . The results are shown in Table 1 below.
（割れ・剥離評価）
実施例１〜２７及び比較例１〜７の各試料をそれぞれ、−６５℃のエタノール及びドライアイスを混合した寒剤の液浴と、１５０℃のオイルバスの液浴と、に交互に投入した。具体的には、寒剤の液浴に５分間投入し、オイルバスの液浴に５分間投入し、これを１サイクルとして合計１０００サイクル繰り返した。そして、各試料が備えるセラミック基板に割れ（クラック）が発生していないか否か、また銅合金材がセラミック基板から剥離している箇所がないか否かを確認し、割れ・剥離評価を行った。セラミック基板に割れが発生しておらず、銅合金材がセラミック基板から剥離している箇所がない試料の評価を「○」とし、セラミック基板に割れが発生していたり、銅合金材がセラミック基板から剥離している箇所がある試料の評価を「×」とした。その結果を下記の表１に示す。
(Evaluation of cracking / peeling)
The samples of Examples 1 to 27 and Comparative Examples 1 to 7 were alternately put into a cryogen liquid bath in which ethanol and dry ice at −65 ° C. were mixed and a liquid bath in an oil bath at 150 ° C., respectively. Specifically, it was put into a cryogen bath for 5 minutes and then put into an oil bath bath for 5 minutes, and this was repeated for 1000 cycles in total. Then, check whether the ceramic substrate provided for each sample has cracks (cracks) and whether there are any places where the copper alloy material is peeled off from the ceramic substrate, and perform crack / peel evaluation. It was. If the ceramic substrate is not cracked and the copper alloy material is not peeled off from the ceramic substrate, the sample is evaluated as “◯”, and the ceramic substrate is cracked or the copper alloy material is ceramic substrate. The evaluation of the sample having a part peeled off from the sample was “x”. The results are shown in Table 1 below.
（寸法安定性の評価）
実施例１〜２７及び比較例１〜７の各試料が備える銅合金材の寸法安定性の評価は、以下に示すように行った。まず、各試料が備える銅合金材の一方の主面（銅合金材のセラミック基板と対向する側の面）上に、幅が１ｍｍで、所定長さのマスキングテープを貼った。そして、各試料が備える銅合金材に対し、塩化第二鉄を用い、２分間のスプレーエッチング処理を行い、各試料であるセラミック配線基板が備える銅合金材から所定箇所（マスキングテープが貼られていない箇所）を除去した。その後、マスキングテープを銅合金材から剥がして除去した。続いて、レーザ顕微鏡を用いて、エッチング部の側面を観察した。具体的には、エッチングされずにセラミック基板上に残った銅合金材の複数個所の厚さ（マスキング部の深さ方向の寸法）を測定する。そして、銅合金材の厚さの平均値（平均厚さ）を算出する。さらに、最も厚い厚さと平均厚さとの差分（最大差分）を算出し、平均厚さに対する最大差分の割合を算出した。最大差分の割合を銅合金材の寸法安定性として評価した。評価結果を下記の表１に示す。なお、最大差分の割合の値が小さいほど、銅合金材の寸法安定性が良いことを示す。
(Evaluation of dimensional stability)
Evaluation of the dimensional stability of the copper alloy materials included in the samples of Examples 1 to 27 and Comparative Examples 1 to 7 was performed as follows. First, a masking tape having a width of 1 mm and a predetermined length was pasted on one main surface of the copper alloy material included in each sample (the surface of the copper alloy material facing the ceramic substrate). Then, ferric chloride is used for the copper alloy material provided for each sample, and spray etching treatment is performed for 2 minutes. Removed). Thereafter, the masking tape was removed from the copper alloy material. Then, the side surface of the etching part was observed using the laser microscope. Specifically, the thickness (dimension in the depth direction of the masking portion) of the copper alloy material remaining on the ceramic substrate without being etched is measured. And the average value (average thickness) of the thickness of a copper alloy material is calculated. Furthermore, the difference (maximum difference) between the thickest thickness and the average thickness was calculated, and the ratio of the maximum difference to the average thickness was calculated. The ratio of the maximum difference was evaluated as the dimensional stability of the copper alloy material. The evaluation results are shown in Table 1 below. In addition, it shows that the dimensional stability of a copper alloy material is so good that the value of the ratio of a maximum difference is small.
（総合評価）
実施例１〜２７及び比較例１〜７の各試料の総合評価を行った。導電率が９０％ＩＡＣＳ以上であり、所定の加熱処理後の銅合金材の（１００）面の配向性が８５％以上であり、割れ・剥離評価が「○」であり、寸法安定性が１５％以下である試料の総合評価を「◎」とした。所定の加熱処理後の銅合金材の（１００）面の配向性が８５％以上であり、割れ・剥離評価が「○」であり、寸法安定性が１５％以下であるが、導電率が９０％ＩＡＣＳ未満である試料の総合評価を「○」とした。所定の加熱処理後の銅合金材の（１００）面の配向性が８５％未満である試料の総合評価を「×」とした。評価結果を下記の表１に示す。
(Comprehensive evaluation)
Comprehensive evaluation of each sample of Examples 1-27 and Comparative Examples 1-7 was performed. The conductivity is 90% IACS or higher, the orientation of the (100) plane of the copper alloy material after a predetermined heat treatment is 85% or higher, the crack / peeling evaluation is “◯”, and the dimensional stability is 15 The overall evaluation of samples that are less than or equal to% is designated as “◎”. The orientation of the (100) plane of the copper alloy material after the predetermined heat treatment is 85% or more, the crack / peeling evaluation is “◯”, the dimensional stability is 15% or less, but the conductivity is 90. The overall evaluation of samples that are less than% IACS was rated as “◯”. The overall evaluation of the sample in which the orientation of the (100) plane of the copper alloy material after the predetermined heat treatment was less than 85% was “x”. The evaluation results are shown in Table 1 below.
実施例１〜２７から、所定の加熱処理後（銅合金材とセラミック基板とを貼り合わせる加熱処理後）の銅合金材の表面に存在する（１００）面の割合が８５％以上であると、つまり銅合金材の（１００）面の配向性が８５％以上であると、銅合金材の昇温と降温とが繰り返された場合であっても、銅合金材の反りの発生が抑制されることを確認した。従って、セラミック配線基板が備えるセラミック基板に割れ（クラック）が生じたり、銅合金材がセラミック基板から剥離することがないことを確認した。また、銅合金材の（１００）面の配向性が８５％以上であると、銅合金材の寸法安定性が良好なことを確認した。つまり、銅合金材のエッチングレートが面内でより均一となることを確認した。その結果、高精細な銅配線を形成できる。 From Examples 1 to 27, when the ratio of the (100) surface existing on the surface of the copper alloy material after the predetermined heat treatment (after the heat treatment for bonding the copper alloy material and the ceramic substrate) is 85% or more, That is, when the orientation of the (100) plane of the copper alloy material is 85% or more, the occurrence of warpage of the copper alloy material is suppressed even when the temperature increase and decrease of the copper alloy material are repeated. It was confirmed. Therefore, it was confirmed that the ceramic substrate included in the ceramic wiring substrate was not cracked or the copper alloy material was not peeled off from the ceramic substrate. Moreover, it was confirmed that the dimensional stability of the copper alloy material was good when the orientation of the (100) plane of the copper alloy material was 85% or more. That is, it was confirmed that the etching rate of the copper alloy material became more uniform in the plane. As a result, high-definition copper wiring can be formed.
比較例１〜７から、所定の加熱処理後の銅合金材の表面に存在する（１００）面の割合が８５％未満であると、銅合金材の昇温と降温とが繰り返された場合、銅合金材に反りが生じることを確認した。従って、セラミック基板に割れが生じたり、銅合金材がセラミック基板から剥離してしまうことを確認した。また、銅合金材の寸法安定性が低下することを確認した。従って、銅合金材から形成される銅配線の寸法を安定させることができず、高精細な銅配線を形成することが難しくなる。 From Comparative Examples 1 to 7, when the ratio of the (100) plane present on the surface of the copper alloy material after the predetermined heat treatment is less than 85%, when the temperature increase and the temperature decrease of the copper alloy material are repeated, It was confirmed that warpage occurred in the copper alloy material. Therefore, it was confirmed that the ceramic substrate was cracked or the copper alloy material was peeled off from the ceramic substrate. Moreover, it confirmed that the dimensional stability of copper alloy material fell. Therefore, the dimension of the copper wiring formed from the copper alloy material cannot be stabilized, and it becomes difficult to form a high-definition copper wiring.
比較例１から、銅合金材がＡｇ、Ｓｎ又はＺｒのいずれも含有しない場合、所定の加熱処理後の銅合金材の表面に存在する（１００）面の割合が８５％未満となることを確認した。 From Comparative Example 1, when the copper alloy material does not contain any of Ag, Sn, or Zr, it is confirmed that the ratio of the (100) plane existing on the surface of the copper alloy material after the predetermined heat treatment is less than 85%. did.
実施例１〜４、２１と比較例２とを比較すると、銅合金材がＡｇのみ（Ａｇ及び不可避不純物のみ）を含有する場合、Ａｇの含有量が０．００５重量％以上であると、所定の加熱処理後の銅合金材の（１００）面の配向性を８５％以上にできることを確認した。 When Examples 1-4, 21 and Comparative Example 2 are compared, when the copper alloy material contains only Ag (only Ag and inevitable impurities), it is predetermined that the content of Ag is 0.005% by weight or more. It was confirmed that the orientation of the (100) plane of the copper alloy material after the heat treatment can be 85% or more.
また、実施例１〜４、２１から、銅合金材中のＡｇの含有量が多くなるほど、銅合金材の導電率が低くなることを確認した。実施例２１から、銅合金材中のＡｇの含有量が０．２０重量％を超えると、つまりＡｇの含有量が０．２５重量％となると、所定の加熱処理後の銅合金材の（１００）面の配向性を８５％以上にでき、導電率も９０％ＩＡＣＳ以上にできるが、製造コストが高くなってしまうことを確認した。 Moreover, from Examples 1-4 and 21, it confirmed that the electrical conductivity of a copper alloy material became low, so that content of Ag in a copper alloy material increased. From Example 21, when the content of Ag in the copper alloy material exceeds 0.20% by weight, that is, when the content of Ag becomes 0.25% by weight, (100 ) The orientation of the surface can be 85% or more and the conductivity can be 90% IACS or more, but it has been confirmed that the manufacturing cost is increased.
実施例５〜８、２２と比較例３とを比較すると、銅合金材がＳｎのみ（Ｓｎ及び不可避不純物のみ）を含有する場合、Ｓｎの含有量が０．００５重量％以上であると、所定の加熱処理後の銅合金材の（１００）面の配向性を８５％以上にできることを確認した。 When Examples 5 to 8 and 22 are compared with Comparative Example 3, when the copper alloy material contains only Sn (only Sn and inevitable impurities), the content of Sn is predetermined to be 0.005% by weight or more. It was confirmed that the orientation of the (100) plane of the copper alloy material after the heat treatment can be 85% or more.
また、実施例５〜８、２２から、銅合金材中のＳｎの含有量が多くなるほど、銅合金材の導電率が低くなることを確認した。実施例２２から、銅合金材中のＳｎの含有量が０．１５重量％を超えると、つまり０．２００重量％になると、所定の加熱処理後の（１００）面の配向性は８５％以上にできるが、導電率が９０％ＩＡＣＳ未満となることを確認した。 Moreover, from Examples 5-8, 22, it confirmed that the electrical conductivity of a copper alloy material became low, so that content of Sn in a copper alloy material increased. From Example 22, when the Sn content in the copper alloy material exceeds 0.15 wt%, that is, 0.200 wt%, the orientation of the (100) plane after the predetermined heat treatment is 85% or more. However, it was confirmed that the conductivity was less than 90% IACS.
実施例９〜１２、２３と比較例４とを比較すると、銅合金材がＺｒのみ（Ｚｒ及び不可避不純物のみ）を含有する場合、Ｚｒの含有量が０．００５重量％以上であると、所定の加熱処理後の銅合金材の（１００）面の配向性を８５％以上にできることを確認した。 When Examples 9 to 12 and 23 are compared with Comparative Example 4, when the copper alloy material contains only Zr (only Zr and inevitable impurities), the Zr content is predetermined to be 0.005% by weight or more. It was confirmed that the orientation of the (100) plane of the copper alloy material after the heat treatment can be 85% or more.
また、実施例９〜１２、２３から、銅合金材中のＺｒの含有量が多くなるほど、銅合金材の導電率が低くなることを確認した。実施例２３から、銅合金材中のＺｒの含有量が０．０５重量％を超えると、つまり０．１００重量％になると、所定の加熱処理後の（１００）面の配向性は８５％以上にできるが、導電率が９０％ＩＡＣＳ未満となることを確認した。 Moreover, from Examples 9-12 and 23, it confirmed that the electrical conductivity of a copper alloy material became low, so that content of Zr in a copper alloy material increased. From Example 23, when the content of Zr in the copper alloy material exceeds 0.05% by weight, that is, 0.100% by weight, the orientation of the (100) plane after the predetermined heat treatment is 85% or more. However, it was confirmed that the conductivity was less than 90% IACS.
実施例１３〜２７と比較例５〜７とを比較すると、銅合金材（鋳塊）中にＡｇ、Ｓｎ又はＺｒのうちの２種以上を含有する場合、０．００５重量％以上のＡｇ、０．００５重量％以上のＳｎ、又は０．００５重量％以上のＺｒのうちの少なくとも２種以上を、合計含有量が０．１５重量％以下となるように含有すると、所定の加熱処理後の銅合金材の（１００）面の配向性を８５％以上にできることを確認した。つまり、Ａｇ、Ｓｎ又はＺｒのうちの２種以上の合計含有量が０．１５重量％未満であっても、Ａｇ、Ｓｎ、Ｚｒのそれぞれの含有量が０．００５重量％未満であると、所定の加熱処理後の銅合金材の（１００）面の配向性が８５％未満となることを確認した。 When Examples 13 to 27 are compared with Comparative Examples 5 to 7, when two or more of Ag, Sn, or Zr are contained in the copper alloy material (ingot), 0.005% by weight or more of Ag, When at least two or more of 0.005 wt% or more of Sn or 0.005 wt% or more of Zr are contained so that the total content is 0.15 wt% or less, It was confirmed that the orientation of the (100) plane of the copper alloy material could be 85% or more. That is, even if the total content of two or more of Ag, Sn, or Zr is less than 0.15% by weight, the content of each of Ag, Sn, and Zr is less than 0.005% by weight. It was confirmed that the orientation of the (100) plane of the copper alloy material after the predetermined heat treatment was less than 85%.
また、実施例２４〜２７から、銅合金材（鋳塊）中にＡｇ、Ｓｎ又はＺｒのうちの２種以上を含有する場合、Ａｇ、Ｓｎ又はＺｒの合計含有量が０．１５重量％を超えると、所定の加熱処理後の（１００）面の配向性は８５％以上にできるが、導電率が９０％ＩＡＣＳ未満となることを確認した。 Moreover, from Examples 24-27, when two or more types of Ag, Sn, or Zr are contained in the copper alloy material (ingot), the total content of Ag, Sn, or Zr is 0.15% by weight. When exceeding, the orientation of the (100) plane after the predetermined heat treatment can be 85% or more, but it was confirmed that the conductivity was less than 90% IACS.
＜本発明の好ましい態様＞
以下に、本発明の好ましい態様について付記する。
<Preferred embodiment of the present invention>
Hereinafter, preferred embodiments of the present invention will be additionally described.
［付記１］
本発明の一態様によれば、
圧延されることで平板状に形成された銅合金材であって、
５００℃以上９００℃以下の条件下で１時間以上加熱した後、表面に存在する複数の結晶面の結晶方位をそれぞれ測定し、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を前記（１００）面とみなしたとき、前記表面の面積に対する前記表面に存在する前記（１００）面の合計面積の割合が８５％以上である銅合金材が提供される。
[Appendix 1]
According to one aspect of the invention,
It is a copper alloy material formed into a flat plate shape by being rolled,
After heating for 1 hour or more under conditions of 500 ° C. or more and 900 ° C. or less, the crystal orientations of a plurality of crystal planes existing on the surface are measured, and the crystal whose inclination from the crystal orientation of the (100) plane is within 10 ° When a crystal plane having an orientation is regarded as the (100) plane, a copper alloy material in which the ratio of the total area of the (100) plane existing on the surface to the area of the surface is 85% or more is provided.
［付記２］
付記１の銅合金材であって、好ましくは、
０．００５重量％以上の銀、０．００５重量％以上のスズ、０．００５重量％以上のジルコニウムのうちのいずれか一つを含有し、残部が銅及び不可避的不純物からなる銅合金で形成されている。
[Appendix 2]
The copper alloy material of Appendix 1, preferably,
It is formed of a copper alloy containing at least 0.005% by weight of silver, 0.005% by weight of tin, or 0.005% by weight of zirconium, with the balance being copper and inevitable impurities. Has been.
［付記３］
付記１の銅合金材であって、好ましくは、
０．００５重量％以上０．２０重量％以下の銀、０．００５重量％以上０．１５重量％以下のスズ、０．００５重量％以上０．０５重量％以下のジルコニウムのうちのいずれか一つを含有し、残部が銅及び不可避的不純物からなる銅合金で形成されている。
[Appendix 3]
The copper alloy material of Appendix 1, preferably,
Any one of 0.005% to 0.20% by weight of silver, 0.005% to 0.15% by weight of tin, and 0.005% to 0.05% by weight of zirconium. The balance is formed of a copper alloy composed of copper and inevitable impurities.
［付記４］
付記１の銅合金材であって、好ましくは、
０．００５重量％以上の銀、０．００５重量％以上のスズ、０．００５重量％以上のジルコニウムのうちの少なくとも２種以上を、合計含有量が０．１５重量％以下となるように含有し、残部が銅及び不可避的不純物からなる銅合金で形成されている。
[Appendix 4]
The copper alloy material of Appendix 1, preferably,
Contains at least two of 0.005 wt% or more of silver, 0.005 wt% or more of tin, and 0.005 wt% or more of zirconium so that the total content is 0.15 wt% or less. The balance is made of a copper alloy composed of copper and inevitable impurities.
［付記５］
付記１の銅合金材であって、好ましくは、
０．００５重量％以上０．１５重量％未満の銀、０．００５重量％以上０．１５重量％未満のスズ、０．００５重量％以上０．０５重量％以下のジルコニウムのうちの少なくとも２種以上を、合計含有量が０．１５重量％以下となるように含有し、残部が銅及び不可避的不純物からなる銅合金で形成されている。
[Appendix 5]
The copper alloy material of Appendix 1, preferably,
At least two of 0.005 wt% or more and less than 0.15 wt% silver, 0.005 wt% or more and less than 0.15 wt% tin, 0.005 wt% or more and 0.05 wt% or less zirconium The above is contained so that total content may be 0.15 weight% or less, and the remainder is formed with the copper alloy which consists of copper and an unavoidable impurity.
［付記６］
付記１ないし５のいずれかの銅合金材であって、好ましくは、
厚さが１００μｍ以上である。
[Appendix 6]
The copper alloy material according to any one of appendices 1 to 5, preferably,
The thickness is 100 μm or more.
［付記７］
付記１ないし６のいずれかの銅合金材であって、好ましくは、
前記銅として無酸素銅が用いられている。
[Appendix 7]
The copper alloy material according to any one of appendices 1 to 6, preferably,
Oxygen-free copper is used as the copper.
［付記８］
本発明の他の態様によれば、
０．００５重量％以上の銀、０．００５重量％以上のスズ、０．００５重量％以上のジルコニウムのうちのいずれか一つを含有し、残部が銅及び不可避的不純物からなる鋳塊を鋳造する工程と、
前記鋳塊に熱間圧延処理を行って熱間圧延材を形成する工程と、
前記熱間圧延材に冷間圧延処理及び再結晶焼鈍処理を繰り返して行うことで再結晶焼鈍材を形成する工程と、
前記再結晶焼鈍材に、１回の加工度が４０％未満である冷間圧延処理を、総加工度が９０％以上となるように複数回連続して行う工程と、を有する銅合金材の製造方法が提供される。
[Appendix 8]
According to another aspect of the invention,
Casting an ingot containing at least 0.005% by weight of silver, 0.005% by weight or more of tin, and 0.005% by weight or more of zirconium, with the balance being copper and inevitable impurities And a process of
Performing a hot rolling treatment on the ingot to form a hot rolled material;
Forming a recrystallized annealed material by repeatedly performing a cold rolling process and a recrystallized anneal process on the hot rolled material;
A step of subjecting the recrystallized annealed material to a cold rolling process in which the degree of workability is less than 40%, and continuously performing a plurality of times so that the total degree of workability is 90% or more. A manufacturing method is provided.
［付記９］
本発明のさらに他の態様によれば、
０．００５重量％以上の銀、０．００５重量％以上のスズ、０．００５重量％以上のジルコニウムのうちの少なくとも２種以上を、合計含有量が０．１５重量％以下となるように含有し、残部が銅及び不可避的不純物からなる鋳塊を鋳造する工程と、
前記鋳塊に熱間圧延処理を行って熱間圧延材を形成する工程と、
前記熱間圧延材に冷間圧延処理及び再結晶焼鈍処理を繰り返して行うことで再結晶焼鈍材を形成する工程と、
前記再結晶焼鈍材に、１回の加工度が４０％未満である冷間圧延処理を、総加工度が９０％以上となるように複数回連続して行う工程と、を有する銅合金材の製造方法が提供される。
[Appendix 9]
According to yet another aspect of the invention,
Contains at least two of 0.005 wt% or more of silver, 0.005 wt% or more of tin, and 0.005 wt% or more of zirconium so that the total content is 0.15 wt% or less. And a step of casting an ingot consisting of copper and inevitable impurities as the balance,
Performing a hot rolling treatment on the ingot to form a hot rolled material;
Forming a recrystallized annealed material by repeatedly performing a cold rolling process and a recrystallized anneal process on the hot rolled material;
A step of subjecting the recrystallized annealed material to a cold rolling process in which the degree of workability is less than 40%, and continuously performing a plurality of times so that the total degree of workability is 90% or more. A manufacturing method is provided.
［付記１０］
本発明のさらに他の態様によれば、
セラミック基板と、
前記セラミック基板のいずれかの主面上に設けられ、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を前記（１００）面とみなしたとき、前記表面の面積に対する前記表面に存在する前記（１００）面の合計面積の割合が８５％以上である銅合金材と、を備えるセラミック配線基板が提供される。
[Appendix 10]
According to yet another aspect of the invention,
A ceramic substrate;
When a crystal plane having a crystal orientation that is provided on any main surface of the ceramic substrate and has an inclination from the crystal orientation of the (100) plane within 10 ° is regarded as the (100) plane, And a copper alloy material having a total area ratio of the (100) plane existing on the surface with respect to the area of 85% or more.
［付記１１］
本発明のさらに他の態様によれば、
セラミック基板と、前記セラミック基板のいずれかの主面上に配置される銅合金材と、を加熱処理によって貼り合わせる工程を有し、
前記加熱処理によって、少なくとも前記銅合金材の表面で再結晶を生じさせ、前記銅合金材の表面に存在する複数の結晶面の結晶方位をそれぞれ測定し、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を前記（１００）面とみなしたとき、前記表面の面積に対する前記表面に存在する前記（１００）面の合計面積の割合を８５％以上にするセラミック配線基板の製造方法が提供される。
[Appendix 11]
According to yet another aspect of the invention,
A step of bonding a ceramic substrate and a copper alloy material disposed on any main surface of the ceramic substrate by heat treatment;
Recrystallization occurs at least on the surface of the copper alloy material by the heat treatment, and the crystal orientations of a plurality of crystal planes existing on the surface of the copper alloy material are measured, respectively, and the inclination from the crystal orientation of the (100) plane When a crystal plane having a crystal orientation within 10 ° is regarded as the (100) plane, the ratio of the total area of the (100) plane existing on the surface to the area of the surface is 85% or more A method for manufacturing a wiring board is provided.
Claims (7)
５００℃以上９００℃以下の条件下で１時間以上加熱した後、表面に存在する複数の結晶面の結晶方位をそれぞれ測定し、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を前記（１００）面とみなしたとき、前記表面の面積に対する前記表面に存在する前記（１００）面の合計面積の割合が８５％以上である
銅合金材。 It is a copper alloy material formed into a flat plate shape by being rolled,
After heating for 1 hour or more under conditions of 500 ° C. or more and 900 ° C. or less, the crystal orientations of a plurality of crystal planes existing on the surface are measured, and the crystal whose inclination from the crystal orientation of the (100) plane is within 10 ° A copper alloy material in which, when a crystal plane having an orientation is regarded as the (100) plane, a ratio of a total area of the (100) plane existing on the surface to an area of the surface is 85% or more.
請求項１に記載の銅合金材。 It is formed of a copper alloy containing at least 0.005% by weight of silver, 0.005% by weight of tin, or 0.005% by weight of zirconium, with the balance being copper and inevitable impurities. The copper alloy material according to claim 1.
請求項１に記載の銅合金材。 Any one of 0.005% to 0.20% by weight of silver, 0.005% to 0.15% by weight of tin, and 0.005% to 0.05% by weight of zirconium. The copper alloy material according to claim 1, wherein the copper alloy material is formed of a copper alloy containing copper and inevitable impurities.
請求項１に記載の銅合金材。 Contains at least two of 0.005 wt% or more of silver, 0.005 wt% or more of tin, and 0.005 wt% or more of zirconium so that the total content is 0.15 wt% or less. And the copper alloy material of Claim 1 currently formed with the copper alloy which a remainder consists of copper and an unavoidable impurity.
請求項１ないし４のいずれかに記載の銅合金材。 The copper alloy material according to any one of claims 1 to 4, wherein the thickness is 100 µm or more.
前記セラミック基板のいずれかの主面上に設けられ、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を前記（１００）面とみなしたとき、前記表面の面積に対する前記表面に存在する前記（１００）面の合計面積の割合が８５％以上である銅合金材と、を備える
セラミック配線基板。 A ceramic substrate;
When a crystal plane having a crystal orientation that is provided on any main surface of the ceramic substrate and has an inclination from the crystal orientation of the (100) plane within 10 ° is regarded as the (100) plane, And a copper alloy material having a total area ratio of the (100) plane existing on the surface with respect to the area of 85% or more.
前記加熱処理によって、少なくとも前記銅合金材の表面で再結晶を生じさせ、前記銅合金材の表面に存在する複数の結晶面の結晶方位をそれぞれ測定し、（１００）面の結晶方位からの傾きが１０°以内である結晶方位を有する結晶面を前記（１００）面とみなしたとき、前記表面の面積に対する前記表面に存在する前記（１００）面の合計面積の割合を８５％以上にする
セラミック配線基板の製造方法。 A step of bonding a ceramic substrate and a copper alloy material disposed on any main surface of the ceramic substrate by heat treatment;
Recrystallization occurs at least on the surface of the copper alloy material by the heat treatment, and the crystal orientations of a plurality of crystal planes existing on the surface of the copper alloy material are measured, respectively, and the inclination from the crystal orientation of the (100) plane When a crystal plane having a crystal orientation within 10 ° is regarded as the (100) plane, the ratio of the total area of the (100) plane existing on the surface to the area of the surface is 85% or more A method for manufacturing a wiring board.
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