CN106544658A - 用于处理裸铜线的方法和试剂及表面处理过的铜线 - Google Patents

用于处理裸铜线的方法和试剂及表面处理过的铜线 Download PDF

Info

Publication number
CN106544658A
CN106544658A CN201611047684.6A CN201611047684A CN106544658A CN 106544658 A CN106544658 A CN 106544658A CN 201611047684 A CN201611047684 A CN 201611047684A CN 106544658 A CN106544658 A CN 106544658A
Authority
CN
China
Prior art keywords
phosphoric acid
copper wire
chelate compound
bare copper
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611047684.6A
Other languages
English (en)
Inventor
张鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung Semiconductor China R&D Co Ltd
Samsung Electronics Co Ltd
Original Assignee
Samsung Semiconductor China R&D Co Ltd
Samsung Electronics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samsung Semiconductor China R&D Co Ltd, Samsung Electronics Co Ltd filed Critical Samsung Semiconductor China R&D Co Ltd
Priority to CN201611047684.6A priority Critical patent/CN106544658A/zh
Publication of CN106544658A publication Critical patent/CN106544658A/zh
Priority to US15/701,924 priority patent/US20180142358A1/en
Priority to KR1020170156609A priority patent/KR20180058205A/ko
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/46—Structure, shape, material or disposition of the wire connectors prior to the connecting process of a plurality of wire connectors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1676—Phosphonic acids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49517—Additional leads
    • H01L23/4952—Additional leads the additional leads being a bump or a wire
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/43—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/43—Manufacturing methods
    • H01L2224/432—Mechanical processes
    • H01L2224/4321—Pulling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/43—Manufacturing methods
    • H01L2224/438—Post-treatment of the connector
    • H01L2224/4382—Applying permanent coating, e.g. in-situ coating
    • H01L2224/43821—Spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/43—Manufacturing methods
    • H01L2224/438—Post-treatment of the connector
    • H01L2224/4382—Applying permanent coating, e.g. in-situ coating
    • H01L2224/43822—Dip coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/43—Manufacturing methods
    • H01L2224/438—Post-treatment of the connector
    • H01L2224/43848—Thermal treatments, e.g. annealing, controlled cooling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/43—Manufacturing methods
    • H01L2224/43985—Methods of manufacturing wire connectors involving a specific sequence of method steps
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45147—Copper (Cu) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/4554—Coating
    • H01L2224/45599—Material
    • H01L2224/456—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45638—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45647—Copper (Cu) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/4554—Coating
    • H01L2224/45599—Material
    • H01L2224/45686—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/4554—Coating
    • H01L2224/45599—Material
    • H01L2224/4569—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • H01L2224/85009—Pre-treatment of the connector or the bonding area
    • H01L2224/8501—Cleaning, e.g. oxide removal step, desmearing
    • H01L2224/85011—Chemical cleaning, e.g. etching, flux
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector

Abstract

本发明公开了一种用于处理裸铜线的方法和试剂及表面处理过的铜线。所述方法包括如下步骤：将磷酸类螯合剂的溶液施加到裸铜线的表面；以及将表面附着有磷酸类螯合剂的溶液的裸铜线干燥。表面处理过的铜线包括铜线基体和包覆在铜线基体的表面上的铜‑有机化合物膜，铜‑有机化合物膜可具有固定的结构单元。

Description

用于处理裸铜线的方法和试剂及表面处理过的铜线
技术领域
本发明涉及金属的表面处理，特别涉及一种用于处理裸铜线的方法和试剂及表面处理过的铜线。
背景技术
在半导体封装工艺中，引线键合(wire bonding)是对裸片进行模塑之前执行的重要步骤。通常，采用金线来执行引线键合。但随着金价飙升，半导体器件的制造成本居高不下，从而降低了产品竞争力。因此，价格相对便宜、导电性能优异的铜线作为金线的替代品引起了广泛的关注和研究。
铜线的制造工艺可包括熔解铸造、铸锭、延展、伸线、热处理和绕线。在铜线的制造工艺中，铜线表面会不可避免地氧化，使得后续的引线键合工艺的工程作业性和信赖性劣化。因此，防止铜线表面的氧化和腐蚀是非常有必要的。
发明内容
本发明的一个目的在于提供一种用于处理裸铜线的方法和试剂及表面处理过的铜线。
本发明的另一目的在于提供一种能够解决上述技术问题中的至少一个技术问题的用于处理裸铜线的方法和试剂及表面处理过的铜线。
本发明的又一目的在于提供一种能够防止铜线表面的氧化和腐蚀的用于处理裸铜线的方法和试剂及表面处理过的铜线。
根据本发明的用于处理裸铜线的方法包括：将磷酸类螯合剂的溶液施加到裸铜线的表面；以及将表面附着有磷酸类螯合剂的溶液的裸铜线干燥。
将磷酸类螯合剂的溶液施加到裸铜线的表面的步骤可包括：将磷酸类螯合剂的溶液喷淋到裸铜线，或者将裸铜线浸在磷酸类螯合剂的溶液中。
将表面附着有磷酸类螯合剂的溶液的裸铜线干燥的步骤可包括：向表面附着有磷酸类螯合剂的溶液的裸铜线吹热风，或者在烘箱中干燥表面附着有磷酸类螯合剂的溶液的裸铜线，或者在环境温度下将表面附着有磷酸类螯合剂的溶液的裸铜线自然晾干。
磷酸类螯合剂的溶液可包括0.5wt％至2wt％的磷酸类螯合剂、0.1wt％至1.5wt％的表面活性剂和96.7wt％至99.2wt％的水。
磷酸类螯合剂可包括以下化合物中的至少一种：
表面活性剂可以是非离子表面活性剂。
根据本发明的用于处理裸铜线的试剂包括0.5wt％至2wt％的磷酸类螯合剂、0.1wt％至1.5wt％的表面活性剂和96.7wt％至99.2wt％的水。
根据本发明的表面处理过的铜线包括铜线基体和包覆在铜线基体的表面上的铜-有机化合物膜。
铜-有机化合物膜的厚度可在1nm至10nm的范围内。
铜-有机化合物膜可具有固定的结构单元。
附图说明
通过下面结合附图对示例性实施例进行的描述，本发明的上述和其他目的和特点将会变得更加清楚，其中：
图1是示出根据示例性实施例的用于处理裸铜线的方法的流程图；
图2是示出根据示例性实施例的表面处理过的铜线的示意性透视图；
图3是示出根据示例性实施例的表面处理过的铜线的示意性剖视图；
图4是示出根据示例性实施例的表面处理过的铜线经过酸处理之后的表面的显微照片；以及
图5是示出裸铜线经过酸处理之后的表面的显微照片。
具体实施方式
现在，将详细地参考本发明的实施例和方法，这些实施例和方法构成了发明人目前已知的实践本发明的最佳方式。附图不一定按照比例绘出，其中，同样的附图标记始终指同样的元件。然而，需要理解的是，所公开的实施例仅是可以以各种替换形式实施的该发明的举例说明。因此，这里公开的具体细节不应被理解为限制，仅是针对该发明的任何方面的代表性基础和/或用于教导本领域技术人员以各种形式应用本发明的代表性基础。
下面，将参照附图详细地描述根据示例性实施例的用于处理裸铜线的方法。
图1是示出根据示例性实施例的用于处理裸铜线的方法的流程图。参照图1，根据示例性实施例的用于处理裸铜线的方法10包括：将磷酸类螯合剂的溶液施加到裸铜线的表面(步骤S11)；以及将表面附着有磷酸类螯合剂的溶液的裸铜线干燥(步骤S12)。
裸铜线可以是不具有被氧化的表面的铜线。在示例性实施例中，裸铜线是在铜线的制造工艺刚刚经过热处理且还未绕线的裸铜线。裸铜线可具有小于0.5mm、小于0.2mm、小于0.1mm、小于0.08mm、小于0.06mm、小于0.04mm、小于0.02mm或小于0.01mm的直径。
磷酸类螯合剂的溶液包括作为溶质的磷酸类螯合剂和表面活性剂与作为溶剂的水。
磷酸类螯合剂可以包括以下化合物中的至少一种：
表面活性剂可以是非离子表面活性剂。非离子表面活性剂可包括聚乙二醇型非离子表面活性剂、多元醇型非离子表面活性剂和非离子氟碳表面活性剂中的至少一种。聚乙二醇型非离子表面活性剂可包括聚乙二醇、烷基酚聚氧乙烯醚、高碳脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯酯、聚氧乙烯胺、聚氧乙烯酰胺、聚丙二醇的环氧乙烷加成物中的至少一种。多元醇型非离子表面活性剂可包括失水山梨醇酯、蔗糖酯和烷基醇酰胺型非离子表面活性剂中的至少一种。优选地，在磷酸类螯合剂的溶液中使用的表面活性剂是非离子表面活性剂。优选地，所述非离子表面活性剂是聚乙二醇型非离子表面活性剂。优选地，聚乙二醇型非离子表面活性剂是聚乙二醇。
在示例性实施例中，可通过喷淋来执行步骤S11。例如，将磷酸类螯合剂的溶液装入与喷头连接的罐中，然后通过喷头将磷酸类螯合剂的溶液喷淋到裸铜线的表面，使裸铜线的表面与磷酸类螯合剂溶液接触。在喷淋的过程中，裸铜线可沿圆周方向匀速转动，使得磷酸类螯合剂的溶液可以均匀地接触裸铜面的表面。可以执行喷淋大约60s至大约90s。
在示例性实施例中，还可以通过将裸铜线浸在磷酸类螯合剂的溶液来执行步骤S11。可以执行浸渍大约60s至大约90s。
在示例性实施例中，可以通过向表面附着有磷酸类螯合剂的溶液的裸铜线吹热风来执行步骤S12。热风可具有大约40℃至大约80℃的温度，可以吹热风大约1min至大约5min。
在示例性实施例中，可以通过在烘箱中干燥表面附着有磷酸类螯合剂的溶液的裸铜线来执行步骤S12。烘箱的内部空间可具有大约40℃至大约70℃的温度，可以通过烘箱执行干燥大约5min至大约20min。
在示例性实施例中，可以通过在例如室温的环境温度下将表面附着有磷酸类螯合剂的溶液的裸铜线自然晾干来执行步骤S12。该自然晾干可以执行大约10min至120min。
在使裸铜线的表面与磷酸类螯合剂的溶液接触时，裸铜线与磷酸类螯合剂反应而生成化学惰性的铜-有机化合物膜。相对于裸铜线的表面，铜-有机化合物膜具有提高的抗氧化性和耐腐蚀性。因此，如此表面处理过的铜线与裸铜线相比具有提高的抗氧化性和耐腐蚀性，从而具有改善的工程作业性和信赖性。
在步骤S12完成后，可以在裸铜线的表面形成厚度在例如1nm-10nm(更具体地，2nm-8nm或3nm-7nm)的范围内的铜-有机化合物膜。如果铜-有机化合物膜太薄，则可能不能提供充分的抗氧化性和耐腐蚀性。如果铜-有机化合物膜的厚度超过10nm，则可能会导致引线键合中的缺陷。
基于磷酸类螯合剂的溶液的总重量，磷酸类螯合剂的溶液可包括0.5wt％至2wt％的磷酸类螯合剂、0.1wt％至1.5wt％的表面活性剂和96.7wt％至99.2wt％的水。在示例性实施例中，磷酸类螯合剂的溶液可包括0.7wt％至1.5wt％的磷酸类螯合剂、0.4wt％至1.2wt％的表面活性剂和97.5wt％至98.6wt％的水。在另一示例性实施例中，磷酸类螯合剂的溶液可包括0.8wt％至1.2wt％的磷酸类螯合剂、0.5wt％至0.9wt％的表面活性剂和98.0wt％至98.5wt％的水。在又一示例性实施例中，磷酸类螯合剂的溶液可包括1wt％的磷酸类螯合剂、0.5wt％的表面活性剂和98.5wt％的水。
如果磷酸类螯合剂的含量小于0.5wt％，则可能难以有效地形成铜-有机化合物膜。如果磷酸类螯合剂的含量大于2wt％，则形成的铜-有机化合物膜可能具有太大的厚度，从而可能导致引线键合中的缺陷。
表面活性剂可以促进裸铜线与磷酸类螯合剂之间的反应。如果表面活性剂的含量小于0.1wt％，则可能无法促进裸铜线与磷酸类螯合剂之间的反应。如果表面活性剂的含量大于1.5wt％，则可能使得裸铜线与磷酸类螯合剂之间的反应不稳定。
在示例性实施例中，磷酸类螯合剂的溶液还可包含其他的组分，例如，有利于磷酸类螯合剂的溶液的长期储存的稳定剂。在示例性实施例中，磷酸类螯合剂的溶液由具有上面描述的含量的磷酸类螯合剂、表面活性剂和水组成。
下面将参照图2至图5详细地描述根据上述方法处理过的铜线。图2是示出根据示例性实施例的表面处理过的铜线的示意性透视图，图3是示出根据示例性实施例的表面处理过的铜线的示意性剖视图。
参照图2和图3，表面处理过的铜线20包括铜线基体22和包覆在铜线基体22的表面上的铜-有机化合物膜21。铜线基体22可具有小于0.5mm、小于0.2mm、小于0.1mm、小于0.08mm、小于0.06mm、小于0.04mm、小于0.02mm或小于0.01mm的直径。铜-有机化合物膜21可具有在例如1nm-10nm(更具体地，2nm-8nm或3nm-7nm)的范围内的厚度。
在使裸铜线的表面与磷酸类螯合剂的溶液接触的过程中，例如，在步骤S11和/或S12中，裸铜线与磷酸类螯合剂反应(更具体地，裸铜线表面的铜离子与磷酸类螯合剂发生配位)而生成化学惰性的铜-有机化合物膜21。相对于铜线基体22的表面，铜-有机化合物膜21具有提高的抗氧化性和耐腐蚀性。因此，表面处理过的铜线20与裸铜线相比具有提高的抗氧化性和耐腐蚀性，从而具有改善的工程作业性和信赖性。
在示例性实施例中，铜-有机化合物膜21具有固定的结构单元，固定的结构单元可由下面的式1表示：
式1
具有由式1表示的固定的结构单元的铜-有机化合物膜21具有提高的抗氧化性和耐腐蚀性，可以保护铜线基体22不受氧化和腐蚀。
磷酸类螯合剂的上述示例具有与铜离子发生配位的作为有效官能团的磷酸根(-H2PO3)或磷酸酯基团(例如，磷酸二甲酯基团)，因此，磷酸类螯合剂可以容易地与铜离子一起产生例如由上面的式1表示的固定的结构单元。
用pH为大约2.5的盐酸溶液处理根据示例性实施例的表面处理过的铜线20和裸铜线。如此酸处理过的表面处理过的铜线20和裸铜线的显微照片分别示出在图4和图5中。
参照图4，确认的是，根据示例性实施例的表面处理过的铜线20在经过酸处理之后具有光滑的表面，而且没有出现变黑的现象。参照图5，确认的是，裸铜线经过相同条件下的酸处理之后，具有粗糙的表面，而且部分表面变黑，也就是说，表现出了明显的氧化和腐蚀现象。
因为裸铜线的外表面与酸直接接触，所以铜的表面被酸氧化生成了黑色的氧化铜。表面处理过的铜线20的表面附着有均匀的铜-有机化合物膜21，铜线基体22的表面不与酸直接接触，而且铜-有机化合物膜21对酸和氧存在化学耐性，因此表面处理过的铜线20经过酸处理之后没有出现氧化和腐蚀的现象。由此可以看出，表面处理过的铜线20具有改善的抗氧化性和耐腐蚀性。
因此，根据本发明示例性实施例的用于处理裸铜线的方法可以提高铜线的抗氧化性和耐腐蚀性，使得处理过的铜线可以满足半导体封装工艺的要求，例如，引线键合工艺的工程作业性和信赖性要求。
此外，根据本发明示例性实施例的用于处理裸铜线的方法具有简单的工艺过程和低的成本，降低了例如半导体封装工艺的成本。
虽然上面参照附图描述了根据本发明示例性实施例的用于处理裸铜线的方法和试剂及表面处理过的铜线，但是本发明不限于此。本领域技术人员理解的是，在不脱离本发明的精神和范围的情况下，可以对其做出形式上和细节上的各种改变。

Claims (10)

1.一种用于处理裸铜线的方法，所述方法包括：
将磷酸类螯合剂的溶液施加到裸铜线的表面；以及
将表面附着有磷酸类螯合剂的溶液的裸铜线干燥。
2.根据权利要求1所述的用于处理裸铜线的方法，其中，将磷酸类螯合剂的溶液施加到裸铜线的表面的步骤包括：将磷酸类螯合剂的溶液喷淋到裸铜线，或者将裸铜线浸在磷酸类螯合剂的溶液中。
3.根据权利要求1所述的用于处理裸铜线的方法，其中，将表面附着有磷酸类螯合剂的溶液的裸铜线干燥的步骤包括：向表面附着有磷酸类螯合剂的溶液的裸铜线吹热风，或者在烘箱中干燥表面附着有磷酸类螯合剂的溶液的裸铜线，或者在环境温度下将表面附着有磷酸类螯合剂的溶液的裸铜线自然晾干。
4.根据权利要求1所述的用于处理裸铜线的方法，其中，磷酸类螯合剂的溶液包括0.5wt％至2wt％的磷酸类螯合剂、0.1wt％至1.5wt％的表面活性剂和96.7wt％至99.2wt％的水。
5.根据权利要求4所述的用于处理裸铜线的方法，其中，磷酸类螯合剂包括以下化合物中的至少一种：
6.根据权利要求4所述的用于处理裸铜线的方法，其中，表面活性剂是非离子表面活性剂。
7.一种用于处理裸铜线的试剂，所述试剂包括0.5wt％至2wt％的磷酸类螯合剂、0.1wt％至1.5wt％的表面活性剂和96.7wt％至99.2wt％的水。
8.一种表面处理过的铜线，所述表面处理过的铜线包括铜线基体和包覆在铜线基体的表面上的铜-有机化合物膜。
9.根据权利要求8所述的表面处理过的铜线，其中，所述铜-有机化合物膜的厚度在1nm至10nm的范围内。
10.根据权利要求8所述的表面处理过的铜线，其中，所述铜-有机化合物膜具有固定的结构单元。
CN201611047684.6A 2016-11-23 2016-11-23 用于处理裸铜线的方法和试剂及表面处理过的铜线 Pending CN106544658A (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201611047684.6A CN106544658A (zh) 2016-11-23 2016-11-23 用于处理裸铜线的方法和试剂及表面处理过的铜线
US15/701,924 US20180142358A1 (en) 2016-11-23 2017-09-12 Method and reagent for treating bare copper wire and surface-treated copper wire
KR1020170156609A KR20180058205A (ko) 2016-11-23 2017-11-22 반도체 장치 및 그의 제조 방법

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611047684.6A CN106544658A (zh) 2016-11-23 2016-11-23 用于处理裸铜线的方法和试剂及表面处理过的铜线

Publications (1)

Publication Number Publication Date
CN106544658A true CN106544658A (zh) 2017-03-29

Family

ID=58395767

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611047684.6A Pending CN106544658A (zh) 2016-11-23 2016-11-23 用于处理裸铜线的方法和试剂及表面处理过的铜线

Country Status (3)

Country Link
US (1) US20180142358A1 (zh)
KR (1) KR20180058205A (zh)
CN (1) CN106544658A (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5376189A (en) * 1993-11-08 1994-12-27 Macdermid, Incorporated Composition and process for treatment of metallic surfaces
CN101266847A (zh) * 2008-04-18 2008-09-17 江苏中煤电缆集团有限公司 2-硫醇基苯并咪唑在电缆导体表面抗氧化上的应用
CN101311315A (zh) * 2007-05-22 2008-11-26 天津晶岭电子材料科技有限公司 金属铜材料清洗剂
CN101629294A (zh) * 2009-07-30 2010-01-20 海宁市科泰克金属表面技术有限公司 利用分子自组合技术的新型铜保护剂
CN102782189A (zh) * 2010-12-01 2012-11-14 吉坤日矿日石金属株式会社 Pd或以Pd为主成分的合金的表面处理剂、和铜表面的表面皮膜层构造

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5376189A (en) * 1993-11-08 1994-12-27 Macdermid, Incorporated Composition and process for treatment of metallic surfaces
CN101311315A (zh) * 2007-05-22 2008-11-26 天津晶岭电子材料科技有限公司 金属铜材料清洗剂
CN101266847A (zh) * 2008-04-18 2008-09-17 江苏中煤电缆集团有限公司 2-硫醇基苯并咪唑在电缆导体表面抗氧化上的应用
CN101629294A (zh) * 2009-07-30 2010-01-20 海宁市科泰克金属表面技术有限公司 利用分子自组合技术的新型铜保护剂
CN102782189A (zh) * 2010-12-01 2012-11-14 吉坤日矿日石金属株式会社 Pd或以Pd为主成分的合金的表面处理剂、和铜表面的表面皮膜层构造

Also Published As

Publication number Publication date
KR20180058205A (ko) 2018-05-31
US20180142358A1 (en) 2018-05-24

Similar Documents

Publication Publication Date Title
TWI249451B (en) Surface treating agent for tin or tin alloy material
CN103069046B (zh) 镀锌系钢板的制造方法和镀锌系钢板
JP4644718B2 (ja) 金属／樹脂接着構造体及び樹脂封止型半導体装置とその製造方法
CN104561943B (zh) 用于线路板的化学镀镍钯合金工艺
JPS61287155A (ja) 半導体装置及び半導体装置の製造方法
CN111344435A (zh) 复合铜箔
CN104928658B (zh) 一种活化pcb电路表面实现化学镀镍的方法
CN103459669B (zh) 防止钢板黑化的成膜组合物以及含有由组合物形成的膜的钢板
CN106544658A (zh) 用于处理裸铜线的方法和试剂及表面处理过的铜线
CN107002240A (zh) 镀金属覆盖不锈钢材料的制造方法
JP6870245B2 (ja) 銅製部材の表面処理方法及び半導体実装用基板の製造方法
JP2001214285A (ja) アルミニウム合金金属化層の腐食抑制保護層およびその製法
CN107502851A (zh) 一种塑胶模具的表面处理工艺
KR0142648B1 (ko) 베어본딩용 동합금 리드프레임
Chyan et al. Mechanistic Investigation and Prevention of Al Bond Pad Corrosion in Cu Wire-bonded Device Assembly
US20100072076A1 (en) Surface treatment method for housings
CN110891616A (zh) Cu线接合器件组件中的al接合焊盘腐蚀的机制调查和预防
CN109275276A (zh) 一种金面氧化物的去除方法
CN106513889B (zh) 一种搪锡方法
JP3726478B2 (ja) 半導体パッケージの端子の表面処理方法
CN108842148A (zh) 汽车散热器表面防腐处理的方法
CN103586599A (zh) 无铅焊锡丝
CN111849286B (zh) 一种抑菌型耐指纹涂层药剂、其制备方法及应用
JPH11286794A (ja) 銅または銅合金材料の表面処理方法
CN115763494A (zh) 显示面板及其制作方法、蚀刻液组合物

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170329