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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/40—Oxides
  • C23C16/401—Oxides containing silicon
  • C23C16/402—Silicon dioxide
• • 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
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/02—Pretreatment of the material to be coated
  • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
  • C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/42—Silicides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
  • H01L2924/0001—Technical content checked by a classifier
  • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

• Copper-based composite substrate for electronic parts electronic component and method for producing copper-based composite substrate for electronic parts
• the present invention relates to a copper-based composite base material for electronic components used for electronic components, an electronic component using the same, and a method for producing the copper-based composite base material for electronic components.
• copper-based metal materials have been used for circuit boards of semiconductor devices and lead frames, electrodes, terminals and the like of various electronic components.
• a composite material in which a coating layer made of tin or a tin-based alloy is formed on the surface of a copper base material or a copper alloy base material (hereinafter also simply referred to as a copper-based composite base material)
• a copper-based composite base material it is particularly preferably used for a terminal connected to electric wiring.
• the coating layer on the surface of the copper-based composite base serves to suppress copper oxidation and to reduce the contact resistance when connecting the electrical wiring and the terminal portion.
• circuit boards, lead frames, electrodes, terminals and the like using such a copper-based composite base material are sealed or bonded with a resin sealing material or a resin adhesive. Therefore, from the viewpoint of ensuring reliability, the adhesion (adhesion) between the copper-based composite base material and the resin sealing material is very important. If the adhesiveness is poor, peeling may occur between the copper-based composite base material and the resin sealing material. When peeling occurs, moisture or corrosive gas may enter through the gap between the peelings, which may cause corrosion of the substrate. As a result, the reliability of the semiconductor device decreases.
• Patent Document 1 a method of treating the substrate surface with a silane coupling agent is known (for example, Patent Document 1).
• Patent Document 1 Japanese Patent Laid-Open No. 2002-270740
• the present invention relates to a copper-based composite base material for electronic components that can further improve the adhesion between the copper-based composite base material and the resin component, an electronic component using the same, and the copper-based composite base for electronic components
• the purpose is to provide a manufacturing method for wood.
• One aspect of the present invention is a copper-based composite base material having a coating layer made of tin or a tin-based alloy on the surface of a copper base material or a copper alloy base material, and a carbonized material deposited on the surface of the coating layer.
• a copper-based composite base material for electronic parts comprising a silicon oxide thin film containing a hydrogen group and Z or hydroxyl group.
• One aspect of the present invention is an electronic component obtained using the copper-based composite base material for electronic components.
• a silicon-containing reaction gas is introduced between at least a pair of electrodes provided to generate plasma by discharge, and plasma is generated between the electrode pairs.
• the silicon-containing reaction gas is decomposed by the above, and the copper-based composite base material is formed by forming a coating layer made of tin or a tin-based alloy on the surface of the copper base material or copper alloy base material in the decomposition product of the silicon-containing reaction gas In which a silicon oxide thin film is formed on the surface of the coating layer.
• FIG. 1 is a schematic explanatory view showing a configuration example of a CVD film forming apparatus for carrying out a method for producing a copper-based composite base material for electronic parts according to an embodiment of the present invention.
• FIG. 2 is a schematic explanatory view showing another configuration example of a CVD film forming apparatus for carrying out a method for producing a copper-based composite base material for electronic parts according to an embodiment of the present invention.
• FIG. 3 is a schematic explanatory view showing another configuration example of a CVD film forming apparatus for carrying out a method for manufacturing a copper-based composite base material for electronic parts according to an embodiment of the present invention.
• FIG. 4 is a schematic explanatory view showing another configuration example of a CVD film forming apparatus for carrying out a method for producing a copper-based composite base material for electronic parts according to an embodiment of the present invention.
• FIG. 5 is a chart showing the reflection spectrum by FT-IR of the silicon oxide thin film obtained in Example 1.
• a copper-based composite base material for electronic components has a copper-based composite base material having a coating layer made of tin or a tin-based alloy on the surface of a copper base material or a copper alloy base material. And a silicon oxide thin film containing a hydrocarbon group and Z or a hydroxyl group deposited on the surface of the coating layer.
• the copper-based composite base material includes various copper alloys, such as Cu-Fe-P-based alloys, Cu-Ni-Si-based alloys, Cu-Cr-Zr-based alloys,
• a substrate made of a Cu-Zn alloy, Cu-Sn alloy, etc. (hereinafter also referred to as a copper-based substrate) is tinned by methods such as electroplating, electroless bonding, melting bonding, and plasma CVD.
• a coating layer made of a tin-based alloy is formed. These are often used as constituent materials for electronic components.
• the coating layer is formed by electroplating of tin or a tin-based alloy (electro-gloss plating)
• a Wies force may be generated due to residual stress in the coating layer.
• the copper-based composite base material may be reflowed (heat treated) at a temperature of 100 to 600 ° C. to remove residual stress.
• the tin plating obtained in this way is usually also called reflow tin plating.
• a Cu—Sn-based alloy or a Cu—Ni—Sn-based alloy is formed when the coating layer contains a Cu—Sn alloy or a copper substrate.
• the thickness of the coating layer is not particularly limited, but is preferably 0.1 to: LO / zm, more preferably 0.5 to 5 / ⁇ ⁇ , and particularly preferably 0.5 to 3 / ⁇ ⁇ . . If the coating layer is too thick, the heat resistance will decrease and it will tend to be economically disadvantageous. Furthermore, when it is used as a pluggable terminal, the insertion / extraction force between the male terminal and female terminal will be low. Tends to be too high. On the other hand, if it is too thin, the effect of suppressing acidification tends to be insufficient.
• the silicon oxide thin film deposited on the surface of the coating layer is composed of a silicon-based alkoxide plasma decomposition product or a silicon-based alkoxide and an oxygen-containing molecule in a silicon oxide thin film having a Si--bonding force.
• Hydrocarbon groups and Z or hydroxyl groups derived from plasma decomposition products contains.
• Such a silicon oxide thin film can be formed, for example, by a plasma CVD method using a source gas containing a silicon alkoxide.
• Such hydrocarbon groups and Z or hydroxyl groups improve the adhesion between the resin component and the copper-based composite substrate.
• hydrocarbon group examples include, for example, methyl groups (—CH 2) derived from plasma decomposition products such as tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, tetraethoxysilane, and the like. Silicon-based alkoxy having an ethyl group (one CH)
• the hydrocarbon group derived from the plasma decomposition product of side is mentioned.
• Specific examples of the hydroxyl group include a hydroxyl group formed by recombination of the plasma decomposition product of the silicon-based alkoxide and the plasma decomposition product of the oxygen atom-containing molecule.
• Reactions such as ⁇ -glycidoxypropyltrimethoxysilane, y-glycidoxypropyltriethoxysilane, j8 (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and ⁇ -aminopropyltriethoxysilane
• hydrocarbon groups and hydroxyl groups derived from a plasma decomposition product of a silicon-based alkoxide having a functional functional group may be just one type or a combination of two or more types! /.
• the content of the hydrocarbon group and the soot or hydroxyl group is not particularly limited, but is preferably a content that exhibits the following FT-IR peak.
• a silicon oxide thin film is formed on a silicon substrate under the same conditions as those for forming a silicon oxide thin film on a copper-based composite substrate, and the absorption spectrum of the thin film is measured by FT-IR.
• the absorbance display obtained by measuring the peak intensity of Si—O with respect to the peak intensity of Si—O (1070 to 1080 cm ” 1 ) the intensity ratio of 3000 to 3400 cm or the Si—O against the peak intensity of Si—O— CH, Si-CH, and Si-CH peak intensities (2800 ⁇
• Strength specific force is 0.01 to 0.5, and further 0.05 to 0.2. If the peak intensity ratio is too small, the effect of improving the adhesion to the resin component is low and tends to be low, and if it is too large, the film strength is low and the durability tends to be low.
• the peak intensity of a silicon oxide thin film formed on an opaque copper base material cannot be directly measured.
• the silicon substrate Because it is transparent in the infrared region and has a relatively flat surface, it can be accurately measured by the transmissive FT-IR method. Therefore, a silicon oxide thin film similar to the silicon oxide thin film on the copper base material is formed on the silicon substrate under the same film formation conditions as those for forming the silicon oxide thin film on the copper base material. This is because more accurate peak intensity can be measured.
• the thickness of the silicon oxide thin film is not particularly limited, but is preferably 1 to: LOOOnm, and more preferably 5 to 10 Onm. If the film thickness is too thick, it takes time to form the film, resulting in an increase in cost, and adhesion to the copper-based composite substrate, particularly adhesion in a high-temperature and high-humidity environment is reduced. On the other hand, if the film thickness is too thin, the effect of improving the adhesion cannot be obtained sufficiently.
• the thin film is caused by a thermal history during mounting in the reflow soldering process. It is particularly preferable that the film thickness is not more than lOOnm, because moisture may be absorbed and the adhesion strength between the copper-based composite substrate and the thin film may be reduced.
• the silicon oxide thin film is not necessarily formed as a continuous film.
• the silicon oxide thin film may be formed discontinuously and in a striped pattern. In this case, it is more preferable that the strength of adhesion with the resin component is improved by the anchor effect.
• the above-described copper-based composite base material for electronic parts of the present invention has high adhesion to a resin component. Therefore, for example, a high die shear strength value is obtained when the resin component is peeled after bonding the copper-based composite base material for electronic parts and the resin component. And the greaves breaking mode tends to peel off by cohesive failure. In addition, when exfoliating the resin component after bonding the conventional copper base material and the resin component, there is a tendency to exfoliate due to interfacial fracture.
• the copper-based composite base material for electronic components is a substrate, lead frame, electrode, terminal, etc. used for various electronic components such as semiconductor devices, and is sealed or bonded with grease. It is preferably used for metal parts.
• ECU electrice control unit
• JB Yon Block
• a silicon-containing reaction gas is introduced between at least a pair of electrodes provided for generating plasma by discharge.
• the copper-based composite is formed by decomposing the silicon-containing reaction gas by generating plasma between the electrode pairs and forming a coating layer made of tin or a tin-based alloy on the surface of the copper base material or copper alloy base material.
• a base material is brought into contact with a decomposition product of the silicon-containing reaction gas to form a silicon oxide thin film on the surface of the coating layer.
• [0031] As a specific example, comprising electrode pairs facing each other, placing a copper-based composite base material on one electrode of the electrode pair, introducing a silicon-containing reaction gas between the electrodes, A method of forming a thin film on the surface of the coating layer of the copper-based composite substrate by converting this into plasma is used.
• a low-pressure plasma CVD method reduced-pressure plasma
• a plasma is generated by glow discharge under a reduced pressure condition of about LOOOPa to form a thin film on a substrate.
• Vapor phase deposition method a method proposed in Japanese Patent Application Laid-Open No. 6-2149 or the like that forms a thin film on a substrate by generating a plasma by glow discharge under a pressure near atmospheric pressure
• a method described in Japanese Patent Application Laid-Open No. 2002-237480 in which a dielectric is formed on at least one of the electrodes to be generated, plasma is generated at atmospheric pressure by a DC pulse or the like, and a raw material gas is blown onto the base material at the gas pressure.
• a method of forming a film using a rotating electrode as disclosed in JP-A-9-104985 is used.
• a thin film is continuously formed with high productivity by, for example, making the gas flow uniform in the width direction along the electrode where the arc discharge frequently rotates because there is no electric field concentration. From the point that can be made, there is a method of forming a film by plasma CVD using a rotating electrode preferable.
• the present invention can be implemented by, for example, a film forming method using a plasma CVD film forming apparatus using a rotating electrode without a chamber.
• a method for forming a silicon oxide thin film on a copper-based composite substrate by plasma CVD using a rotating electrode will be described.
• a plasma CVD film-forming apparatus provided with a chamber and an electrode pair facing inside the chamber, the discharge electrode side of the facing electrode pair is a rotating electrode, and the counter electrode side is a flat electrode.
• a copper-based composite base material is placed on a planar electrode.
• a silicon-containing reaction gas is introduced into the chamber.
• plasma is generated by performing glow discharge between the rotating electrode and the copper-based composite substrate (hereinafter referred to as “narrow gap”) under a pressure near atmospheric pressure.
• the plasma becomes a line-shaped plasma in a narrow gap.
• a silicon oxide thin film is formed on the copper-based composite substrate by scanning the copper-based composite substrate so as to cross the line-shaped plasma space. According to the above method, a silicon oxide thin film can be easily formed on the surface of the coating layer of a large-area copper-based composite base material without increasing the size of the apparatus.
• rotating electrode a cylindrical rotating electrode as shown in the configuration example of the CVD film forming apparatus shown in FIG. 1, an endless belt electrode as shown in FIG. 2, or the like is used. .
• the surface of the rotating electrode may be a smooth surface or a surface on which irregularities are formed.
• the uneven shape is used to adjust the distance between a specific position of the copper-based composite base material and the rotating electrode. For example, when a convex part is formed along the rotation direction, only the distance between the copper-based composite substrate and the convex part of the rotating electrode is reduced, and plasma is preferentially generated in the part where the convex part is formed. Can be made. As a result, the silicon oxide thin film can be formed preferentially only at the position facing the convex portion on the surface of the copper-based composite substrate. Therefore, the surface of the formed silicon oxide thin film is formed in an uneven shape. In addition, when unevenness is provided on the rotating electrode, it contains silicon that is laminar (viscous) near atmospheric pressure. There is also an effect of diffusing the reaction gas.
• a desired shape is selected according to a specific application.
• the copper-based composite substrate placed on the planar electrode In order to improve the adhesion of the silicon oxide thin film to the copper-based composite substrate, it is preferable to heat the copper-based composite substrate placed on the planar electrode.
• the heating temperature tin or a tin-based alloy does not melt, and the silicon-containing reaction gas described later does not condense! ⁇ 70 ° C or higher and 232 ° C or lower is preferable.
• the oxidation of tin or tin-based alloy is difficult to proceed 200 ° C or lower, and more preferably 150 ° C or lower.
• the distance between the rotating electrode and the copper-based composite substrate placed on the planar electrode is the high-frequency power applied to the rotating electrode, the type of silicon-containing reaction gas used, and the composition.
• the force appropriately adjusted depending on the ratio or the like is preferably 0.5 to 5 mm, and more preferably 1 to 3 mm.
• the silicon-containing reaction gas is not stably supplied to the narrow gap, and therefore, the narrow gap varies in the width direction of the rotating electrode, resulting in non-uniform film thickness.
• the interval is too narrow, it is necessary to capture plasma charged particles of electrons and ions in order to generate stable plasma. In this case, high frequency power of 100 MHz or more is required, which is disadvantageous in terms of cost.
• the film formation rate decreases due to a decrease in electric field and a decrease in plasma density.
• the laminar flow generated by the rotation of the rotating electrode causes the deposition precursor to be discharged on the copper composite substrate, resulting in a decrease in deposition rate and contamination of the chamber. Problems may occur.
• the peripheral speed of the rotating electrode is preferably 3000 cmZmin or more, more preferably lOOOOcmZmin or more.
• the film forming speed tends to be slow. Further, from the viewpoint of improving the yield, it is preferably lOOOOOcmZmin or less.
• a silicon-containing reaction gas is introduced into the chamber.
• the pressure in the chamber is preferably adjusted to be close to atmospheric pressure.
• the pressure in the vicinity of the atmospheric pressure means a pressure of about 0.01-0.1 MPa. From the viewpoint that the pressure adjustment is easy and the apparatus configuration can be simplified, it is particularly preferable that the pressure is about 0.08-0. IMPa.
• the silicon-containing reaction gas is preferably a raw material gas containing an inert gas and oxygen in addition to the silicon-based alkoxide.
• Examples of the silicon-based alkoxide include tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - Examples thereof include glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and ⁇ -aminopropyltriethoxysilane. These can be used alone or in combination of two or more. Among these, tetraethoxysilane is preferable because it is easily available industrially.
• silicon-based alkoxide is said to have low reactivity with soot even under high pressure when the plasma is turned off when plasma CVD is applied under pressure near atmospheric pressure.
• the inert gas is a component that does not generate a reactive radical! And is used to stably generate a glow discharge in an atmosphere.
• Specific examples thereof include noble gases such as helium (He), argon (Ar), xenon (Xe), and krypton (Kr), and N gas.
• metastable excited states have a long lifetime, and helium is preferred.
• the silicon-containing reaction gas further contains other components, specifically silicon compounds other than silicon-based alkoxides, nitrogen oxides such as oxygen (O 2) and nitrogen oxide (NO), and
• the silicon-containing reaction gas contains oxygen
• the oxidation and crosslinking reaction of the silicon-based alkoxide is promoted.
• oxygen is contained at a relatively high rate
• silicon oxide fine particles can be generated to form a particle-like silicon oxide thin film.
• the particle-like silicon oxide thin film has an uneven shape.
• the oxygen content is preferably about 0.1 to 2 in terms of a volume ratio with respect to the silicon-based alkoxide (oxygen Z silicon-based alkoxide).
• this ratio is less than 0.1, the effect of promoting the oxidation and crosslinking reaction is small, and the silicon oxide fine particles do not grow sufficiently. Also, if it exceeds 2, it tends to accumulate as particles.
• the proportion of each component in the silicon-containing reaction gas is such that the silicon-based alkoxide is 0.1 to 5% by volume in 1 atm, further 1 to 5% by volume, and oxygen is 0 to: LO volume%. It is preferable.
• high-frequency power is applied to the discharge electrode, and glow discharge is performed at a pressure close to atmospheric pressure to generate plasma, thereby converting the silicon-containing reaction gas into plasma.
• the lifetime until recombination after ionization of molecules of the silicon-containing reactive gas converted into plasma is short and the mean free path of electrons is also short. Therefore, in order to stably generate a glow discharge between opposing narrow gap electrodes, it is necessary to capture charged particles of electrons and ions in a narrow gap. Therefore, when applying high-frequency power to the rotating electrode, it is preferable to apply high-frequency power having a frequency of lOOKHz or higher, particularly a frequency of 10 MHz or higher.
• High-frequency power of 10 MHz or more for example, the most readily available commercial frequency 13.56 MHz is available as a power source, such as 70 MHz, 100 MHz, and 150 MHz. Can be generated.
• FIG. 1 is a schematic explanatory view showing a configuration example of a CVD film forming apparatus for forming a silicon oxide thin film, which is preferably used for manufacturing the copper-based composite base material for electronic parts.
• 1 is a film forming chamber
• 2a is a load lock chamber for introducing a substrate
• 2b is a load lock chamber for discharging a substrate
• 3a to 3d are gate valves
• 4a to 4d are gas inlets
• 5a and 5b are Leak port
• 5c is exhaust port
• 6 is a base material holder
• 7 is a base material made of a copper-based composite base material
• 8 is a bearing
• 9 is a rotating electrode
• 10 is a mount
• 11a ⁇ : Lie is a rotating electrode Support insulator
• 12 is synthetic quartz glass
• 13 is near infrared lamp
• 14 is a window
• 15 is a radiation thermometer
• 16 and 19 are high frequency power supplies
• 17 and 20 are matching
• a substrate introduction load lock chamber 2a and a substrate carry-out load lock chamber 2b are connected to the film forming chamber 11 through gate valves 3b and 3c, respectively.
• An inert gas such as helium is always introduced into the load lock chambers 2a and 2b from the gas inlets 4a and 4b (VI and V2 are flow control valves), and the load lock chambers 2a and 2b are respectively supplied to the load lock chambers 2a and 2b.
• the pressure is adjusted by the provided leak ports 5a and 5b (V3 and V4 are flow adjustment valves), and the load lock chambers 2a and 2b are kept at normal pressure (about 0. IMPa). It is.
• the flow rate of a mixed gas of an inert gas such as He and oxygen (O 2) is adjusted through a mass flow (not shown) through a gas inlet 4 c as necessary.
• silicon-based alkoxide diluted by piling with an inert gas such as helium whose flow rate is adjusted through a mass flow (not shown) is introduced from the gas inlet 4d.
• the pressure in the chamber 11 is adjusted by adjusting the flow rate from the exhaust port 5c.
• a base material 7 which is a copper-based composite base material is placed on the base material holder 6.
• the base material holder 6 is first transferred to the load lock chamber 2a with the gate valve 3a opened. And stored. Thereafter, with the gate valve 3a closed and the gate valve 3b opened, the substrate holder 7 is scanned in the direction of arrow A and stored in the chamber 11, and then the gate valve 3b is Closed.
• a silicon oxide thin film is formed on the surface of the base material 7 placed on the base material holder 6.
• the gate valve 3c is opened, and the base material holder 6 is stored in the load lock chamber 2b. Subsequently, the gate valve 3c is closed and the gate valve 3d is opened, and the substrate holder 6 and the substrate 7 placed thereon are carried out of the load lock chamber 2b. A series of these operations are continuously performed, and the stop and progress of the substrate holder 6 can be freely controlled.
• each wall temperature is as high as 100 ° C.
• the temperature of the gantry 10 and the insulators lla to llc that support the rotating electrode 9 in the film forming chamber 11 is adjusted to about 100 ° C. by a built-in heater.
• the rotating electrode 9 is preferably heated by infrared rays emitted from the near-infrared lamp 13 through the synthetic quartz glass 12 and heated to about 150 ° C. Note that the temperature of the rotary electrode 9 is measured by the radiation thermometer 15 through a glazing window 14 having a BaF force, for example.
• the CVD film forming apparatus forms a silicon oxide thin film on the base material 7 by forming plasma by the glow discharge 21 in a narrow gap between the rotating electrode 9 and the base material 7. is there. The principle of this film formation will be described below.
• the rotating electrode 9 is made of, for example, aluminum and has a cylindrical shape with a width of about 120 mm and a diameter of about 100 mm, and its edge is rounded with a radius of curvature of R5 (mm) to prevent electric field concentration. Is formed.
• the surface of the rotating electrode 9 is coated with a dielectric material to prevent arcing. The dielectric coating at this time is formed, for example, by spraying white alumina (thickness: about 150 m).
• the surface of the rotary electrode 9 that forms a narrow gap with the base material 7 has a polishing specification, and is provided with an uneven shape as necessary.
• the rotating electrode 9 is supported by a bearing 8 and a mount 10.
• One shaft end of the rotating electrode 9 is a magnetic coupling, which is coupled with a motor end magnet (not shown) arranged outside the film forming chamber 11 to rotate the rotating electrode 9 at 0 to 3000 rpm. It can be rotated within the range.
• the gantry 10 is made of, for example, stainless steel.
• the high frequency power from the high frequency power source 16 can be applied to the gantry 10 via the matching unit 17.
• the high frequency power is applied.
• glow discharge is started in a narrow gap between the rotating electrode 9 and the substrate holder 6 (that is, the substrate holder 6 corresponds to the counter electrode).
• the substrate holder 6 is sequentially moved in the direction A in the figure. After the base material 7 placed on the base material holder 6 arrives directly under the rotary electrode 9, a narrow gap is formed between the rotary electrode 9 and the base material 7.
• a heater 18 is embedded in the substrate holder 6.
• the substrate holder 6 is heated by this heater 18 from room temperature to a temperature of about 300 ° C.
• the surface of the substrate holder 6 is sprayed with white alumina to a thickness of about 100 m.
• the substrate holder 6 may basically be in an electrically grounded state, but is configured to apply high-frequency power from a high-frequency power source 19 via a matching unit 20 as shown in FIG. May be. In this way, by applying high-frequency power to the substrate holder 6, the plasma density can be increased and plasma can be contained.
• Application of high-frequency power from the high-frequency power source 19 to the substrate holder 6 applies power from the high-frequency power source 16 to the rotating electrode 9. What is necessary is just to apply immediately after applying.
• the matching unit 17 performs frequency tuning and impedance adjustment to match the high-frequency power source 16 side and the load side including the matching unit 17, and the entire load circuit including the matching unit 17 The power consumption is maximized, and the high-frequency power supply 16 and the high-frequency oscillation circuit are protected (the same applies to the relationship between the matching unit 20 and the high-frequency power supply 19).
• FIG. 2 is a schematic explanatory view showing another example of a CVD film forming apparatus using a rotating electrode, and its basic configuration is similar to the apparatus configuration shown in FIG. Avoid duplicate explanations by assigning the same reference numerals.
• the base material introduction load lock chamber 2a in this apparatus as well as the apparatus shown in FIG. 1, the base material introduction load lock chamber 2a , the base material unloading load lock chamber 2b, and the same. An accompanying member is arranged.
• an endless belt electrode 22 is provided in place of the cylindrical rotating electrode 9, and the endless belt electrode 22 is made of, for example, a conductive material made of thin steel. It is made up of members and is configured to run around two rollers 23 and 24.
• Each of the rollers 23 and 24 has a cylindrical outer peripheral surface, and in the plasma generation region P, the surface of the endless belt electrode 22 and the surface of the base material 7 extending horizontally are parallel to each other. They are arranged so that the gap distance is constant.
• the endless belt electrode 22 travels in the same direction as the movement direction of the base material 7 in the plasma generation region P.
• the one located on the right side in FIG. 2 is a metallic drive / feed roller 24.
• the roller 24 is rotated by rotating the roller 24 by a belt driving motor (not shown).
• the base material 7 placed on the base material holder 6 is moved in the horizontal direction (arrow B direction) by the base material transport mechanism 25.
• the silicon-containing reaction gas is introduced into the film forming chamber 11 from the gas inlet 4e and exhausted through the exhaust duct 5e. Maintain the bar 1 at the specified atmospheric pressure. Then, the endless belt electrode 22 is caused to travel by the rollers 23 and 24, and a relatively wide line-shaped plasma is generated by the glow discharge in the narrow gap between the belt electrode 22 and the base material 7, and the base material 7 is moved. However, a silicon oxide thin film is formed on the substrate 7 by a chemical reaction of gas.
• FIG. 3 is a schematic explanatory view showing another example of a CVD film forming apparatus using a rotating electrode.
• This example increases productivity by omitting the gas exhaust and replacement process, and allows the direct insertion and removal of substrates from the atmosphere to avoid the use of expensive vacuum vessels.
• the basic structure of the rotating electrode portion is the same as that shown in FIG. 1, and the description of the same portion is omitted.
• the base material 7 is conveyed in one direction by the belt conveyor 26.
• the base material 7 is placed on one end of the belt conveyor at regular intervals by a substrate nodding robot (not shown). Thereafter, the base material 7 is guided into the reaction container as the belt conveyor moves.
• the entrance and the exit are limited to the opening necessary for the conveyance of the base material 7, and the air curtain 27 is provided to block the outside air using the gas flow. Is doing.
• the reaction space is filled with an inert gas, and a separately introduced raw material gas is guided to the plasma space by the flow of the rotating electrode 9 to form a silicon oxide thin film on the copper-based composite substrate.
• FIG. 4 is a schematic explanatory view showing still another example of a CVD film forming apparatus using a rotating electrode.
• the base material 7 that also serves as the copper-based composite base material is coiled, the base material 7 is sent out from the feed roll 29, and the base material 7 is wound up by the take-up roll 30.
• the reaction vessel is separated from the outside air by a gas blocking roll 31 installed at the inlet and outlet.
• Example 1 to: LO A silicon oxide thin film was formed using the rotating electrode type CVD film deposition system shown in Fig. 1.
• a substrate holder 6 having a width of 170 mm and a length (scanning direction length) of 170 mm is used, and a copper-based composite substrate is formed on the substrate holder 6.
• the base material 7 was placed and stored in the chamber 1.
• the substrate 7 also made of copper-based composite matrix mosquito, width: 100 mm, length (scan direction length): 0.99 mm, thickness: of 0. 4mm Cu- 0. 1 mass 0/0 Fe - use the 0.03 mass 0/0 P (C19210) thickness from 0.6 to 5 forces et become a copper alloy substrate by electric gloss plated tin lm copper composite substrate coating layer formed of. It was.
• high-frequency power (frequency: 13.56 MHz, 500 W) was also applied to the rotating electrode 9 with 16 high-frequency power sources.
• the base material holder 6 was connected to ground.
• the set temperature of the substrate holder 6 is 100 to 250.
• the temperature of the rotating electrode 9 was set to 150 ° C
• the film forming chamber 1 and its members were set to 100 ° C.
• the rotational speed of the rotating electrode 9 was 500-1500 rpm (peripheral speed: 15000-45000 cmZmin), and the narrow gap between the rotating electrode 9 and the substrate 7 was set to lmm. At this time, since the scanning speed of the substrate 7 was 3.3 to 17 mmZsec, the discharge time between the ends in the scanning direction of the substrate 7 was about 8 to 51 seconds.
• the pressure in the film forming chamber 11 was controlled by an automatic pressure control (not shown) installed in the exhaust port 5c, and was adjusted to a total pressure of 101 KPa (0. IMPa) in this production example.
• the reaction gas introduced into the deposition chamber 11 was a mixed gas of helium and tetraethoxysilane (TEOS), and the partial pressure was adjusted by adjusting the flow rate.
• the TEOS partial pressure was set to 0.013 to 2.66 KPa (0.013 / 101 in terms of partial pressure ratio).
• the peak intensity around the frequency: 3000-3400 cm- 1 is the —OH group in the thin film
• the peak intensity around the frequency: 2800-2900 cm- 1 is the alkyl group (methyl group, ethyl). Group).
• the measurement was performed by transmission Fourier transform infrared spectroscopy and analyzed in the absorbance mode. As a result, the presence of OH group, methyl group, and ethyl group was confirmed.
• a silicon chip made by Kojundo Chemical Laboratory Co., Ltd.
• a thermosetting polyolefin-based resin Silicone 3M ( And was cured under the curing conditions of 150 ° C. for 2 hours.
• the die shear strength of the silicon chip adhered to the surface of the copper-based composite base material for electronic parts was evaluated using a die shear strength evaluation apparatus based on US MIL STD-883.
• the dice strength after being subjected to a pressure tacker device at 105 ° C and 100% RH for 24 hours was also measured. The results are shown in Table 1.
• width 100mm
• thickness 0.4mm
• Cu 0.1 mass% Fe 0.03 mass% P (C19210) force of copper alloy base material Using a copper-based composite base material with a coating layer with a thickness of 0.5-5 / ⁇ ⁇ that has been subjected to reflow treatment after electric light is applied to the surface, and according to the thin film formation conditions described in Table 2.
• a sample was prepared and evaluated in the same manner except that a thin film was formed. The results are shown in Table 2.
• a silicon oxide thin film containing no hydroxyl group or alkyl group was formed on the same copper-based composite substrate as in Example 1, and the same comparison was performed.
• Film formation uses magnetron sputtering, plasma is generated by applying RF power, and SiO target
• a silicon oxide thin film was fabricated by sputtering 2 with plasmaized argon ions.
• a film thickness of 10 to 200 nm was formed by changing the sputtering time based on the film formation speed calculated in advance.
• a copper-based composite base material for electronic components having high adhesion to a resin component, an electronic component using the same, and a method for producing the copper-based composite base material for electronic components. I can do it.
• Such a copper-based composite base material for electronic components is preferably used as a component of a semiconductor device such as a control unit mounted on an automobile, which requires high reliability.

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