WO2015159367A1 - 透過性評価方法 - Google Patents
透過性評価方法 Download PDFInfo
- Publication number
- WO2015159367A1 WO2015159367A1 PCT/JP2014/060726 JP2014060726W WO2015159367A1 WO 2015159367 A1 WO2015159367 A1 WO 2015159367A1 JP 2014060726 W JP2014060726 W JP 2014060726W WO 2015159367 A1 WO2015159367 A1 WO 2015159367A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid
- heavy metal
- permeability
- test piece
- evaluation method
- Prior art date
Links
- 230000035699 permeability Effects 0.000 title claims abstract description 80
- 238000011156 evaluation Methods 0.000 title claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 124
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 114
- 150000002500 ions Chemical class 0.000 claims abstract description 101
- 238000012360 testing method Methods 0.000 claims abstract description 69
- 239000004065 semiconductor Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 31
- 229910001431 copper ion Inorganic materials 0.000 claims description 31
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
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- 210000004027 cell Anatomy 0.000 description 55
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- 238000000034 method Methods 0.000 description 22
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- 210000005056 cell body Anatomy 0.000 description 8
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- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 229910052799 carbon Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
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- 238000002360 preparation method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
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- 239000002966 varnish Substances 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000000576 coating method Methods 0.000 description 3
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
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- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 2
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- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
- G01N2013/003—Diffusion; diffusivity between liquids
Definitions
- the present invention relates to a method for evaluating the permeability of heavy metal ions. Specifically, the present invention relates to a permeability evaluation method capable of easily and quickly evaluating the permeability of heavy metal ions to a test piece containing an insulating material used for semiconductor manufacture.
- a method of providing a gettering layer inside the wafer (intrinsic gettering, hereinafter referred to as “IG”) and a method of providing a gettering layer on the back surface of the wafer (extrinsic gettering, hereinafter referred to as “EG”).
- IG intrinsic gettering
- EG extentrinsic gettering
- the thickness of the gettering layer that can be formed inside is reduced, and the effect cannot be said to be sufficient.
- a minute crack is formed on the back surface of the wafer, so that the bending strength of the chip is lowered.
- Patent Document 3 one surface of a silicon wafer is contaminated with heavy metal, heavy metal is diffused by heating, a film to be evaluated is attached to the contaminated one surface, and heat treatment is performed under pseudo-reflow conditions.
- a technique for measuring the amount of heavy metal ions on the other side (non-contaminated surface) of the substrate is shown.
- Patent Document 4 a film to be evaluated is attached to one side of a silicon wafer, the film surface is contaminated with heavy metal, and then heat treated under pseudo reflow conditions, and the other side of the silicon wafer (no film is attached). A method for measuring the amount of heavy metal ions on the surface) is shown.
- the present invention has been made in view of such circumstances, and provides a permeability evaluation method capable of easily and quickly evaluating the permeability of heavy metal ions to a test piece containing an insulating material used in semiconductor manufacturing. For the purpose.
- the inventor As a result of intensive studies, the inventor as a permeability evaluation method for evaluating the permeability of heavy metal ions to a test piece containing an insulating material used for semiconductor manufacture, a first liquid containing heavy metal ions, A positive electrode provided on the first liquid side and a negative electrode provided on the second liquid side in a state where the second liquid containing water and an organic solvent is separated via a test piece. It has been found that the above-described problems can be solved by a specific evaluation method in which a voltage is applied between them.
- the permeability of heavy metal ions to a test piece containing an insulating material used for semiconductor manufacture can be easily and quickly evaluated.
- the permeability evaluation method according to the present invention the permeability of heavy metal ions can be evaluated easily and in a short time without using a special apparatus. Further, the permeability evaluation method according to the present invention can be applied to regular evaluation such as product inspection. Furthermore, according to the permeability evaluation method according to the present invention, the gettering property for heavy metal ions and the permeability for heavy metal ions can be evaluated simultaneously.
- the second liquid preferably contains N-methyl-2-pyrrolidone as the organic solvent.
- the content of N-methyl-2-pyrrolidone in the second liquid is preferably 20% by mass or more and 60% by mass or less.
- the electrical conductivity of the second liquid is preferably 1 ⁇ S or more at 23 ° C.
- the first liquid may contain copper ions as the heavy metal ions.
- the copper ion concentration in the first liquid is preferably 50000 mg / kg or less.
- the insulating material used for manufacturing the semiconductor may be a semiconductor adhesive tape.
- the present invention it is possible to provide a permeability evaluation method capable of easily and quickly evaluating the permeability of heavy metal ions to a test piece containing an insulating material used for semiconductor manufacture.
- the permeability evaluation method according to the present invention the permeability of heavy metal ions can be evaluated easily and in a short time without using a special apparatus. Further, the permeability evaluation method according to the present invention can be applied to regular evaluation such as product inspection. Furthermore, according to the permeability evaluation method according to the present invention, the gettering property for heavy metal ions and the permeability for heavy metal ions can be evaluated simultaneously.
- FIG. 1 It is a schematic diagram which shows an example of the cell used for evaluation of the permeability
- FIG. It is a figure which shows the measurement result of the copper ion concentration of Example 5.
- the permeability evaluation method according to the present embodiment evaluates the permeability of heavy metal ions to a test piece containing an insulating material (insulating material for semiconductor) used in semiconductor manufacturing.
- This is a permeability evaluation method.
- the A liquid (first liquid) and the B liquid (second liquid) are separated via a test piece, the anode provided on the A liquid side, and B A voltage is applied between the cathode provided on the liquid side.
- Liquid A contains heavy metal ions.
- Liquid B contains water and an organic solvent.
- the heavy metal ion concentration of A liquid is 0.5 mg / kg or more.
- step (I) the permeability of heavy metal ions to the test piece is evaluated based on the value of the current flowing between the anode and the cathode.
- step (II) the permeability of heavy metal ions to the test piece is evaluated based on the heavy metal ion concentration of the B liquid.
- the test piece is not particularly limited as long as it contains an insulating material and has an insulating property.
- Examples of the shape of the test piece include a film shape and a sheet shape.
- the insulating material that is liquid at normal temperature (23 ° C.) can be used as long as it is a material that is cured and solidified by heat, light, electron beam, or the like.
- Insulating materials used in semiconductor manufacturing include, for example, adhesive films and adhesive pastes used for chip-to-chip or chip-substrate bonding; Non-Conductive Film and Non-Conductive Paste used for flip chip connection; Materials: Solder resist used for protecting substrate surface; Buffer coating material used for protecting chip circuit surface.
- Insulating materials used in semiconductor manufacturing are, for example, resins (epoxy resins, phenol resins, vinyl resins, acrylic resins, phenoxy resins, polyamide resins, polyimide resins, polyamideimide resins, silicone resins, etc.), inorganic fillers (silica filler, alumina, etc.) A filler, a titanium oxide filler, a carbon filler, etc.), a silane coupling material, a coin accelerator, an acrylic monomer, a methacrylic monomer, and a vinyl compound.
- resins epoxy resins, phenol resins, vinyl resins, acrylic resins, phenoxy resins, polyamide resins, polyimide resins, polyamideimide resins, silicone resins, etc.
- inorganic fillers silicon filler, alumina, etc.
- silane coupling material a coin accelerator, an acrylic monomer, a methacrylic monomer, and a vinyl
- two cells separated by a test piece are used.
- the material and size of the cell include various glasses, various metals, and various resins.
- cells using various glasses or various resins are preferable because there is no influence of metal impurities contained in the material itself.
- Glass is preferable because it is harder than resin and the cell is not easily deformed, and since it is transparent, it is easy to observe the state of the electrode under measurement and the state of each liquid.
- the volume (amount of liquid that can be retained) of a cell is not particularly limited, but considering the ease of manufacturing the cell and the waste liquid treatment after measurement. 10 ml or more and 1000 ml or less are preferable.
- the measuring device includes two cells separated by a test piece which is a measurement object.
- the shape of each cell is such that the liquid A filled in one cell and the measurement object are in direct contact, the liquid B filled in the other cell is in direct contact with the measurement object, and the liquid A If it is a shape which does not mix with B liquid, there will be no restriction
- the cell holding the A liquid and the cell holding the B liquid may be the same or different.
- FIG. 1 is a schematic diagram showing an example of a cell used for evaluating the permeability of heavy metal ions.
- the cell 10 includes a cell main body 12, an opening (sampling port, electrode insertion port) 14, and a flange (test piece contact portion, test piece mounting portion) 16.
- the cell body 12 has an internal space capable of holding a liquid.
- the opening 14 is tubular and is disposed at the upper part of the cell body 12.
- the internal space of the cell body 12 communicates with the outside through the opening 14.
- the flange portion 16 has a tubular shape (for example, an annular shape), and is disposed on a side portion of the cell body 12.
- the internal space of the cell body 12 communicates with the outside through the flange portion 16.
- FIG. 2 is a schematic diagram showing a measuring apparatus used for evaluating permeability based on a current value as an example of a measuring apparatus used for evaluating the permeability of heavy metal ions.
- FIG. 2A is a diagram illustrating the entire measurement apparatus.
- FIG. 2B is an enlarged view showing the connection portion C between the cells.
- FIG. 2C is a schematic cross-sectional view taken along the line IIc-IIc in FIG.
- the measuring apparatus 100 includes a first cell 10a, a second cell 10b, a DC power source 20, and an ammeter 30.
- the cells 10a and 10b have the same configuration as the cell 10 in FIG. 1, and are, for example, transmission cells.
- the cell 10a has a cell body 12a, an opening 14a, and a flange portion 16a.
- the cell 10b has a cell main body 12b, an opening 14b, and a flange portion 16b.
- Liquid A is held in the internal space of the cell body 12a.
- Liquid B is held in the internal space of the cell body 12b.
- the flange portion 16a of the cell 10a and the flange portion 16b of the cell 10b are connected to each other via the first packing 50a, the test piece 40, and the second packing 50b.
- the test piece 40 is, for example, circular, and has a first main surface 40a and a second main surface 40b facing the main surface 40a.
- the packing 50a is annular (for example, annular) and is in contact with the flange portion 16a.
- the packing 50b is annular (for example, annular) and is in contact with the flange portion 16b.
- the test piece 40 is disposed between the packing 50a and the packing 50b.
- the main surface 40a of the test piece 40 is in contact with the packing 50a.
- the main surface 40b of the test piece 40 is in contact with the packing 50b.
- these members are arranged so that the center axes of the flange portions 16a and 16b, the test piece 40, and the packings 50a and 50b coincide.
- the inner diameter D of the packings 50a and 50b is 0.5 to 2.0 cm.
- the inner diameters of the flange portions 16a and 16b are, for example, 0.5 to 2.5 cm.
- the outer diameters of the packings 50a and 50b are, for example, an inner diameter D + 0.2 cm to an inner diameter D + 1.0 cm.
- the diameter of the test piece 40 is, for example, an inner diameter D + 0.2 cm to an inner diameter D + 2.0 cm.
- the thickness of the test piece 40 is, for example, 0.0005 to 0.02 cm (5 to 200 ⁇ m).
- the liquid A held in the cell 10a is in contact with the main surface 40a of the test piece 40 at the flange portion 16a.
- the liquid B held in the cell 10b is in contact with the main surface 40b of the test piece 40 at the flange portion 16b.
- the liquid A and the liquid B are separated via the test piece 40.
- the anode 60a is inserted into the internal space of the cell 10a through the opening 14a.
- the lower end side (one end side) of the anode 60a is in contact with the liquid A by being immersed in the liquid A in the internal space of the cell 10a.
- the upper end side (the other end side) of the anode 60a is located outside the opening 14a.
- a clip 62a is attached to the upper end of the anode 60a.
- the clip 62a has conductivity.
- the cathode 60b is inserted into the internal space of the cell 10b through the opening 14b.
- the lower end side (one end side) of the cathode 60b is in contact with the liquid B by being immersed in the liquid B in the internal space of the cell 10b.
- the upper end side (the other end side) of the cathode 60b is located outside the opening 14b.
- a clip 62b is attached to the upper end of the cathode 60b.
- the clip 62b has conductivity.
- the anode side of the DC power supply 20 is connected to the clip 62a through the electric wiring 70a.
- the cathode side of the DC power supply 20 is connected to the ammeter 30 via the electric wiring 70b.
- the DC power supply 20 and the ammeter 30 are connected in series.
- the ammeter 30 is connected to the clip 62b through the electrical wiring 70c.
- FIG. 3 is a schematic diagram showing a measuring apparatus used for evaluating permeability based on heavy metal ion concentration as an example of a measuring apparatus used for evaluating permeability of heavy metal ions.
- FIG. 3A is a diagram illustrating the entire measurement apparatus.
- FIG. 3B is an enlarged view showing the connection part C between the cells.
- FIG. 4 is a schematic cross-sectional view taken along line IIIc-IIIc in FIG.
- the measuring apparatus 200 has the same configuration as the measuring apparatus 100 except that the ammeter 30 is not provided and the DC power supply 20 and the clip 62b are directly connected via the electric wiring 70d. Yes.
- the solution A is preferably a solution obtained by mixing a heavy metal salt (ionic compound) containing heavy metal ions and a solvent and dissolving the heavy metal salt in the solvent. Since the liquid A containing heavy metal ions (cations) is held in the cell on the anode side, by applying a voltage between the anode and the cathode, the heavy metal ions contained in the liquid A are measured. It passes through the test piece and moves to the cathode side cell. Thereby, the permeability
- heavy metal ions contained in the liquid A there are no particular restrictions on the heavy metal ions contained in the liquid A.
- copper ions are particularly preferable from the viewpoint of further improving the permeability of the insulating material used for semiconductor manufacture.
- heavy metal salts include chloride salts, sulfate salts, acetate salts, iodide salts, and nitrate salts.
- the heavy metal salt is easily dissolved in a solvent (for example, water) (for example, the solubility in water at 23 ° C. is 0.5 mg / kg or more).
- a solvent for example, water
- the solubility in water at 23 ° C. is 0.5 mg / kg or more.
- soluble copper metal salts include copper chloride (I), copper chloride (II), copper sulfate (I), copper sulfate (II), copper acetate (I), copper acetate (II), iodine Examples thereof include copper (I) chloride and copper (II) nitrate.
- the liquid A is an aqueous solution.
- various heavy metal salts can be used and adjusted to various concentrations.
- a solvent of A liquid unless the test piece used for a measurement melt
- the heavy metal ion concentration (for example, copper ion concentration) of the liquid A is 0.5 mg / kg or more. Thereby, since there is a sufficient amount of heavy metal ions (for example, copper ions), the permeability of heavy metal ions to the test piece can be evaluated.
- the heavy metal ion concentration (for example, copper ion concentration) of the liquid A has the following concentration from the viewpoint that permeation of heavy metal ions (for example, copper ions) to the test piece is easily detected by a change in current value and quantitative analysis of heavy metal ions. preferable.
- the heavy metal ion concentration is preferably 5 mg / kg or more from the viewpoint of easy evaluation of the permeability of heavy metal ions since a sufficient amount of heavy metal ions (for example, copper ions) are present.
- the heavy metal ion concentration is 50000 mg / kg or less from the viewpoint of suppressing the precipitation of a part of heavy metals during the measurement and suppressing an excessive increase in the amount of permeation to easily determine a significant difference in permeability.
- Preferably, 5000 mg / kg or less is more preferable.
- the heavy metal ion concentration of the liquid A is, for example, the concentration before applying a voltage between the anode and the cathode.
- the heavy metal ion concentration for example, copper ion concentration
- the heavy metal ion concentration is preferably adjusted to the above range in terms of heavy metal (for example, in terms of copper element).
- the B liquid does not contain heavy metal ions (for example, heavy metal salts).
- the organic solvent contained in the liquid B is preferably an organic solvent excellent in miscibility with water (for example, completely miscible with water).
- the organic solvent having excellent miscibility with water include methanol, ethanol, 1-propanol, 2-propanol, tetrahydrofuran, N, N-dimethylformamide and N-methyl-2-pyrrolidone.
- N-methyl-2-pyrrolidone is preferable from the viewpoint of a high boiling point and low flammability of the mixed solution.
- a B liquid unless the test piece used for a measurement melt
- the content (mixing ratio) of the organic solvent is 20% by mass or more based on the total amount of the liquid B from the viewpoint of reducing the time required for the permeation of heavy metal ions. Preferably, 40 mass% or more is more preferable.
- the content of the organic solvent suppresses that the permeation rate is too high and makes it easy to determine a significant difference in permeability, and easily suppresses dissolution of the test piece. From a viewpoint, 80 mass% or less is preferable and 60 mass% or less is more preferable on the basis of the whole quantity of B liquid.
- the electrical conductivity of the B liquid is preferably 1 ⁇ S or more at 23 ° C., more preferably 200 ⁇ S or more. As described above, since the liquid B has a slight conductivity, the time required for permeation of heavy metal ions is shortened, and the evaluation can be made more quickly.
- the upper limit value of the conductivity of the B liquid is not particularly limited.
- the conductivity of the B liquid can be measured using, for example, an SD data logger multi-water quality measuring instrument CD-4307SD manufactured by Mother Tool Co., Ltd.
- a method for adjusting the conductivity of the B liquid to 1 ⁇ S or more includes adding a small amount of a compound that ionizes in water.
- a compound that ionizes in water examples include light metal salts, inorganic salts (for example, sodium sulfate), acids, and alkalis.
- light metal salts and inorganic salts for example, sodium sulfate are preferable from the viewpoint of easily suppressing chemical changes in the test piece.
- the electrode (anode and cathode) inserted in each cell will be described.
- the electrode material may be an electrical conductor, and is not limited to a commercially available material for the electrode, and various materials can be used. Moreover, it may not be a commercially available electrode, and as an electrode, what processed the metal plate into arbitrary shapes may be used, for example, and cores, such as a pencil and a mechanical pencil, can also be used as it is.
- the electrode include metal electrodes such as platinum, gold, and palladium; carbon electrodes (carbon material electrodes). Among these, a carbon electrode is preferable from a viewpoint of being inexpensive.
- the voltage that can be output from the DC power supply is preferably 1 V or more from the viewpoint that the time required for permeation of heavy metal ions is shortened and the evaluation can be performed more quickly.
- the voltage applied between the anode and the cathode at the time of measurement varies depending on the type of the test piece, heavy metal ions, A liquid and B liquid, but for example, a test piece having a thickness of 20 ⁇ m (for example, an adhesive tape for semiconductor) is used.
- a test piece having a thickness of 20 ⁇ m for example, an adhesive tape for semiconductor
- a solution of copper sulfate in solution A and a solution of water: N-methyl-2-pyrrolidone: sodium sulfate in a mass ratio of 50: 50: 0.05 in solution B about 6 to 24 V can be applied to the electrode. It can be measured more quickly.
- a voltage is applied between the anode and the cathode, and a permeation phenomenon of heavy metal ions with respect to the test piece is detected to evaluate the permeability of the heavy metal ions with respect to the test piece.
- Examples of a method for detecting the permeation phenomenon of heavy metal ions with respect to a test piece include a method of measuring a current value flowing between an anode and a cathode after applying a voltage between the anode and the cathode, and an anode and a cathode.
- a method of quantifying the heavy metal ion concentration of the B liquid after applying a voltage between the two can be used.
- the test piece In the method of measuring the value of the current flowing between the anode and the cathode, when a voltage is applied between the anode and the cathode and heavy metal ions pass through the test piece and move from the A liquid to the B liquid, the test piece is partitioned. A slight current begins to flow between the liquid A and the liquid B, and the current value gradually increases.
- the difference in permeability can be evaluated. For example, when using a test specimen to be measured, the time required to reach a predetermined current value and the time required to reach a predetermined current value when using a test specimen to be compared are respectively acquired.
- the permeability can be evaluated by comparing the required times with each other. For example, it can be evaluated that the shorter the time required to reach a predetermined current value, the higher the permeability.
- the type of ammeter used is not particularly limited. For example, by using an ammeter with a detection lower limit of 1 ⁇ A or more, the permeability of heavy metal ions is evaluated with good reproducibility. be able to.
- the heavy metal ions pass through the test piece and move from the A liquid to the B liquid, and gradually the heavy metal ion concentration in the B liquid. Will increase.
- the change in heavy metal ion concentration for example, the time required to reach a predetermined heavy metal ion concentration, the heavy metal ion concentration after a predetermined time
- the difference in permeability can be evaluated. For example, the time required to reach a predetermined heavy metal ion concentration when using a test specimen to be measured and the time required to reach a predetermined heavy metal ion concentration when using a test specimen to be compared are acquired, respectively. Then, the permeability can be evaluated by comparing the required times with each other. For example, the shorter the time required to reach a predetermined heavy metal ion concentration, the higher the permeability can be evaluated.
- the method for quantifying the heavy metal ion concentration contained in the solution B is not particularly limited, and for example, colorimetric analysis using an ion chromatography method or bathocuproine method is used as a simple method.
- the permeability evaluation method according to the present embodiment may be used in a semiconductor manufacturing method.
- the semiconductor manufacturing method according to the present embodiment includes a step of manufacturing a semiconductor using an insulating material used for semiconductor manufacturing, and an insulating material used for semiconductor manufacturing by the permeability evaluation method according to the present embodiment. And evaluating the permeability of heavy metal ions to the test piece.
- a carrier film was provided by applying a varnish on a polyethylene terephthalate film having a thickness of 35 ⁇ m and then drying by heating at 140 ° C. for 5 minutes to form a B-stage coating film having a thickness of 20 ⁇ m.
- a die bonding film (die bonding adhesive film A, hereinafter referred to as “adhesive film A”) was produced.
- YDCN-703 (trade name, cresol novolac type epoxy resin, epoxy equivalent 210, molecular weight 1200, softening point 80 ° C.) 15 parts by mass as an epoxy resin, and Mirex XLC-LL (Mitsui Chemicals Co., Ltd.) as a phenol resin Company product, trade name, phenol resin, hydroxyl group equivalent 175, water absorption 1.8%, heating mass reduction rate 4% at 350 ° C.
- a varnish is applied on a 35 ⁇ m thick polyethylene terephthalate film that has been subjected to a release treatment, and then heated and dried at 140 ° C. for 5 minutes to form a B-stage coating film having a thickness of 20 ⁇ m, thereby providing a carrier film.
- a die bonding film (die bonding adhesive film B, hereinafter referred to as “adhesive film B”) was produced.
- This aqueous solution was cast on a cover glass. And it dried at 175 degreeC for 10 minutes after drying at 100 degreeC on a hotplate, and the glass substrate contaminated with the copper ion was produced.
- a silicon die having a thickness of 30 ⁇ m whose back surface was dry polished was diced into a size of 10 mm ⁇ 10 mm to produce a silicon die.
- the adhesive films A and B produced above were cut into 10 mm ⁇ 10 mm together with the carrier film.
- the carrier film was peeled off, and adhesive films A and B were laminated at 80 ° C. on the back side of the silicon die to obtain a silicon die.
- sample 1 A silicon die sample with glass substrate-adhesive film (sample 1) was cured at 150 ° C. for 1 hour, then at 175 ° C. for 3 hours, and further at 265 ° C. for 1 hour as a simple reflow condition to prepare sample 2.
- the silicon wafer surface was lightly wiped with a cotton swab soaked with N-methyl-2-pyrrolidone. Next, after further cleaning using a cotton swab soaked with acetone, it was air-dried at room temperature.
- the silicon side surfaces of Sample 1 and Sample 2 were measured at five locations using time-of-flight secondary ion mass spectrometry (primary ion: Au, neutralization gun combined, measurement area: 400 ⁇ m ⁇ ). From the copper ion intensity in the positive ion mass spectrum and the intensity of the silicon portion on the substrate surface, the intensity ratio of copper existing on the silicon surface (Cu / Si intensity ratio, average value at five locations) was determined. Further, as the rate of change of the intensity ratio, the rate of change of the intensity ratio of sample 2 relative to the intensity ratio of sample 1 (the intensity ratio of sample 2 / the intensity ratio of sample 1 and the Cu / Si intensity change rate) was obtained. The results are shown in Table 1 below.
- the adhesive film B tends to transmit copper ions existing on the substrate surface more easily than the adhesive film A.
- the permeability of heavy metal ions to the test piece was evaluated based on this result.
- Example 1 Sulfuric acid adjusted to have a copper ion concentration of 500 mg / kg in terms of Cu element by dissolving 2.0 g of anhydrous copper (II) sulfate in 1020 g of distilled water and stirring well until the copper sulfate is completely dissolved. A copper aqueous solution was prepared. This aqueous solution was used as A liquid.
- II anhydrous copper
- the conductivity (23 ° C.) of solution B was measured using an SD data logger multi-water quality measuring instrument CD-4307SD manufactured by Mother Tool Co., Ltd. and found to be 210 ⁇ S.
- the adhesive film A (thickness 20 ⁇ m) produced above was cut out into a circle having a diameter of about 3 cm.
- two silicon packing sheets having a thickness of 1.5 mm, an outer diameter of about 3 cm, and an inner diameter of 1.8 cm were produced.
- the adhesive film A was sandwiched between two silicon packing sheets.
- the adhesive film A sandwiched between the silicon packing sheets was sandwiched between the flange portions of two glass cells (cells having the configuration of FIG. 1) having a volume of 50 ml and fixed with rubber bands.
- the copper ion permeation time of the adhesive film B was determined by the same operation. Further, the ratio of the transmission time of the adhesive film A to the transmission time of the adhesive film B (the transmission time of the adhesive film A / the transmission time of the adhesive film B) was calculated. The results are shown in Table 2 below.
- the measurement result of the current value of Example 1 is shown in FIG.
- the solid line A1 is the measurement result of the adhesive film A
- the broken line B1 is the measurement result of the adhesive film B.
- Examples 2 to 4 and Comparative Examples 1 and 3 Evaluation was performed in the same manner as in Example 1 except that the components of liquid B were changed to the components shown in Tables 2 and 3 below. The results are shown in Tables 2 and 3.
- the permeability of heavy metal ions can be easily and quickly evaluated without requiring an evaluation after the package is manufactured.
- Comparative Example 1 in which no organic solvent was used for the B liquid and Comparative Example 2 in which no voltage was applied, the permeability could not be evaluated quickly.
- the film used as a measuring object melt
- Example 5 Evaluation Based on Heavy Metal Ion Concentration> (Example 5) Liquid A and liquid B similar to those in Example 1 were prepared.
- the adhesive film A (thickness 20 ⁇ m) produced above was cut into a circle with a diameter of about 3 cm. Next, two silicon packing sheets having a thickness of 1.5 mm, an outer diameter of about 3 cm, and an inner diameter of 1.8 cm were produced. The adhesive film A was sandwiched between two silicon packing sheets. The adhesive film A sandwiched between the silicon packing sheets was sandwiched between the flange portions of two glass cells (cells having the configuration of FIG. 1) having a volume of 50 ml and fixed with rubber bands.
- liquid A was injected into one glass cell, and then 50 g of liquid B was injected into the other glass cell.
- STAEDTLER Mars Carbon ( ⁇ 2 mm / 130 mm) was inserted into each cell as a carbon electrode.
- the liquid A side was the anode
- the liquid B side was the cathode
- the anode and the cathode were connected via a DC power supply (DC power supply device AD-9723D manufactured by A & D Co., Ltd.).
- a voltage was applied at an applied voltage of 24.0 V, and the liquid B was sampled every 48 hours (2880 minutes) at regular intervals after the application to measure the copper ion concentration.
- the sampled B solution was colored using a pack test WAK-Cu manufactured by Kyoritsu Riken Co., Ltd., and quantified using a digital pack test DPM-Cu manufactured by Kyoritsu Riken Co., Ltd.
- the point at which the sampled B liquid copper ion concentration was 0.15 mg / kg or more was defined as the copper ion permeation time.
- the copper ion permeation time of the adhesive film B was determined by the same operation. Further, the ratio of the transmission time of the adhesive film A to the transmission time of the adhesive film B (the transmission time of the adhesive film A / the transmission time of the adhesive film B) was calculated. The results are shown in Table 4 below.
- Example 5 the measurement result of the copper ion concentration of Example 5 is shown in FIG. In FIG. 5, the solid line A2 is the measurement result of the adhesive film A, and the broken line B2 is the measurement result of the adhesive film B.
- Examples 5 to 10 and Comparative Example 4 Evaluation was performed in the same manner as in Example 5 except that the components of the liquid B were changed to the components shown in Tables 4 and 5 below. The results are shown in Tables 4 and 5.
- Example 10 Although the copper salt precipitated in the A liquid, it was confirmed that the permeability of heavy metal ions can be evaluated. On the other hand, in Comparative Example 4 having a small copper ion concentration, the permeability could not be evaluated quickly.
- the permeability evaluation method according to the present invention can easily and quickly evaluate the permeability of heavy metal ions to an insulating material (insulating material for semiconductor) used in semiconductor manufacturing, for example, an insulating material for semiconductor It can be used for evaluation of gettering function, evaluation of barrier ability, and inspection method of materials. As a result, it can be used for development of a highly reliable material, quality control, etc. in an ultrathin PKG structure.
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Abstract
Description
エポキシ樹脂としてYDCN-703(東都化成株式会社製、商品名、クレゾールノボラック型エポキシ樹脂、エポキシ当量210、分子量1200、軟化点80℃)55質量部と、フェノール樹脂としてミレックスXLC-LL(三井化学株式会社製、商品名、フェノール樹脂、水酸基当量175、吸水率1.8%、350℃における加熱質量減少率4%)45質量部と、シランカップリング剤としてNUC A-189(日本ユニカー株式会社製、商品名、γ-メルカプトプロピルトリメトキシシラン)1.7質量部及びNUCA-1160(日本ユニカー株式会社製、商品名、γ-ウレイドプロピルトリエトキシシラン)3.2質量部と、フィラーとしてアエロジルR972(シリカ表面にジメチルジクロロシランを被覆し、400℃の反応器中で加水分解させた、メチル基等の有機基を表面に有するフィラー、日本アエロジル株式会社製、商品名、シリカ、平均粒径0.016μm)32質量部とからなる組成物にシクロヘキサノンを加えて攪拌混合した後、ビーズミルを用いて90分混練した。
エポキシ樹脂としてYDCN-703(東都化成株式会社製、商品名、クレゾールノボラック型エポキシ樹脂、エポキシ当量210、分子量1200、軟化点80℃)15質量部と、フェノール樹脂としてミレックスXLC-LL(三井化学株式会社製、商品名、フェノール樹脂、水酸基当量175、吸水率1.8%、350℃における加熱質量減少率4%)12質量部と、フィラーとして球状シリカ(株式会社アドマテックス製、商品名:SO-25R、平均粒径0.5μm)200質量部と、シクロヘキサノンとを加えて攪拌混合した後、ビーズミルを用いて90分混練した。
ポリアクリル酸水溶液(Nv=25%、粘度8000~12000mPa・s)、硫酸銅水溶液(銅元素換算500mg/kg)及び蒸留水を適宜混合し、Nv=1%、銅イオン含有量5000mg/kg(対固形分)となる銅イオン含有ポリアクリル酸水溶液を調製した。この水溶液をカバーガラス上にキャストした。そして、ホットプレート上にて100℃10分乾燥した後に175℃10分乾燥することにより、銅イオンで汚染されたガラス基板を作製した。
(実施例1)
[A液の調製]
無水硫酸銅(II)2.0gを蒸留水1020gに溶解し、完全に硫酸銅が溶解するまでよく撹拌することにより、銅イオン濃度がCu元素換算で濃度500mg/kgとなるように調整した硫酸銅水溶液を調製した。この水溶液をA液として用いた。
無水硫酸ナトリウム1.0gを蒸留水1000gに溶解し、完全に硫酸ナトリウムが溶解するまでよく撹拌した。これにN-メチル-2-ピロリドン(NMP)を1000g加え、よくかき混ぜた。その後、室温になるまで空冷して溶液を得た。この溶液をB液として用いた。
上記で作製した接着フィルムA(厚さ20μm)を、直径約3cmの円状に切り抜いた。次に、厚さ1.5mm、外径約3cm、内径1.8cmのシリコンパッキンシートを2枚作製した。接着フィルムAを2枚のシリコンパッキンシートで挟んだ。シリコンパッキンシートで挟んだ接着フィルムAを容積50mlの2つのガラス製セル(図1の構成を有するセル)のフランジ部で挟み、ゴムバンドで固定した。
B液の構成成分を下記表2,3に示す成分に変更したことを除き実施例1と同様に評価を行った。結果を表2,3に示す。
電圧を印加しなかったことを除き実施例1と同様に評価を行った。結果を下記表3に示す。
(実施例5)
実施例1と同様のA液及びB液を準備した。
B液の構成成分を下記表4,5に示す成分に変更したことを除き実施例5と同様に評価を行った。結果を表4,5に示す。
Claims (8)
- 試験片に対する重金属イオンの透過性を評価する透過性評価方法であって、
重金属イオンを含有する第1の液と、水及び有機溶媒を含有する第2の液とが試験片を介して隔てられた状態で、前記第1の液側に設けられた陽極と、前記第2の液側に設けられた陰極との間に電圧を印加して前記陽極と前記陰極との間に流れる電流値を測定する工程を備え、
前記試験片が、半導体製造に用いられる絶縁材料を含有し、
前記第1の液の重金属イオン濃度が0.5mg/kg以上である、透過性評価方法。 - 試験片に対する重金属イオンの透過性を評価する透過性評価方法であって、
重金属イオンを含有する第1の液と、水及び有機溶媒を含有する第2の液とが試験片を介して隔てられた状態で、前記第1の液側に設けられた陽極と、前記第2の液側に設けられた陰極との間に電圧を印加した後に前記第2の液の重金属イオン濃度を測定する工程を備え、
前記試験片が、半導体製造に用いられる絶縁材料を含有し、
前記第1の液の重金属イオン濃度が0.5mg/kg以上である、透過性評価方法。 - 前記第2の液が前記有機溶媒としてN-メチル-2-ピロリドンを含有する、請求項1又は2に記載の評価方法。
- 前記第2の液のN-メチル-2-ピロリドンの含有量が20質量%以上80質量%以下である、請求項3に記載の評価方法。
- 前記第2の液の導電率が23℃において1μS以上である、請求項1~4のいずれか一項に記載の評価方法。
- 前記第1の液が前記重金属イオンとして銅イオンを含有する、請求項1~5のいずれか一項に記載の評価方法。
- 前記第1の液の銅イオン濃度が50000mg/kg以下である、請求項6に記載の評価方法。
- 前記半導体製造に用いられる絶縁材料が半導体用接着テープである、請求項1~7いずれか一項に記載の評価方法。
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