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WO2017221613A1 - Feuille de liaison thermique, et feuille de liaison thermique doté de ruban de découpage en dés - Google Patents

Feuille de liaison thermique, et feuille de liaison thermique doté de ruban de découpage en dés Download PDF

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Publication number
WO2017221613A1
WO2017221613A1 PCT/JP2017/019187 JP2017019187W WO2017221613A1 WO 2017221613 A1 WO2017221613 A1 WO 2017221613A1 JP 2017019187 W JP2017019187 W JP 2017019187W WO 2017221613 A1 WO2017221613 A1 WO 2017221613A1
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WIPO (PCT)
Prior art keywords
heat bonding
phase
bonding sheet
sheet
precursor layer
Prior art date
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Application number
PCT/JP2017/019187
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English (en)
Japanese (ja)
Inventor
哲士 本田
悠樹 菅生
菜穂 鎌倉
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.)
Nitto Denko Corp
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Nitto Denko Corp
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
Priority claimed from JP2017046481A external-priority patent/JP6864505B2/ja
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to EP17815082.7A priority Critical patent/EP3477688A4/fr
Priority to CN201780038817.XA priority patent/CN109462991A/zh
Priority to US16/308,931 priority patent/US11817415B2/en
Publication of WO2017221613A1 publication Critical patent/WO2017221613A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09J1/00—Adhesives based on inorganic constituents
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • H10W72/071—
    • H10W72/073—
    • H10W72/884—

Definitions

  • the present invention relates to a heat bonding sheet and a heat bonding sheet with a dicing tape.
  • the method of adhering a semiconductor element to an adherend such as a metal lead frame has started with conventional gold-silicon eutectic, and has shifted to a method using solder and resin paste.
  • a conductive resin paste is sometimes used.
  • Si Insulated Gate Bipolar Transistor
  • MOSFET Metal-Oxide-Semiconductor Field-Effect Transistor
  • a semiconductor using SiC or GaN has features such as a large band gap and a high dielectric breakdown electric field, and can operate at low loss, high speed, and high temperature.
  • High-temperature operation is advantageous in automobiles and small power conversion devices that have severe thermal environments.
  • Semiconductor devices for applications with severe thermal environments are expected to operate at a high temperature of about 250 ° C., and solder and conductive adhesives, which are conventional bonding / adhesive materials, have problems in thermal characteristics and reliability. Therefore, a paste material containing sintered metal particles has been proposed (for example, Patent Document 1).
  • the sintered metal particle-containing paste material contains nano-sized to micro-sized metal particles, and these metal particles are melted at a temperature lower than the normal melting point due to the nano-size effect, and sintering between the particles proceeds.
  • the paste material containing sintered metal particles is literally in a paste state, the thickness becomes non-uniform as in the case of the conductive resin paste, and as a result, uneven bonding occurs, resulting in a decrease in bonding reliability especially at high temperatures. There is a case. Therefore, in order to solve the non-uniformity of thickness and problems caused by this, a technique for forming a joining material containing sinterable metal particles into a sheet shape is being studied.
  • the decomposition temperature of the polymer material may shift to a high temperature side. If the degree of high temperature shift of the decomposition temperature becomes strong, the decomposition temperature of the polymer material may be the same as or higher than the sintering temperature of the sinterable metal particles. In this case, even when the sinterable metal particles are sintered, the polymer material remains without disappearing, and the undisappeared polymer material inhibits the sintering of the sinterable metal particles. There is a possibility that the sintering of the conductive metal particles becomes insufficient and the bonding reliability of the power semiconductor device is lowered.
  • the present invention has been made in view of the above-described problems, and its purpose is to perform heat bonding that can suppress the inhibition of sintering of sinterable metal particles by an organic component and can provide sufficient bonding reliability to a power semiconductor device. It is providing the sheet
  • the sheet for heat bonding has a precursor layer that becomes a sintered layer by heating,
  • the precursor layer includes sinterable metal particles and an organic component,
  • the precursor layer has a phase separation structure that is a sea-island structure or a co-continuous structure,
  • the maximum value of the diameters of the maximum inscribed circles in the region occupied by each phase of the phase separation structure is 1 ⁇ m or more and 50 ⁇ m or less.
  • the precursor layer of the heat bonding sheet has a phase separation structure in which the sinterable metal particles and the organic component have a sea-island structure or a co-continuous structure, and are separated into two or more phases.
  • the maximum diameter is 1 ⁇ m or more and 50 ⁇ m or less. Yes. If each phase is finely dispersed or phase-separated, the diameter of the maximum inscribed circle in the region occupied by each phase is also reduced.
  • the diameter of the maximum inscribed circle in the region occupied by each phase increases. That is, the maximum value of the diameter of the maximum inscribed circle obtained for each phase (hereinafter also referred to as “maximum diameter”) is significant as an index representing the degree of dispersion or aggregation of the phase separation structure in the precursor layer. Will have.
  • the maximum diameter in the phase separation structure is in the above range, and the degree of aggregation (aggregation degree) of each phase is relatively high, in other words, the degree of phase separation is in a sparse state.
  • a high degree of decomposition temperature of the organic component due to the coexistence of the organic component and the sinterable metal particles by forming an appropriate separation state between the phase in which the sinterable metal particles and the phase in which the organic component collects.
  • the shift is suppressed and the decomposition and disappearance of the organic component can be promoted, and the penetration of the phase of the organic component into the phase of the sinterable metal particles is suppressed.
  • inhibition of sintering of the sinterable metal particles by the organic component can be prevented, and the bonding reliability of the power semiconductor device can be improved.
  • each phase will be finely dispersed, resulting in a high temperature shift in the decomposition temperature of the organic component and an inhibition of sintering of the sinterable metal particles by the organic component, resulting in reduced bonding reliability.
  • the maximum diameter is too large, the phase separation structure becomes too sparse, and each component is present in an uneven manner, which may impair the uniformity of the characteristics of the heat bonding sheet.
  • the organic component includes a low molecular component having a weight average molecular weight of 1000 or less and a polymer component having a weight average molecular weight of 5000 or more, It is preferable that the maximum absolute value of the difference between the polarity term of the solubility parameter of the low molecular component and the polarity term of the solubility parameter of the polymer component is 3 or more and 15 or less.
  • the high molecular component and the low molecular component are hardly dissolved in each other, and a phase separation structure is exhibited between the two components.
  • the low-molecular component has more liquid components and has a higher affinity with the sinterable metal particles in terms of wettability and molecular mobility. Many stay in the component phase. That is, a phase separation structure between the sinterable metal particles and the polymer component can be efficiently formed using the phase separation action of the polymer component and the low molecular component.
  • phase separation structure having a maximum diameter in a specific range can be efficiently formed.
  • the area ratio of the black portion in the entire SEM surface observation image is 10 to 80%
  • the SEM central portion observation image of the central portion in the thickness direction of the precursor layer is binarized to display in black and white
  • the area ratio of the black portion in the entire SEM central portion observation image is 1 to 60%. preferable.
  • the heat bonding sheet is used to heat bond a semiconductor chip and an adherend, and at least a part of each surface of the semiconductor chip and the adherend includes gold, silver, or copper. preferable. Since the heat bonding sheet has high bonding reliability, it can be suitably used for heat bonding between a semiconductor chip and an adherend such as a lead frame. In addition, since at least a part of each surface of the adherend and the chip contains gold, silver or copper, the affinity with the heat bonding sheet or bonding wire is increased, and the bonding reliability with them is further improved. Can do.
  • a sheet for heat bonding with a dicing tape according to another embodiment of the present invention a dicing tape, And the heat bonding sheet laminated on the dicing tape.
  • the step of bonding to the dicing tape can be omitted.
  • seat for heat joining is provided, sintering of a sinterable metal particle can be advanced by sufficient level, and favorable joining reliability can be acquired.
  • FIG. 1 is a schematic cross-sectional view showing a heat bonding sheet with a dicing tape according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another heat bonding sheet with dicing tape according to another embodiment of the present invention.
  • a heat bonding sheet 10 with a dicing tape has a configuration in which a heat bonding sheet 3 is laminated on a dicing tape 11.
  • the dicing tape 11 is configured by laminating the pressure-sensitive adhesive layer 2 on the substrate 1, and the heat bonding sheet 3 is provided on the pressure-sensitive adhesive layer 2.
  • seat for heat joining with a dicing tape of this invention may be the structure which formed sheet
  • the heat bonding sheets 3 and 3 ′ have a sheet shape. Since it is not a paste but a sheet, good thickness uniformity and handling properties can be obtained.
  • seats 3 and 3 ' which concern on this embodiment consist of the precursor layer 31 used as a sintered layer by heating.
  • the heat bonding sheet includes a single precursor layer that becomes a sintered layer by heating will be described, but the present invention is not limited to this example.
  • the precursor layer that becomes a sintered layer by heating may have a configuration in which a plurality of the precursor layers are laminated.
  • this embodiment demonstrates the case where the sheet
  • stacked the precursor layer which becomes a sintered layer by heating, and the other layer (layer which does not become a sintered layer by heating) may be sufficient. That is, the heat-bonding sheet in the present invention is not particularly limited as long as it has at least a precursor layer that becomes a sintered layer by heating.
  • the precursor layer 31 (hereinafter also simply referred to as “precursor layer 31”) that becomes a sintered layer by heating contains sinterable metal particles and organic components (details of each component will be described later).
  • the precursor layer 31 has a phase separation structure resulting from phase separation between the sinterable metal particles and the organic component on at least one surface.
  • FIG. 3A shows a mode in which the phase separation structure is a sea-island structure
  • FIG. 3B shows a case where the phase separation structure is a co-continuous structure.
  • the phase separation structure may be a sea-island structure or a co-continuous structure, and the sea-island structure and the co-continuous structure may coexist.
  • the sea-island structure shown in FIG. 3A is separated into two phases, a sea phase (for example, an organic component phase) Ps and an island phase (for example, a phase of sinterable metal particles) Pi.
  • the number of phases included in the phase separation structure is not limited to 2, and may be separated into three or more phases according to the components included in the precursor layer 31.
  • the sea phase and the island phase are not limited to the organic component phase and the sinterable metal particle phase, respectively, and the sea phase and island are included depending on the components contained in the precursor layer 31 and their blending ratio.
  • These phases may be a phase of a sinterable metal particle and a phase of an organic component, respectively.
  • the sea-island structure shown in FIG. 3A is separated into two phases of a first phase P1 and a second phase P2 that are continuous to some extent.
  • the number of phases included in the phase separation structure is not limited to 2, and may be separated into three or more phases depending on the components included in the precursor layer 31 and the like.
  • the first phase and the second phase may be either a sinterable metal particle phase or an organic component phase, respectively.
  • the maximum value of the diameters of the maximum inscribed circles in the region occupied by each phase of the phase separation structure is 1 ⁇ m or more and 50 ⁇ m or less.
  • FIG. 3A is viewed as a schematic diagram of an SEM surface observation image of at least one surface of the precursor layer 31, in the sea-island structure shown in FIG. 3A, the region occupied by the island phase Pi is in the region occupied by the sea phase Ps.
  • the inscribed circle for the region occupied by the phase Pi of the island (for example, when looking at the region occupied by one island, the largest area of the circles in contact with the boundary line between the island phase and the sea phase) A plurality of circles) are obtained for each island, and the inscribed circle having the largest diameter among these inscribed circles is set as the maximum inscribed circle Ci for the region occupied by the phase Pi of the island.
  • the inscribed circle (for example, the largest area among the circles in contact with the boundary line between the region of the localized sea phase and the region of the island) occupies the region occupied by the sea phase Ps.
  • a plurality of circles) are obtained for each limited region, and the inscribed circle having the largest diameter among these inscribed circles is defined as the maximum inscribed circle Cs for the region occupied by the sea phase Ps.
  • the diameter Di of the maximum inscribed circle Ci for the region occupied by the island phase Pi is compared with the diameter Ds of the maximum inscribed circle Cs for the region occupied by the sea phase Ps, and the maximum value (ie, , Diameter Di) is the maximum diameter. Even if there are three or more phases in the phase separation structure, the maximum diameter can be obtained by obtaining the diameter of the maximum inscribed circle for each phase in the same manner as described above, and obtaining the maximum value of these diameters. it can.
  • the maximum diameter can be obtained similarly to the embodiment shown in FIG. 3A.
  • the region occupied by the first phase P1 and the region occupied by the second phase P2 coexist.
  • an inscribed circle for the region occupied by the first phase P1 (for example, when one continuous region of the regions occupied by the first phase P1 is viewed, the boundary between the phase and the second phase) A circle having the maximum area among circles in contact with the line) is obtained for each continuous region, and the maximum inscribed circle C1 for the region in which the first phase P1 occupies the inscribed circle having the maximum diameter among the plurality of inscribed circles.
  • an inscribed circle (for example, when one continuous region of the region occupied by the second phase P2 is viewed in the region occupied by the second phase P2 is the phase and the first phase) A circle having the maximum area among the circles in contact with the boundary line with each other) is determined for each continuous region, and the maximum inner diameter of the region in which the second phase P2 occupies the inscribed circle having the maximum diameter among these inscribed circles. Let it be a tangent circle C2. Then, the diameter D1 of the maximum inscribed circle C1 for the region occupied by the first phase P1 is compared with the diameter D2 of the maximum inscribed circle C2 for the region occupied by the second phase P2, and the maximum value of these is compared.
  • the diameter D1 (That is, the diameter D1) is the maximum diameter. Even if there are three or more continuous phases in the phase separation structure, the maximum inscribed circle diameter is obtained for each continuous phase in the same manner as described above, and the maximum diameter is obtained by obtaining the maximum value of these diameters. be able to.
  • the maximum diameter is 1 ⁇ m or more and 50 ⁇ m or less, preferably 1.5 ⁇ m or more and 30 ⁇ m or less, and more preferably 2 ⁇ m or more and 10 ⁇ m or less.
  • the invasion of the organic component phase into the phase of the sinterable metal particles is suppressed, so that inhibition of sintering of the sinterable metal particles by the organic component can be prevented, and the bonding reliability of the power semiconductor device can be improved. Can be improved.
  • the average thickness of the precursor layer 31 is 5 ⁇ m to 200 ⁇ m, preferably 10 ⁇ m to 150 ⁇ m, more preferably 15 ⁇ m to 100 ⁇ m. By keeping the average thickness of the precursor layer 31 before heating in the above range, it is possible to ensure sheet shape maintenance and thickness uniformity.
  • the precursor layer 31 has a tensile modulus obtained by the following tensile test method of preferably 10 MPa to 3000 MPa, more preferably 12 MPa to 2900 MPa, and further preferably 15 MPa to 2500 MPa.
  • Tensile test method (1) As a test sample, a heat bonding sheet (thickness test heat bonding sheet) having a thickness of 200 ⁇ m, a width of 10 mm, and a length of 40 mm is prepared. (2) A tensile test was performed under the conditions of a distance between chucks of 10 mm, a tensile speed of 50 mm / min, and 23 ° C. (3) The slope of the straight line portion of the obtained stress-strain diagram is the tensile modulus.
  • the tensile elastic modulus of the precursor layer 31 is 10 MPa or more, it is possible to further suppress the constituent material of the heat bonding sheet from protruding or creeping up to the chip surface during die attachment. Further, when the tensile elastic modulus is 3000 MPa or less, for example, the semiconductor wafer can be fixed during dicing.
  • the precursor layer 31 has a carbon concentration of 15% by weight or less obtained by energy dispersive X-ray analysis after heating from 23 ° C. to 400 ° C. under a nitrogen atmosphere under a temperature rising rate of 10 ° C./min. Preferably, it is 12% by weight or less, more preferably 10% by weight or less. When the carbon concentration is 15% by weight or less, the precursor layer 31 contains almost no organic matter after being heated to 400 ° C. As a result, after the heat bonding step, the heat resistance is excellent, and high reliability and thermal characteristics are obtained even in a high temperature environment.
  • the sinterable metal particles an aggregate of metal fine particles can be suitably used.
  • the metal fine particles include fine particles made of metal.
  • the metal include gold, silver, copper, silver oxide, and copper oxide.
  • the metal fine particles are at least one selected from the group consisting of silver, copper, silver oxide, and copper oxide, heat bonding can be more suitably performed.
  • the average particle size of the sinterable metal particles is preferably 0.0005 ⁇ m or more, more preferably 0.001 ⁇ m or more.
  • Examples of the lower limit of the average particle diameter include 0.01 ⁇ m, 0.05 ⁇ m, and 0.1 ⁇ m.
  • the average particle size of the sinterable metal particles is preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less.
  • Examples of the upper limit of the average particle diameter include 20 ⁇ m, 15 ⁇ m, 10 ⁇ m, and 5 ⁇ m.
  • the average particle size of the sinterable metal particles is measured by the following method. That is, the sinterable metal particles are observed with an SEM (scanning electron microscope), and the average particle diameter is measured.
  • the SEM observation is, for example, observing at a magnification of 5000 when the sinterable metal particles are in a micro size, observing at a magnification of 50000 in the case of a submicron size, and observing at a magnification of 300000 in the case of a nano size. preferable.
  • the shape of the sinterable metal particles is not particularly limited, and may be, for example, a spherical shape, a rod shape, a scale shape, or an indefinite shape.
  • the precursor layer 31 preferably contains sinterable metal particles in the range of 60 to 98 wt% with respect to the entire precursor layer 31.
  • the content of the sinterable metal particles is more preferably in the range of 65 to 97% by weight, and still more preferably in the range of 70 to 95% by weight.
  • the sinterable metal particles are included in the range of 60 to 98% by weight, the sinterable metal particles are sintered or melted to join two objects (for example, a semiconductor chip and a lead frame). it can.
  • the organic component preferably includes a low molecular component having a weight average molecular weight of 1000 or less.
  • a low molecular component preferably contains a low boiling point binder.
  • the low boiling point binder is used to facilitate handling of the metal fine particles. Specifically, it can be used as a metal fine particle-containing paste in which the metal fine particles are dispersed in the low boiling point binder.
  • the low boiling point binder include, for example, pentanol, hexanol, heptanol, octanol, 1-decanol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, ⁇ -terpineol, 1,6-hexanediol, isobornyl.
  • Monovalent and polyhydric alcohols such as cyclohexanol (MTPH), ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol isobutyl ether, diethylene glycol hexyl ether, triethylene glycol methyl ether, diethylene glycol Dimethyl ether, diethylene glycol Cole diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, propylene glycol propyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol Ethers such as propyl ether, dipropylene glycol butyl ether, dipropy
  • the organic component includes a polymer component having a weight average molecular weight of 5000 or more.
  • a polymer component preferably contains a thermally decomposable binder.
  • the thermally decomposable binder is contained, it is easy to maintain the sheet shape before the heat bonding step. Moreover, it is easy to thermally decompose at the time of a heat joining process.
  • the “thermally decomposable binder” refers to a binder that can be thermally decomposed in the heat bonding step. It is preferable that the thermally decomposable binder hardly remains in the sintered layer (precursor layer 31 after heating) after the heat bonding step.
  • the thermally decomposable binder for example, even if included in the precursor layer 31, energy dispersion after heating from 23 ° C. to 400 ° C. under a nitrogen atmosphere under a temperature rising rate of 10 ° C./min. Examples thereof include materials whose carbon concentration obtained by the type X-ray analysis is 15% by weight or less.
  • thermally decomposable binder For example, if a material that is more easily thermally decomposed is used as the thermally decomposable binder, even if the content is relatively increased, it hardly remains in the sintered layer (preheated precursor layer 31) after the heat bonding step. Can be.
  • thermally decomposable binder examples include polycarbonate, acrylic resin, ethyl cellulose, and polyvinyl alcohol. These materials can be used alone or in admixture of two or more. Of these, polycarbonate is preferable from the viewpoint of high thermal decomposability.
  • the polycarbonate is not particularly limited as long as it can be thermally decomposed in the heat bonding step, but an aromatic compound (for example, benzene) is interposed between the carbonic acid ester groups (—O—CO—O—) of the main chain.
  • an aromatic compound for example, benzene
  • an aliphatic polycarbonate having an aliphatic chain and an aromatic compound having an aromatic compound between carbonic acid ester groups (—O—CO—O—) of the main chain are preferable.
  • the aliphatic polycarbonate include polyethylene carbonate and polypropylene carbonate. Among these, polypropylene carbonate is preferable from the viewpoint of solubility in an organic solvent in producing a varnish for forming a sheet.
  • the aromatic polycarbonate include those containing a bisphenol A structure in the main chain.
  • the polycarbonate preferably has a weight average molecular weight in the range of 10,000 to 1,000,000.
  • the weight average molecular weight is a value measured by GPC (gel permeation chromatography, HLC-8320 GPC manufactured by TOSOH) and calculated in terms of polystyrene.
  • the measurement conditions are as follows. Column: TSKgel SuperHZM-H / HZ4000 / HZ3000 / HZ2000, column size: 6.0 mm inner diameter ⁇ 150 mm, solvent: tetrahydrofuran (THF), solution concentration: 0.03-0.1 wt%, flow rate: 0.6 mL / min , Detector: differential refractometer (RI), column temperature: 40 ° C., injection volume: 20 ⁇ L
  • the acrylic resin is an ester of acrylic acid or methacrylic acid ester having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms, as long as it can be thermally decomposed in the heat bonding step.
  • Polymers (acrylic copolymers) containing seeds or two or more kinds as components are listed.
  • alkyl group examples include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, cyclohexyl group, 2- Examples include ethylhexyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, and dodecyl group.
  • the other monomer forming the polymer is not particularly limited, and for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid Or a carboxyl group-containing monomer such as crotonic acid, an acid anhydride monomer such as maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4 -Hydroxymethyl cycle Hexyl) -hydroxyl group-containing monomers such as methyl acrylate, styrene sulfonic
  • acrylic resins those having a weight average molecular weight of 10,000 to 1,000,000 are more preferable, and those having a weight average molecular weight of 30,000 to 700,000 are more preferable. It is because it is excellent in the adhesiveness before a heat joining process and the thermal decomposability in the heat joining process as it is in the said numerical range.
  • the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
  • acrylic resins acrylic resins that thermally decompose at 200 ° C. to 400 ° C. are preferable.
  • the maximum absolute value of the difference between the polarity term of the solubility parameter of the high molecular component and the polarity term of the solubility parameter of the low molecular component is preferably 3 or more and 15 or less, and more preferably 5 or more and 12 or less.
  • the absolute value of the difference between the polar terms of the solubility parameters becomes the maximum value as it is.
  • there are combinations of differences in polar terms corresponding to the product of the number of types of low-molecular components and the number of types of high-molecular components.
  • the maximum value of the absolute values of the differences be in the above range.
  • the high molecular component and the low molecular component are hardly dissolved from each other, and the formation of a phase separation structure is promoted between the two components.
  • the low-molecular component has more liquid components and has a higher affinity with the sinterable metal particles in terms of wettability and molecular mobility. Many stay in the component phase. That is, a phase separation structure between the sinterable metal particles and the polymer component can be efficiently formed using the phase separation action of the polymer component and the low molecular component.
  • phase separation structure having a maximum diameter in a specific range can be efficiently formed.
  • the area ratio of the black portion in the entire SEM surface observation image is preferably 10 to 80%, more preferably 15 to 70%.
  • the area ratio of the black portion in the entire SEM central portion observation image is 1 to 60%. It is preferably 5 to 50%.
  • the method for measuring the area ratio of the black part when the SEM surface observation image and the SEM center part observation image are binarized is as described in the examples.
  • the integral phase in which the phase of the sinterable metal particles and the low molecular component phase are integrated is a white portion.
  • the polymer component phase is displayed as a black part.
  • the precursor layer 31 may contain, for example, a plasticizer as appropriate in addition to the above components.
  • the heat bonding sheets 3, 3 ' can be manufactured by a usual method.
  • a varnish containing the above components for forming the precursor layer 31 is prepared, and the varnish is applied on the base separator so as to have a predetermined thickness to form a coating film, and then the coating film is dried. Thereby, the sheet
  • the solvent used in the varnish is not particularly limited, but an organic solvent or an alcohol solvent that can uniformly dissolve, knead, or disperse the above components is preferable.
  • the organic solvent include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like.
  • alcohol solvent examples include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2- Examples include butene-1,4-diol, 1,2,6-hexanetriol, glycerin, octanediol, 2-methyl-2,4-pentanediol, and terpineol.
  • the application method is not particularly limited.
  • the solvent coating method include a die coater, a gravure coater, a roll coater, a reverse coater, a comma coater, a pipe doctor coater, and screen printing.
  • a die coater is preferable in terms of high uniformity of coating thickness.
  • the drying conditions for the coating film are not particularly limited, and for example, the drying can be performed at a drying temperature of 70 to 160 ° C. and a drying time of 1 to 5 minutes. Even after the coating film is dried, depending on the type of solvent, the entire solvent may remain in the coating film without being vaporized.
  • the precursor layer 31 contains the low boiling point binder
  • a part of the low boiling point binder may volatilize depending on the drying conditions. Therefore, the ratio of each component constituting the precursor layer 31 changes according to the drying conditions. For example, even in the precursor layer 31 formed from the same varnish, the higher the drying temperature and the longer the drying time, the content of the metal fine particles in the entire precursor layer 31 and the content of the thermally decomposable binder Will be more. Therefore, it is preferable to set the drying conditions so that the content of the metal fine particles and the thermally decomposable binder in the precursor layer 31 is a desired amount.
  • polyethylene terephthalate (PET) polyethylene
  • polypropylene polypropylene
  • a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate release agent
  • a method for producing the heat-bonding sheets 3 and 3 ′ for example, a method for producing the heat-bonding sheets 3 and 3 ′ by mixing the respective components with a mixer and press-molding the obtained mixture is also suitable. It is. A planetary mixer etc. are mentioned as a mixer.
  • the dicing tape 11 is configured by laminating an adhesive layer 2 on a substrate 1.
  • the base material 1 is a strength base of the heat bonding sheets 10 and 12 with a dicing tape, and preferably has ultraviolet transparency.
  • the substrate 1 include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, polymethylpentene, and the like.
  • Polyolefin ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, ethylene -Hexene copolymer, Polyester such as polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyetherimide, polyamide, wholly aromatic polyamide, polyphenyls Fuido, aramid (paper), glass, glass cloth, fluorine resin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, metal (foil), paper, and the like.
  • Polyester such as polyurethane, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyetheretherketone, polyetherimide, polyamide, wholly aromatic polyamide,
  • examples of the material of the substrate 1 include polymers such as a crosslinked body of the resin.
  • the plastic film may be used unstretched or may be uniaxially or biaxially stretched as necessary.
  • the adhesive area between the pressure-sensitive adhesive layer 2 and the heat bonding sheets 3 and 3 ′ is reduced by thermally shrinking the base material 1 after dicing, The collection of the semiconductor chip can be facilitated.
  • the surface of the substrate 1 is chemically treated by conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. in order to improve adhesion and retention with adjacent layers.
  • a physical treatment or a coating treatment with a primer for example, an adhesive substance described later can be performed.
  • the thickness of the substrate 1 is not particularly limited and can be appropriately determined, but is generally about 5 to 200 ⁇ m.
  • the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer 2 is not particularly limited, and for example, a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive can be used.
  • a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive
  • an acrylic pressure-sensitive adhesive having an acrylic polymer as a base polymer from the viewpoint of cleanability with an organic solvent such as ultrapure water or alcohol of an electronic component that is difficult to contaminate a semiconductor wafer or glass Is preferred.
  • acrylic polymer examples include (meth) acrylic acid alkyl esters (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Isopentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester , Octadecyl esters, eicosyl esters, etc., alkyl groups having 1 to 30 carbon atoms, especially 4 to 18 carbon atoms, such as
  • the acrylic polymer contains units corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester or cycloalkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance and the like. You may go out.
  • Such monomer components include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride Acid anhydride monomers such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate Hydroxyl group-containing monomers such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; Styrene Contains sulfonic acid groups such as phonic acid, allyl sulf
  • a polyfunctional monomer or the like can be included as a monomer component for copolymerization as necessary.
  • examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) An acrylate etc. are mentioned. These polyfunctional monomers can also be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably
  • the acrylic polymer can be obtained by subjecting a single monomer or a mixture of two or more monomers to polymerization.
  • the polymerization can be performed by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like.
  • the content of the low molecular weight substance is preferably small.
  • the number average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably about 200,000 to 3,000,000, and particularly preferably about 300,000 to 1,000,000.
  • an external cross-linking agent can be appropriately employed for the pressure-sensitive adhesive in order to increase the number average molecular weight of an acrylic polymer as a base polymer.
  • the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, a melamine crosslinking agent, and reacting them.
  • a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, a melamine crosslinking agent, and reacting them.
  • the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked, and further depending on the intended use as an adhesive. In general, it is preferable to add about 5 parts by weight or less, and further 0.1 to 5 parts by weight with respect to 100 parts by weight of the base polymer.
  • additives such as conventionally well-known various tackifiers and anti-aging agent, other than the said component as needed to an adhesive.
  • the pressure-sensitive adhesive layer 2 can be formed of a radiation curable pressure-sensitive adhesive.
  • the radiation curable pressure-sensitive adhesive can increase the degree of cross-linking by irradiation with radiation such as ultraviolet rays, and can easily reduce its adhesive strength, and a portion 2a corresponding to the work pasting portion of the pressure-sensitive adhesive layer 2 shown in FIG.
  • the difference in adhesive strength with the other part 2b can be provided by irradiating only with radiation.
  • the portion 2 a having a significantly reduced adhesive force can be easily formed. Since the heat bonding sheet 3 ′ is attached to the portion 2 a that has been cured and has reduced adhesive strength, the interface between the portion 2 a of the pressure-sensitive adhesive layer 2 and the heat bonding sheet 3 ′ is easily peeled off during pick-up. Have. On the other hand, the portion not irradiated with radiation has a sufficient adhesive force, and forms the portion 2b. In addition, you may perform irradiation of the radiation to an adhesive layer after dicing and before pick-up.
  • the portion 2b formed of the uncured radiation-curing pressure-sensitive adhesive adheres to the heat bonding sheet 3, and dicing is performed. It is possible to secure a holding force when performing. In this way, the radiation curable pressure-sensitive adhesive can support the heat bonding sheet 3 for fixing a chip-like work (semiconductor chip or the like) to an adherend such as a substrate with a good balance of adhesion and peeling.
  • the portion 2b can fix the wafer ring.
  • the radiation curable pressure-sensitive adhesive those having a radiation curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation.
  • the radiation curable pressure sensitive adhesive for example, an addition type radiation curable pressure sensitive adhesive in which a radiation curable monomer component or an oligomer component is blended with a general pressure sensitive pressure sensitive adhesive such as an acrylic pressure sensitive adhesive or a rubber pressure sensitive adhesive. An agent can be illustrated.
  • Examples of the radiation curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol.
  • Examples include stall tetra (meth) acrylate, dipentaerystol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4-butanediol di (meth) acrylate.
  • the radiation curable oligomer component examples include urethane, polyether, polyester, polycarbonate, and polybutadiene oligomers, and those having a molecular weight in the range of about 100 to 30000 are suitable.
  • the compounding amount of the radiation-curable monomer component or oligomer component can be appropriately determined in accordance with the type of the pressure-sensitive adhesive layer, and the amount capable of reducing the adhesive strength of the pressure-sensitive adhesive layer. In general, the amount is, for example, about 5 to 500 parts by weight, preferably about 40 to 150 parts by weight with respect to 100 parts by weight of the base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.
  • the radiation-curable pressure-sensitive adhesive has a carbon-carbon double bond in the polymer side chain, main chain, or main chain terminal as a base polymer.
  • Intrinsic radiation curable pressure sensitive adhesives using Intrinsic radiation curable pressure-sensitive adhesive does not need to contain an oligomer component, which is a low-molecular component, or does not contain much, so that the oligomer component or the like does not move in the pressure-sensitive adhesive over time and is stable. Since the adhesive layer of a layer structure can be formed, it is preferable.
  • the base polymer having a carbon-carbon double bond those having a carbon-carbon double bond and having adhesiveness can be used without particular limitation.
  • those having an acrylic polymer as a basic skeleton are preferable.
  • the basic skeleton of the acrylic polymer include the acrylic polymers exemplified above.
  • the method for introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted. However, it is easy in terms of molecular design to introduce the carbon-carbon double bond into the polymer side chain. It is. For example, after a monomer having a functional group is copolymerized in advance with an acrylic polymer, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is converted into a radiation-curable carbon-carbon double bond. A method of performing condensation or addition reaction while maintaining the above.
  • combinations of these functional groups include carboxylic acid groups and epoxy groups, carboxylic acid groups and aziridyl groups, hydroxyl groups and isocyanate groups, and the like.
  • a combination of a hydroxyl group and an isocyanate group is preferable because of easy tracking of the reaction.
  • the functional group may be on either side of the acrylic polymer and the compound as long as the combination of these functional groups generates an acrylic polymer having the carbon-carbon double bond.
  • it is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group.
  • examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, and the like.
  • the acrylic polymer a copolymer obtained by copolymerizing the above-mentioned exemplified hydroxy group-containing monomers, ether compounds of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like is used.
  • the base polymer (particularly acrylic polymer) having the carbon-carbon double bond can be used alone, but the radiation curable monomer does not deteriorate the characteristics.
  • Components and oligomer components can also be blended.
  • the radiation-curable oligomer component or the like is usually in the range of 30 parts by weight, preferably in the range of 0 to 10 parts by weight, with respect to 100 parts by weight of the base polymer.
  • the radiation curable pressure-sensitive adhesive contains a photopolymerization initiator when cured by ultraviolet rays or the like.
  • the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxypropio ⁇ -ketol compounds such as phenone and 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- ( Acetophenone compounds such as methylthio) -phenyl] -2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketal compounds such as benzyldimethyl ketal; 2-naphthalene
  • the radiation curable pressure-sensitive adhesive examples include photopolymerizable compounds such as an addition polymerizable compound having two or more unsaturated bonds and an alkoxysilane having an epoxy group disclosed in JP-A-60-196956. And a rubber-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive containing a photopolymerization initiator such as a carbonyl compound, an organic sulfur compound, a peroxide, an amine, and an onium salt-based compound.
  • photopolymerizable compounds such as an addition polymerizable compound having two or more unsaturated bonds and an alkoxysilane having an epoxy group disclosed in JP-A-60-196956.
  • a rubber-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive containing a photopolymerization initiator such as a carbonyl compound, an organic sulfur compound, a peroxide, an amine, and an onium salt-based compound.
  • a compound that is colored by irradiation with radiation may be contained as necessary.
  • a compound to be colored in the pressure-sensitive adhesive layer 2 by irradiation with radiation only the irradiated portion can be colored. That is, the portion 2a corresponding to the workpiece pasting portion 3a shown in FIG. 1 can be colored. Accordingly, whether or not the pressure-sensitive adhesive layer 2 has been irradiated with radiation can be immediately determined by visual observation, the workpiece pasting portion 3a can be easily recognized, and workpieces can be easily pasted together.
  • the detection accuracy is increased, and no malfunction occurs when the semiconductor chip is picked up.
  • the compound that is colored by irradiation with radiation is a colorless or light color compound before irradiation with radiation, but becomes a color by irradiation with radiation, and examples thereof include leuco dyes.
  • the use ratio of the compound colored by radiation irradiation can be set as appropriate.
  • the thickness of the pressure-sensitive adhesive layer 2 is not particularly limited, but is preferably about 1 to 50 ⁇ m from the viewpoint of preventing chipping of the chip cut surface and compatibility of fixing and holding the heat bonding sheets 3 and 3 ′.
  • the thickness is preferably 2 to 30 ⁇ m, more preferably 5 to 25 ⁇ m.
  • the dicing tape 11 is manufactured as follows, for example.
  • the base material 1 can be formed by a conventionally known film forming method.
  • the film forming method include a calendar film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry lamination method.
  • the coating film is dried under predetermined conditions (heat-crosslinked as necessary), and the pressure-sensitive adhesive layer 2 is formed.
  • a coating method For example, roll coating, screen coating, gravure coating, etc. are mentioned.
  • drying conditions for example, a drying temperature of 80 to 150 ° C. and a drying time of 0.5 to 5 minutes are performed.
  • the coating film may be dried on the said drying conditions, and the adhesive layer 2 may be formed. Then, the adhesive layer 2 is bonded together with the separator on the base material 1. Thereby, the dicing tape 11 is produced.
  • the heat bonding sheets 10 and 12 with a dicing tape can be manufactured by a usual method.
  • seat 10 for heat joining with a dicing tape can be manufactured by bonding the adhesive layer 2 of the dicing tape 11 and the sheet
  • the heat bonding sheet 10 with dicing tape the heat bonding sheet 3 is preferably covered with a separator.
  • the base separator laminated on the heat bonding sheet 3 is peeled off, and the front base separator is peeled off, followed by heat joining with the dicing tape.
  • the method of sticking a separator on the exposed surface of the heat bonding sheet 3 of the sheet 10 for use is mentioned. That is, it is preferable that the dicing tape 11, the heat bonding sheet 3, and the separator are stacked in this order.
  • the heat bonding sheet with dicing tape in which the dicing tape and the heat bonding sheet are laminated has been described.
  • the heat bonding sheet of the present invention may be provided in a state where it is not bonded to a dicing tape.
  • the heat bonding sheet is preferably a heat bonding sheet with a double-sided separator sandwiched between two separators. That is, it is preferable to use a heat bonding sheet with a double-sided separator in which the first separator, the heat bonding sheet, and the second separator are laminated in this order.
  • FIG. 4 is a schematic cross-sectional view showing an embodiment of a heat-bonding sheet with a double-sided separator.
  • the heat bonding sheet 30 with a double-sided separator shown in FIG. 4 has a configuration in which a first separator 32, a heat bonding sheet 3, and a second separator 34 are laminated in this order.
  • the 1st separator 32 and the 2nd separator 34 the same thing as the above-mentioned substrate separator can be used.
  • seat for heat joining may be the form on which the separator was laminated
  • the method of manufacturing a semiconductor device includes the step of preparing the heat bonding sheet; A heat bonding step of heat bonding the semiconductor chip onto the adherend via the heat bonding sheet (hereinafter also referred to as a first manufacturing method).
  • the method for manufacturing a semiconductor device includes the step of preparing the heat bonding sheet with dicing tape described above, A bonding step of bonding the heat bonding sheet of the heat bonding sheet with the dicing tape and the back surface of the semiconductor wafer; A dicing step of dicing the semiconductor wafer together with the heat bonding sheet to form a chip-like semiconductor chip; Picking up the semiconductor chip together with the heat bonding sheet from the heat bonding sheet with the dicing tape; A heat bonding step of heat bonding the semiconductor chip onto the adherend via the heat bonding sheet (hereinafter also referred to as a second manufacturing method).
  • the manufacturing method of the semiconductor device according to the first manufacturing method is the same as the manufacturing method of the semiconductor device according to the second manufacturing method, while the heating bonding sheet with dicing tape is used. Then, it differs in the point which uses the sheet
  • the manufacturing method of the semiconductor device according to the first manufacturing method after preparing the heat-bonding sheet, the step of bonding the sheet to the dicing tape is performed, and thereafter the same as the manufacturing method of the semiconductor device according to the second manufacturing method. can do. Therefore, hereinafter, a method for manufacturing a semiconductor device according to the second manufacturing method will be described.
  • the heat bonding sheets with dicing tape 10 and 12 are prepared (preparing step).
  • the dicing tape-attached heat bonding sheets 10 and 12 are used in the following manner by appropriately separating the separator arbitrarily provided on the heat bonding sheets 3 and 3 ′.
  • a case where the heat bonding sheet with dicing tape 10 is used will be described as an example with reference to FIG.
  • the semiconductor wafer 4 is pressure-bonded onto the semiconductor wafer bonding portion 3a of the heat bonding sheet 3 in the heat bonding sheet 10 with dicing tape, and this is bonded and held (fixing step). This step is performed while pressing with a pressing means such as a pressure roll.
  • the attaching temperature at the time of mounting is not particularly limited, and is preferably in the range of 23 ° C. to 90 ° C., for example.
  • the semiconductor wafer 4 is preferably one in which an electrode pad is formed on one surface and a gold thin film, a silver thin film, or a copper thin film is formed on the outermost surface of the other surface (hereinafter also referred to as the back surface). Moreover, it is preferable to form a thin film containing the same kind of metal as the sinterable metal fine particles contained in the precursor layer 31 on the outermost surface of the back surface of the semiconductor wafer 4. Examples of the thickness of the silver thin film include 10 nm to 1000 nm. Further, a titanium thin film may be further formed between the semiconductor wafer 4 and the silver thin film. Examples of the thickness of the titanium thin film include 10 nm to 1000 nm.
  • the semiconductor chip 5 and the heat bonding sheet 3 can be strongly heat bonded in the heat bonding step described later. Further, when the titanium thin film is formed, the reliability of the electrode is improved.
  • the silver thin film and the titanium thin film can be formed by vapor deposition, for example.
  • the semiconductor wafer 4 is diced (dicing process). Thereby, the semiconductor wafer 4 is cut into a predetermined size and separated into individual pieces, and the semiconductor chip 5 is manufactured.
  • the method of dicing is not particularly limited, for example, the dicing is performed from the circuit surface side of the semiconductor wafer 4 according to a conventional method. Further, in this step, for example, a cutting method called full cut in which cutting is performed up to the heat bonding sheet with dicing tape 10 can be adopted. It does not specifically limit as a dicing apparatus used at this process, A conventionally well-known thing can be used. Further, since the semiconductor wafer 4 is bonded and fixed by the heat bonding sheet 10 with a dicing tape, chip chipping and chip jumping can be suppressed, and damage to the semiconductor wafer 4 can also be suppressed.
  • the semiconductor chip 5 is picked up in order to peel the semiconductor chip 5 adhered and fixed to the heat bonding sheet 10 with dicing tape (pickup process).
  • the pickup method is not particularly limited, and various conventionally known methods can be employed. For example, there is a method in which each semiconductor chip 5 is pushed up by a needle from the heating bonding sheet 10 with dicing tape, and the pushed-up semiconductor chip 5 is picked up by a pickup device.
  • the needle push-up speed is preferably 0.5 to 100 mm / sec, more preferably 5 to 10 mm / sec in terms of preventing chipping.
  • the pickup is performed after the pressure-sensitive adhesive layer 2 is irradiated with ultraviolet rays.
  • seat 3 for heat bonding of the adhesive layer 2 falls, and peeling of the semiconductor chip 5 becomes easy.
  • the pickup can be performed without damaging the semiconductor chip 5.
  • Conditions such as irradiation intensity and irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be set as necessary.
  • a well-known thing can be used as a light source used for ultraviolet irradiation.
  • the adhesive layer is preliminarily irradiated with ultraviolet rays and cured, and the cured adhesive layer and the heat bonding sheet are bonded together, the ultraviolet irradiation here is not necessary.
  • the picked-up semiconductor chip 5 is die-attached (heat bonded) to the adherend 6 via the heat bonding sheet 3 (heat bonding process).
  • the adherend 6 include a lead frame, a TAB film, a substrate, and a separately manufactured semiconductor chip.
  • the adherend 6 may be, for example, a deformable adherend that can be easily deformed or a non-deformable adherend (such as a semiconductor wafer) that is difficult to deform.
  • the lead frame examples include metal lead frames such as a Cu lead frame and a 42 Alloy lead frame.
  • a conventionally well-known thing can be used as said board
  • examples thereof include organic substrates made of glass epoxy, BT (bismaleimide-triazine), polyimide, and the like.
  • BT bismaleimide-triazine
  • polyimide polyimide
  • the substrate may be an insulating circuit substrate in which a copper circuit substrate is laminated on an insulating substrate such as a ceramic plate. If an insulated circuit board is used, for example, a power semiconductor device that controls and supplies power can be manufactured.
  • the surface of the adherend contains gold, silver, or copper.
  • the surface of the adherend preferably contains the same type of metal as the sinterable metal fine particles contained in the precursor layer 31.
  • the affinity with the heat bonding sheet or the bonding wire is increased, and the bonding reliability with them can be further improved. From the viewpoint of improving durability and weather resistance, gold or silver is preferred, and copper is preferred for cost reduction.
  • the metal fine particles are sintered by heating, and the thermally decomposable binder is thermally decomposed as necessary. Further, the residual low boiling point binder that has not been volatilized by the drying step is volatilized.
  • the heating temperature is preferably 180 to 400 ° C, more preferably 190 to 370 ° C, and further preferably 200 to 350 ° C.
  • the heating time is preferably 0.3 to 300 minutes, more preferably 0.5 to 240 minutes, and still more preferably 1 to 180 minutes.
  • the pressurizing condition is preferably in the range of 1 to 500 kg / cm 2 , more preferably in the range of 5 to 400 kg / cm 2 .
  • the heat bonding under pressure can be performed with an apparatus capable of simultaneously performing heating and pressure, such as a flip chip bonder. Moreover, a parallel plate press may be used.
  • the tip of the terminal portion (inner lead) of the adherend 6 and an electrode pad (not shown) on the semiconductor chip 5 are electrically connected by a bonding wire 7.
  • a bonding wire 7 for example, a gold wire, an aluminum wire, a copper wire or the like is used.
  • the temperature for wire bonding is 23 to 300 ° C., preferably 23 to 250 ° C.
  • the heating time is several seconds to several minutes.
  • the connection is performed by a combination of vibration energy by ultrasonic waves and crimping energy by applying pressure while being heated so as to be within the temperature range.
  • the semiconductor chip 5 is sealed with a sealing resin 8 as shown in FIG. 5 (sealing step).
  • This step is performed to protect the semiconductor chip 5 and the bonding wire 7 mounted on the adherend 6.
  • This step can be performed by molding a sealing resin with a mold.
  • the sealing resin 8 for example, an epoxy resin is used.
  • the heating temperature at the time of resin sealing is usually 175 ° C. for 60 to 90 seconds, but the present invention is not limited to this. For example, it can be cured at 165 to 185 ° C. for several minutes. Thereby, the sealing resin 8 is cured.
  • a method of embedding the semiconductor chip 5 in a sheet-like sealing sheet (for example, see JP2013-7028A) can also be employed.
  • a gel sealing type in which silicone gel is poured into a case type container may be used.
  • heating is performed as necessary to completely cure the insufficiently cured sealing resin 8 in the sealing process (post-curing process).
  • the heating temperature in this step varies depending on the type of the sealing resin, but is in the range of 165 to 185 ° C., for example, and the heating time is about 0.5 to 8 hours.
  • seat for heat joining with a dicing tape can be used suitably also when laminating
  • the heat bonding sheet and the spacer may be stacked between the semiconductor chips, or only the heat bonding sheet may be stacked between the semiconductor chips without stacking the spacer. It can be changed as appropriate.
  • the heat bonding sheet and the heat bonding sheet with dicing tape of the present invention are not limited to the applications exemplified above, and can be used for heat bonding two things.
  • Sinterable metal particle-containing paste 6 parts by weight of isobornylcyclohexanol (MTPH, molecular weight 236), which is a low boiling point binder, per 100 parts by weight of copper powder (Mitsui Metal Mining Co., Ltd., average particle size 0.2 ⁇ m) Parts, 5 parts by weight of methyl ethyl ketone (MEK) added and stirred (each component was put into a rotation / revolution mixer (ARE-310, manufactured by Shinky Corporation) and stirred for 15 minutes at 2000 rpm).
  • MTPH isobornylcyclohexanol
  • MEK methyl ethyl ketone
  • Thermally decomposable binder A PPC (polypropylene carbonate resin), manufactured by Empower, "QPAC40", weight average molecular weight 289,000
  • Thermally decomposable binder B PiBMA (polyisobutyl methacrylate resin), manufactured by Fujikura Kasei Co., Ltd., “MM2002”, weight average molecular weight 170,000
  • Organic solvent Methyl ethyl ketone (MEK)
  • Examples 1 to 3 and Comparative Example 1 100 parts by weight of a paste containing sinterable metal particles, 7 parts by weight of a thermally decomposable binder shown in Table 1, and 45 parts by weight of an organic solvent are put into a rotating / revolving mixer (ARE-310, manufactured by Sinky) and stirred at 2000 rpm for 8 minutes. And varnish was produced. The obtained varnish was applied and dried on a release treatment film (“MRA38” manufactured by Mitsubishi Resin Co., Ltd.). The application was performed using an applicator so that the thickness of the dried coating film was 70 ⁇ m. Drying was performed with an explosion-proof dryer. The drying conditions were 80 ° C. and 2 minutes. As a result, a heat bonding sheet having a thickness of 70 ⁇ m was obtained.
  • ARE-310 rotating / revolving mixer
  • Example 6 the SEM surface observation image obtained about the sheet
  • FIG. 6 shows an observation visual field at one of them.
  • imageJ an open source software developed at the National Institutes of Health, USA
  • a circle is drawn about the area occupied by each phase.
  • the bright phase and the dark phase of the SEM surface observation image are binarized to display black and white, and the boundary between the white portion and the black portion is defined for each phase that defines phase separation.
  • a boundary line was used.
  • the binarization of the bright part and the dark part was performed as follows. If the histogram displayed in the “B & C” window appears by selecting the commands in the menu bar of the image analysis software in the order of “Image”, “Adjust”, and “Brightness / Contrast”, it is the first. The lowest frequency between the most frequent peak and the second most frequent peak was used as the boundary, and less than that was binarized with black and more than that with white.
  • the SEM central part observation image of the central part in the thickness direction of the sheet was obtained by the following procedure.
  • a heat-bonding sheet is cut out along a plane perpendicular to the longitudinal direction of the sheet passing through the center of the sheet surface, and cryoion polish polishing (using Leica TIC-3X. Acceleration voltage: 6 kV, processing temperature: ⁇ 20) ° C). It was obtained by taking an SEM observation image of the central portion of the obtained polished surface.
  • the imaging conditions at the center in the thickness direction were an acceleration voltage of 2 kV and a magnification of 2000 times.
  • Vm is the molecular weight of the target compound (when the target compound is a polymer, the molecular weight of the main monomer) and the density of the target compound (when the target compound is a polymer, the main weight is obtained by multiplying ⁇ ′ by 0.8).
  • the main monomer is a monomer having the highest molar ratio in the target polymer component, and the monomer constituting the polymer component is extracted from the sheet by solvent extraction or the like. (The organic component is extracted, and after GPC fractionation, the polymer component can be identified by determining its structure by nuclear magnetic resonance (NMR).)
  • a silicon chip (silicon chip thickness 350 ⁇ m, length 5 mm, width 5 mm) having a Ti layer (thickness 50 nm) and an Ag layer (thickness 100 nm) formed in this order on the back surface was prepared.
  • the prepared heat bonding sheet was stacked on the Ag layer surface of the prepared silicon chip. In this state, I passed the laminator.
  • the laminator conditions were a temperature of 70 ° C., a pressure of 0.3 MPa, and a speed of 10 mm / second.
  • a copper plate (copper plate thickness 3 mm) whose entire surface was covered with an Ag layer (thickness 5 ⁇ m) was prepared.
  • a heat bonding sheet with a silicon chip (prepared above) was temporarily bonded onto the prepared copper plate.
  • the pressure at the time of temporary adhesion was 0.1 MPa.
  • the copper plate was preheated to 70 ° C. during the temporary bonding. This was used for evaluation of Example 1 and Comparative Example 1.
  • a copper plate (copper plate thickness 3 mm) whose entire surface was covered with an Au layer (thickness 0.1 ⁇ m) was prepared.
  • a heat bonding sheet with a silicon chip (prepared above) was temporarily bonded onto the prepared copper plate.
  • the pressure at the time of temporary adhesion was 0.1 MPa.
  • the copper plate was preheated to 70 ° C. during the temporary bonding. This was used for the evaluation of Example 2.
  • Example 3 a copper plate (thickness of copper plate: 3 mm) with no surface coating was prepared.
  • a heat bonding sheet with a silicon chip (prepared above) was temporarily bonded onto the prepared copper plate.
  • the pressure at the time of temporary adhesion was 0.1 MPa.
  • the copper plate was preheated to 70 ° C. during the temporary bonding. This was used for the evaluation of Example 3.
  • the heat bonding sheet temporarily bonded as described above was sintered under pressure and heating conditions to bond the silicon chip and the copper plate (pressure 10 MPa, temperature increase rate 90 ° C./min, sintering temperature). 300 ° C., sintering time 5 minutes).
  • a sintering apparatus HTM-3000, manufactured by Hakutosha
  • the pressurization was performed by a flat plate press, and the pressurization was always maintained during the temperature raising process and the sintering process.
  • the atmosphere at the time of temperature rising and sintering was a nitrogen atmosphere.
  • the sample for evaluation was put into a thermal shock tester (Espec Corp., “TSE-103ES”) and subjected to 100 thermal shocks of ⁇ 40 ° C. to 200 ° C. At this time, the temperature was kept at ⁇ 40 ° C. and 200 ° C. for 15 minutes, respectively.
  • TSE-103ES thermal shock tester
  • the area (remaining bonding area) where the bonding remains in the obtained image is obtained, and the ratio of the remaining bonding area to the entire area (remaining bonding area ratio) was calculated.
  • the image obtained by the ultrasonic imaging apparatus the part where the silicon chip and the copper plate are peeled is displayed in white, and the part where the bonding remains is displayed in black (the threshold is 127. 0 to 255 floors).
  • the binarization was performed with 0 to 127 among the 256 divided tones as black portions and 128 to 255 as white portions.
  • the case where the remaining bonding area ratio was 70% or more was evaluated as “ ⁇ ”, and the case where the remaining bonding area ratio was lower than 70% was evaluated as “X”.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dicing (AREA)
  • Die Bonding (AREA)

Abstract

L'invention porte sur une feuille pour liaison thermique qui peut fournir une fiabilité de liaison suffisante pour un dispositif à semi-conducteur de puissance en supprimant l'inhibition du frittage de particules métalliques frittables par un composant organique, et une feuille de liaison thermique avec une bande de découpage en dés qui comprend ladite feuille pour une liaison thermique. La feuille pour liaison thermique comporte une couche précurseur qui devient une couche frittée par chauffage, la couche de précurseur contenant des particules métalliques frittables et un composant organique, la couche précurseur est une structure à phases séparées qui est une structure mer-île ou une structure co-continue, et, dans une image de microscopie de surface SEM d'au moins une surface de la couche de précurseur, la plus grande valeur des diamètres des cercles inscrits maximaux dans les régions occupées par chaque phase de la structure à phases séparées est de 1-50 µm.
PCT/JP2017/019187 2016-06-24 2017-05-23 Feuille de liaison thermique, et feuille de liaison thermique doté de ruban de découpage en dés Ceased WO2017221613A1 (fr)

Priority Applications (3)

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EP17815082.7A EP3477688A4 (fr) 2016-06-24 2017-05-23 Feuille de liaison thermique, et feuille de liaison thermique doté de ruban de découpage en dés
CN201780038817.XA CN109462991A (zh) 2016-06-24 2017-05-23 加热接合用片及带有切割带的加热接合用片
US16/308,931 US11817415B2 (en) 2016-06-24 2017-05-23 Thermal bonding sheet and thermal bonding sheet with dicing tape

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JP2016-125317 2016-06-24
JP2016125317 2016-06-24
JP2017-046481 2017-03-10
JP2017046481A JP6864505B2 (ja) 2016-06-24 2017-03-10 加熱接合用シート及びダイシングテープ付き加熱接合用シート

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Publication number Priority date Publication date Assignee Title
WO2020202971A1 (fr) * 2019-03-29 2020-10-08 三井金属鉱業株式会社 Matériau de liaison, et structure de liaison

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JPS60196956A (ja) 1984-03-12 1985-10-05 Nitto Electric Ind Co Ltd 半導体ウエハ固定用接着薄板
JP2003249471A (ja) * 2002-02-22 2003-09-05 Nitto Denko Corp 半導体ウエハ加工用保護シート
JP2013007028A (ja) 2011-05-20 2013-01-10 Nitto Denko Corp 封止用シートおよび電子部品装置
JP2014111800A (ja) 2012-12-05 2014-06-19 Nippon Handa Kk ペースト状金属微粒子組成物、固形状金属または固形状金属合金の製造方法、金属製部材の接合方法、プリント配線板の製造方法および電気回路接続用バンプの製造方法
WO2016031551A1 (fr) * 2014-08-29 2016-03-03 古河電気工業株式会社 Film adhésif conducteur

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* Cited by examiner, † Cited by third party
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JPS60196956A (ja) 1984-03-12 1985-10-05 Nitto Electric Ind Co Ltd 半導体ウエハ固定用接着薄板
JP2003249471A (ja) * 2002-02-22 2003-09-05 Nitto Denko Corp 半導体ウエハ加工用保護シート
JP2013007028A (ja) 2011-05-20 2013-01-10 Nitto Denko Corp 封止用シートおよび電子部品装置
JP2014111800A (ja) 2012-12-05 2014-06-19 Nippon Handa Kk ペースト状金属微粒子組成物、固形状金属または固形状金属合金の製造方法、金属製部材の接合方法、プリント配線板の製造方法および電気回路接続用バンプの製造方法
WO2016031551A1 (fr) * 2014-08-29 2016-03-03 古河電気工業株式会社 Film adhésif conducteur

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Title
J. APPL. POLYM. SCI., vol. 19, 1975, pages 1163
See also references of EP3477688A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020202971A1 (fr) * 2019-03-29 2020-10-08 三井金属鉱業株式会社 Matériau de liaison, et structure de liaison
US12070801B2 (en) 2019-03-29 2024-08-27 Mitsui Mining & Smelting Co., Ltd. Bonding material and bonded structure

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