Method for flip-chip bonding using anisotropic adhesive polymer
11240918 · 2022-02-01
Assignee
Inventors
Cpc classification
H01L2924/00014
ELECTRICITY
H05K3/323
ELECTRICITY
H05K2203/0278
ELECTRICITY
C09J2203/326
CHEMISTRY; METALLURGY
H01L2224/83192
ELECTRICITY
H01L2924/00014
ELECTRICITY
H05K2201/023
ELECTRICITY
H01L2224/32225
ELECTRICITY
H05K1/11
ELECTRICITY
H01L2224/2929
ELECTRICITY
H01L2224/2929
ELECTRICITY
C09J201/00
CHEMISTRY; METALLURGY
C09J5/00
CHEMISTRY; METALLURGY
International classification
H05K1/11
ELECTRICITY
H05K3/32
ELECTRICITY
Abstract
The present invention discloses flip-chip bonding method using an anisotropic adhesive polymer. The method includes applying an adhesive polymer solution containing metal particles dispersed therein onto a circuit substrate to form an adhesive polymer layer such that the adhesive polymer layer covers the metal particles; drying the adhesive polymer layer; and positioning an electronic element to be electrically connected to the circuit substrate on the dried adhesive polymer layer and causing dewetting of the polymer from the metal particles.
Claims
1. A structure for flip-chip bonding, comprising: a circuit substrate; an anisotropic adhesive polymer layer disposed on the circuit substrate, the anisotropic adhesive polymer layer having an interface location; and a metal particle entirely covered by the anisotropic adhesive polymer layer to thereby form an air-adhesive-metal location at the interface location with a thickness of the anisotropic adhesive polymer layer covering the metal particle between the metal particle and air, wherein, at the interface location, the anisotropic adhesive polymer layer has an effective interfacial potential in a metastable state, such that the anisotropic adhesive polymer layer is spinodally dewetted from the metal particle upon reduction of the thickness of the anisotropic polymer layer covering the metal particle, wherein the anisotropic adhesive polymer layer is coated to have a thickness of 100 nm to 500 nm, and a diameter of the metal particle is 50 nm to 300 nm, wherein a function of the effective interfacial potential is expressed as a following Equation 1:
2. The structure for flip-chip bonding of claim 1, wherein the anisotropic adhesive polymer layer is UV curable.
3. A structure for flip-chip bonding, comprising: a circuit substrate; a relief electrode partially formed on the circuit substrate; and an anisotropic adhesive polymer layer disposed on the circuit substrate and entirely covering the relief electrode with a thickness of the anisotropic adhesive polymer layer, wherein, in the locality of the relief electrode, the anisotropic adhesive polymer layer has an effective interfacial potential in a metastable state, such that the anisotropic adhesive polymer layer is spinodally dewetted from the relief electrode upon reduction the thickness of the anisotropic polymer layer covering the relief electrode, wherein the anisotropic adhesive polymer layer is coated to have a thickness of 100 nm to 500 nm, and a relief height of the relief electrode is 50 nm to 300 nm, wherein a function of the effective interfacial potential is expressed as a following Equation 1:
4. The structure for flip-chip bonding of claim 3, wherein the anisotropic adhesive polymer layer is UV curable.
5. A structure for flip-chip bonding, comprising: a circuit substrate having a surface; an anisotropic adhesive polymer layer disposed on the surface of the circuit substrate, the anisotropic adhesive polymer layer having a first interface location and a second interface location; and a metal conductor disposed on the surface of the circuit substrate and separated from air by a first thickness of the anisotropic adhesive polymer layer to thereby form an air-adhesive-metal location at the first interface location, wherein the surface of the circuit substrate is separated from air by a second thickness of the anisotropic adhesive polymer layer to thereby form an air-adhesive-substrate location at the second interface location, wherein, at the first interface location, the anisotropic adhesive polymer layer has an effective interfacial potential in a metastable state, such that the anisotropic adhesive polymer layer has a property to be dewetted from the metal conductor in response to a stimulus effective to reduce the first thickness of the anisotropic polymer layer covering the metal conductor and the second thickness of the anisotropic polymer layer covering the substrate, and wherein, at the second interface location, the anisotropic adhesive polymer layer has an effective interfacial potential in a metastable state or in a stable state, such that the anisotropic adhesive polymer layer has a property to remain spread on the surface of the circuit substrate in response to a stimulus effective to reduce the first thickness of the anisotropic polymer layer covering the metal conductor and the second thickness of the anisotropic polymer layer covering the substrate, wherein the anisotropic adhesive polymer layer is coated to have a thickness of 100 nm to 500 nm, and a thickness of the metal conductor is 50 nm to 300 nm, wherein a function of the effective interfacial potential is expressed as a following Equation 1:
6. A flip-chip structure, comprising: a circuit substrate having an adhesion region and an exposure region; an electronic element adhered to the circuit substrate in the adhesion region of the circuit substrate by an anisotropic adhesive polymer layer, at least a portion of the anisotropic adhesive polymer layer being in a metastable state; and a metal conductor disposed between the circuit substrate and the electronic element, the exposure region of the circuit substrate conforming to a shape of the metal conductor, the shape corresponding to a dewetting of the metastable state of the anisotropic adhesive polymer layer, wherein a surface of the metal conductor and a surface of the circuit substrate are exposed to air in the exposure region, and wherein the metal conductor directly contacts the electronic element, wherein the anisotropic adhesive polymer layer is coated to have a thickness of 100 nm to 500 nm, and a thickness of the metal conductor is 50 nm to 300 nm, wherein a function of the effective interfacial potential is expressed as a following Equation 1:
7. The flip-chip structure of claim 6, wherein the exposure region is at least partially surrounded by the adhesion region.
8. The structure for flip-chip bonding of claim 1, wherein, at the interface location, the anisotropic adhesive polymer layer is sensitive to an external pressurization force that is below or equal to 1N and that is effective to reduce the thickness of the anisotropic polymer layer covering the metal particle, such that the anisotropic adhesive polymer layer is spinodally dewetted from the metal particle upon application of the external pressurization force.
9. The structure for flip-chip bonding of claim 1, wherein, at the interface location, the anisotropic adhesive polymer layer is sensitive to heat treatment below or equal to 100° C., such that the anisotropic adhesive polymer layer is spinodally dewetted from the metal particle upon application of the heat treatment.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The accompanying drawings, which are incorporated in and form a part of this specification and in which like numerals depict like elements, illustrate embodiments of the present disclosure and, together with the description, serve to explain the principles of the disclosure.
(2)
(3)
(4)
(5)
(6)
(7)
DETAILED DESCRIPTIONS
(8) For simplicity and clarity of illustration, elements in the figures are not necessarily drawn to scale. The same reference numbers in different figures denote the same or similar elements, and as such perform similar functionality. Further, descriptions and details of well-known steps and elements are omitted for simplicity of the description. Furthermore, in the following detailed description of the present disclosure, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be understood that the present disclosure may be practiced without these specific details. In other instances, well-known methods, procedures, components, and circuits have not been described in detail so as not to unnecessarily obscure aspects of the present disclosure.
(9) Examples of various embodiments are illustrated and described further below. It will be understood that the description herein is not intended to limit the claims to the specific embodiments described. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the present disclosure as defined by the appended claims.
(10) The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular forms “a” and “an” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises”, “comprising”, “includes”, and “including” when used in this specification, specify the presence of the stated features, integers, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, operations, elements, components, and/or portions thereof. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expression such as “at least one of” when preceding a list of elements may modify the entire list of elements and may not modify the individual elements of the list.
(11) Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
(12)
(13)
(14) In order to form
(15) Further, in order to form
(16) In this connection, the polymer type and a thickness (h.sub.1) of the polymer layer on the metal particle and a thickness (h.sub.2) of the polymer layer on the substrate may be determined in consideration of van der Waals forces, surface tension, and contact angle between the polymer and the metal particle or the substrate such that the polymer has a metastable state of the effective interfacial potential at the metal particle location (the location of the air-adhesive polymer-metal particle in
(17) In this connection, the stable state of the effective interfacial potential means a state in which dewetting does not occur even with a change in the thickness of the polymer. The unstable state of the effective interfacial potential refers to the state where dewetting occurs spontaneously regardless of the thickness change. The metastable state of the effective interfacial potential refers to the state in which dewetting may occur due to a change in thickness.
(18) The three states of this effective interfacial potential may be represented using the graph in
(19)
(20) In the Equation 1, h represents a thickness of the polymer, c represents a short-range interaction strength between the polymer and the metal particle or the relief electrode. A represents an effective Hamaker constant of the metal particle or the relief electrode. Φ.sub.vd(h) refers to a function of van der Waals forces based on the thickness h.
(21) Based on the Equation 1, the effective interfacial potential at the metal particle position (h.sub.1) is given by a following Equation 1 of the h.sub.1, while the effective interfacial potential at the substrate position (h.sub.2) is given by a following Equation 3 of the h.sub.2.
(22)
(23) c in the Equation 1 may be obtained from a following Equation 2.
(24)
(25) In the Equation 2, θ represents a contact angle between the metal particle and the polymer. σ represents a surface tension of the polymer. h* denotes an equilibrium film thickness, which is a thickness of the polymer formed after the dewetting.
(26) All values except c can be obtained. The equilibrium film thickness (h*) may be measured using X-ray reflectivity. Finally, c may be obtained using the Equation 2.
(27) Using c obtained using the Equation 2, the effective interfacial potential function according to the thickness at the stable state, the unstable state, and the metastable state for the Equation 1 may be expressed as shown in
(28) In the metastable state, a value of the function of the effective interfacial potential may vary from a negative value to a positive value as the value of h increases and, then, a slope of the function of the effective interfacial potential is changed to a negative value. In the stable state, the function of the effective interfacial potential has a positive value when the h value increases.
(29) Referring to
(30) In addition, in the stable state represented by (1) in the graph of
(31) In the metastable state Φ(h)≈0, metastable) represented by (3) in the graph in
(32) In accordance with the present disclosure, the polymer at the location of the metal particle exhibits the metastable state defined in relation to the metal particle. For example, the polymer that exhibits the behavior shown in
(33) In accordance with the present disclosure, the polymer at the substrate location preferably exhibits the stable state defined in relation to the substrate or the metastable state above defined. That is, the polymer at the substrate location preferably exhibits the metastable state at a sufficiently large thickness greater than or equal to h.sub.b, for example, has a thickness change that may be achieved by an applicable external force during use.
(34) A minimum thickness of the dried adhesive polymer at the metal particle position may be a thickness at which the slope of the effective interfacial potential at the metal particle position is changed to a negative value. That is, in the graph (3) of
(35) As illustrated in
(36) That is, a thickness of the polymer at the metal particle location which is in the metastable state becomes smaller than the minimum thickness due to simple pressurization (hand pressing force or 1N or smaller) or warming (for example, temperature below 100° C.) after positioning of the electronic element on the polymer. Thus, the thickness of the polymer at the metal particle location becomes smaller such that the polymer is brought into the unstable state, thereby causing dewetting of the polymer.
(37) In one embodiment, the polymer may be coated to have a thickness of 100 nm to 500 nm. A diameter of the metal particle or a relief height of the relief electrode may be between 50 nm and 300 nm.
(38) In one embodiment, the polymer may be a curable polymer. Preferably, the polymer may be an ultraviolet curable polymer. The polymer may lose adhesion via curing. At this time, the electronic element contacts the metal particle or the relief electrode when the anisotropic adhesive polymer in accordance with the present disclosure is dewetted. When ultraviolet rays are irradiated, the ultraviolet rays are not transmitted to a region where the electronic element is disposed, the adhesive power remains in that region. The adhesive force of the polymer is lost by the ultraviolet rays in a region where the electronic element is not disposed.
(39) In one embodiment, the anisotropic adhesive polymer may be dewetted from the metal particle or relief electrode via heat treatment at a temperature below or equal to 100° C. and/or pressurization at a pressure below or equal to 1 N.
Example 1
(40) Actually, the adhesive polymer in the metastable state was not spontaneously dewetted in a prepared state. The dewetting occurs only through the pressurization, thereby to expose the metal nanoparticles (indium nanoparticles) and relief electrode (gold). This dewetting and the resulting exposure were checked as follows.
(41) As an anisotropic adhesive polymer in accordance with the present disclosure, bisphenol A based adhesive polymer solution was prepared. The adhesive polymer solution contains monomers in anhydrous ethanol solvent (Bisphenol A glycerolate diacrylate), crosslinking agent (MPS, 3-(trimethoxysilyl) propyl methacrylate), Spin-on-Glass (SOG), photo-initiator (benzyl-2-(dimethylamino)-4′-mopholinobutyrophenone).
(42) The surface tension of this polymer and the contact angle between this polymer and the indium and gold were determined as follows.
(43) TABLE-US-00001 TABLE 1 Contact angle Θ (degrees) Contact Contact Contact Ultrapure Cosine θ of angle angle angle water contact angle unit unit unit (DI Ethylene Ethylene (mJ * m.sup.−2) (mJ * m.sup.−2) (mJ * m.sup.−2) water) glycol DI water glycol γ.sub.s.sup.d γ.sub.s.sup.P γ.sub.s Example 75.675° 47.92° 0.247422 0.670168 24.4279778 9.254093238 33.68207103 Polymer Substrate 23.2° 31.4° 0.919135 0.853551 0.300481449 92.46907051 92.76955196 (glass) Gold 67.37° 54.13° 0.384779 0.585948 8.090467587 27.30580895 35.39627654 Indium 84° 67.6° 0.104528 0.381070 11.64668026 11.34120052 22.98788077
(44) Contact angles [Θ] between ultrapure water and ethylene glycol and the example polymer, glass, gold and indium were measured. The measurement is shown in Table 1.
γ.sub.S=γ.sub.SL+γ.sub.L cos θ (Equation 3)
γ.sub.i=γ.sub.i.sup.d+γ.sub.i.sup.p (Equation 4)
γ.sub.SL=γ.sub.S+γ.sub.L−2(γ.sub.x.sup.dγ.sub.L.sup.d).sup.1/2−2(γ.sub.S.sup.pγ.sub.L.sup.p).sup.1/2 (Equation 5)
γ.sub.L(1+cos θ)=2(γ.sub.s.sup.dγ.sub.L.sup.d).sup.1/2+2(γ.sub.S.sup.pγ.sub.L.sup.p).sup.1/2 (Equation 6)
(45) We may achieve the Equation (6) by combining the equations (3) to (5). In this case, a surface tension of a solid material may be obtained by measuring contact angles between the solid material and two liquids (ultra-pure water and ethyl glycol) whose surface tension are known relative to the solid material. Using this method, surface tensions of the polymer adhesive, indium and gold were obtained. The surface tensions thereof are listed in the Table 1.
(46) Similarly, the contact angle between indium-polymer or gold-polymer was determined using the surface tensions of polymer, indium and gold as follows:
(47) Indium-polymer contact angle: 29.8171°
(48) Gold-polymer contact angle: 38.862°
(49) The example polymer was applied to a glass substrate. The coating thickness of the polymer containing the indium particles dispersed therein was about 500 nm. The coating thickness of the polymer on the gold relief electrode was about 1 μm. The size of each of the indium particles was about 250 nm. The height of the relief electrode was about 400 nm. Therefore, the polymer thickness at the metal particle position is about 250 nm. The thickness of the polymer on the relief electrode was about 600 nm. In this case, the polymer was not spontaneously dewetted.
(50) We pressed the polymer using a finger lightly. Thus, it was confirmed that the polymer was dewetted at the indium particle position and the electrode relief position.
(51) The equilibrium film thickness (h*) of the dewetted polymer was measured. The equilibrium film thickness (h*) of the dewetted polymer at a position corresponding to indium was 4 nm. The equilibrium film thickness (h*) of the dewetted polymer at a position corresponding to gold was 5 nm. The effective Hamaker constant of indium is 3.0.sup.−19 J. The effective Hamaker constant for gold is 4.5.sup.−19 J.
(52) Using Equation 2 below, the value of c was obtained using the obtained contact angles. The c value for indium was 5.31.sup.−78 J and the c value for gold was 3.82.sup.−77 J.
(53)
(54) Using Equation 1 below, the effective interfacial potential of the polymer of Example 1 was obtained. The results are shown in
(55)
(56) In
(57) The preceding Example 1 and results thereof confirm that the polymer of Example 1 of the present disclosure exhibits the behavior of the metastable state of the effective interfacial potential. It was also found that in an initial thickness of the polymer, the effective interfacial potential has the stable state and then the dewetting of the polymer occurs due to the thickness change thereof resulting from small external force applied thereto.
(58) Although the present disclosure has been described with reference to the drawings illustrating the present disclosure, the present disclosure is not limited to the embodiments and drawings disclosed in the present specification. It will be apparent that various modifications may be made by those skilled in the art within the scope of the present disclosure. In addition, it should be appreciated that effects to be achieved from configurations of the present disclosure as not expressly mentioned may be acknowledged.