Patent Application
20090197090
This application claims priority under 35 U.S.C. §119 to Korean Patent Application No. 2008-10651, filed on Feb. 1, 2008, the entire contents of which are hereby incorporated by reference.
1. Field
Example embodiments are directed to a composition, an anti-oxide film and electronic component including the same, and methods of forming an anti-oxide film and an electronic component. Other example embodiments are directed to a composition, which may include a fluorine-based polymer or a perfluoropolyether (PFPE) derivative and a PFPE-miscible polymer, an anti-oxide film and electronic component including the same, and methods of forming an anti-oxide film and an electronic component.
2. Description of the Related Art
Aluminum (Al) may be used as a material for wiring pads employed in memory and processing microdevices, but the intrinsic nature of aluminum allows for relatively low conductivity and relatively high processing costs, as compared to other metal materials. Copper (Cu) may exhibit improved electrical properties compared with other metal materials and may be relatively inexpensive. However, copper may have a higher degree of oxidation which consequently leads to difficulty in application thereof to conventional processes due to formation of an oxide film upon formation of a thin film. Therefore, research has been undertaken on development of an anti-oxide film for inhibiting or preventing formation of the oxide film of copper.
A conventional anti-oxide film inhibiting formation of the copper oxide film may be an anti-oxide film of a self-assembled monolayer (SAM) formed using an organic material. A conventional example of the organic material used in formation of such an anti-oxide film may be (3-mercaptopropyl)-trimethoxysilane. When the anti-oxide film is formed of SAM, a need for long-term dipping, complicated process conditions and increased rejection rates may occur, even though achieving increased antioxidative effects is possible.
Example embodiments provide a composition, which may include a fluorine-based polymer or a perfluoropolyether (PFPE) derivative of formula (1) or (2):
A-CF2O(CF2CF2O)m(CF2O)nCF2-A (1)
CF3O(CF2CF2O)m(CF2O)nCF2-A (2)
wherein:
A is A′ or RA′ wherein A′ is a functional group selected from the group consisting of COF, SiX1X2X3 (X1, X2 and X3 are independently C1-C10 alkyl and at least one of X1, X2 and X3 is C1-C10 alkoxy), silanol, chlorosilane, carboxylic acid, alcohol, amine, phosphoric acid and derivatives thereof, and R is C1-C30 alkylene which may be optionally substituted by at least one selected from the group consisting of hydroxy, C1-C10 alkyl, hydroxyalkyl, amide, nitro, C2-C30 alkenyl, C1-C30 alkoxy, and C2-C30 alkoxyalkyl;
m is 1 to 50; and
n is 1 to 50; and
a PFPE-miscible polymer.
The aforesaid composition may be capable of inhibiting or retarding oxidation of a metal surface.
Other example embodiments provide an anti-oxide film including the composition and a metal surface and an electronic component including the anti-oxide film. Other example embodiments provide a method of forming an anti-oxide film, which may include coating a metal surface with the above composition. Use of this method may allow for formation of an anti-oxide film via a solution treatment process. Other example embodiments provide a method of manufacturing an electronic component including the method of forming the anti-oxide film.
Example embodiments will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings.
It should be noted that these Figures are intended to illustrate the general characteristics of methods, structure and/or materials utilized in certain example embodiments and to supplement the written description provided below. These drawings are not, however, to scale and may not precisely reflect the precise structural or performance characteristics of any given embodiment, and should not be interpreted as defining or limiting the range of values or properties encompassed by example embodiments. For example, the relative thicknesses and positioning of molecules, layers, regions and/or structural elements may be reduced or exaggerated for clarity. The use of similar or identical reference numbers in the various drawings is intended to indicate the presence of a similar or identical element or feature.
Hereinafter, a detailed description will be given of example embodiments with reference to the accompanying drawings. In the drawings, the thicknesses of layers and regions are exaggerated for clarity, and the same reference numerals in the drawings denote the same element.
It will be understood that when an element or layer is referred to as being “on,” “interposed,” “disposed,” or “between” another element or layer, it can be directly on, interposed, disposed, or between the other element or layer or intervening elements or layers may be present.
It will be understood that, although the terms first, second, third, and the like may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, first element, component, region, layer or section discussed below could be termed second element, component, region, layer or section without departing from the teachings of the example embodiments.
As used herein, the singular forms “a,” “an” and “the” are intended to comprise the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It will be understood that when an element is referred to as being “connected” or “coupled” to another element, it can be directly connected or coupled to the other element or intervening elements may be present. In contrast, when an element is referred to as being “directly connected” or “directly coupled” to another element, there are no intervening elements present. Like numbers indicate like elements throughout. As used herein the term “and/or” includes any and all combinations of one or more of the associated listed items.
Spatially relative terms, such as “beneath,” “below,” “lower,” “above,” “upper” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the exemplary term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
Example embodiments are described herein with reference to cross-sectional illustrations that are schematic illustrations of idealized embodiments (and intermediate structures) of example embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, example embodiments should not be construed as limited to the particular shapes of regions illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, an implanted region illustrated as a rectangle will, typically, have rounded or curved features and/or a gradient of implant concentration at its edges rather than a binary change from implanted to non-implanted region. Likewise, a buried region formed by implantation may result in some implantation in the region between the buried region and the surface through which the implantation takes place. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the actual shape of a region of a device and are not intended to limit the scope of example embodiments.
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 these example embodiments belong. 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.
According to example embodiments, a composition may be provided, wherein the composition may include a fluorine-based polymer or a perfluoropolyether (PFPE) derivative of formula (1) or (2):
A-CF2O(CF2CF2O)m(CF2O)nCF2-A (1)
CF3O(CF2CF2O)m(CF2O)nCF2-A (2)
wherein:
A is A′ or RA′ wherein A′ is a functional group selected from the group consisting of COF, SiX1X2X3 (X1, X2 and X3 are independently C1-C10 alkyl, and at least one of X1, X2 and X3 is C1-C10 alkoxy), silanol, chlorosilane, carboxylic acid, alcohol, amine, phosphoric acid and derivatives thereof, and R is C1-C30 alkylene which may be optionally substituted by at least one selected from the group consisting of hydroxy, C1-C10 alkyl, hydroxyalkyl, amide, nitro, C2-C30 alkenyl, C1-C30 alkoxy, and C2-C30 alkoxyalkyl;
m is 1 to 50; and
n is 1 to 50; and
a PFPE-miscible polymer.
The composition may maximize or increase antioxidative effects due to improved water repellency and diffusion barrier effects via the incorporation of a fluorine-based polymer per se, or perfluoropolyether, a hydrophobic fluorine-based material capable of exhibiting properties of the fluorine-based polymer when mixed with a polymer.
The fluorine-based polymer contained in the composition may be at least one selected from the group consisting of silicon rubber, polyvinylidene fluoride (PVDF), fluoroolefin, vinyl ether copolymer, ethylene trifluoride, vinylidene fluoride copolymer, polytetrafluoroethylene, perfluoroethylenepropylene resin, perfluoroalkoxy resin, Teflon®, Nafion®, and Cytop®.
A weight-average molecular weight of perfluoropolyether may be in the range of about 1,000 to about 20,000. An example of perfluoropolyether of formula (I) may be a compound of formulas (3), (4) or (5):
The perfluoropolyether and PFPE-miscible polymer may be used in the form of a mixture or copolymer thereof. As used herein, the term “PFPE-miscible polymer” may be intended to encompass all kinds of polymers that may be mixed with perfluoropolyether. For example, the PFPE-miscible polymer may have functional group(s), e.g., —OH, —COOH, —NH2, and —CONH2.
The PFPE-miscible polymer may be a photosensitive polymer having at least one photosensitive functional group at either or both of the main and side chains. As used herein, the term “photosensitive polymer” refers to a polymer that converts into a photosensitive material when mixed with a polymer or photocrosslinking agent containing photosensitive functional group(s) which may be photodegradable or photocrosslinkable.
There may be no particular limit to the photosensitive functional group, as long as it is a conventional photosensitive functional group known in the art. Therefore, the photosensitive functional group may be at least one selected from the group consisting of acrylate, siloxane, imide, amide, vinyl, urethane, ester, epoxy, and alcohol.
Further, the photosensitive polymer may be a water-soluble photosensitive polymer. For example, the water-soluble photosensitive polymer may be at least one selected from the group consisting of polyvinyl alcohol, polyvinyl chloride, polyacrylic amide, polyethylene glycol, polyethylene oxide, polymethylvinylether, polyethyleneimine, polyphenylenevinylene, polyaniline, polypyrrole and copolymers thereof. However, the water-soluble photosensitive polymer may not be limited thereto. The PFPE-miscible polymer may have a weight-average molecular weight of about 500 to about 1,000,000, for example, about 20,000 to about 100,000.
A volume ratio of perfluoropolyether:PFPE-miscible polymer in the composition may be in the range of about 15:85 to about 1:99. If a content of perfluoropolyether is relatively high, decreased crosslinkability may result. On the other hand, if a content of perfluoropolyether is relatively low, deterioration in the hydrophobicity and diffusion barrier properties of the resulting thin film may result.
The anti-oxide film-forming composition may further include a photocuring agent. The photocuring agent may be added to accelerate curing of the coating film by UV irradiation. There may be no particular limit to types of the photocuring agent that may be used herein, for example, ammonium dichromate, pentaerythritol triacrylate, and urethane acrylate. These materials may be used alone or in any combination thereof. The photocuring agent may be added to the PFPE-miscible polymer dissolved in deionized water, in a ratio of about 0.005:1 to about 0.05:1, for example, about 0.01:1 to about 0.04:1, based on a content of solids.
In addition to aforesaid essential components, the film-forming composition may further include compatible polymers or various additives, for example, colorants, plasticizers, surfactants, and coupling agents, if necessary. These materials may be used alone or in any combination thereof.
The composition may be applied to at least one metal surface selected from the group consisting of copper, aluminum, iron, and molybdenum. Further, the composition may be capable of achieving formation of patterns by the solution process and may provide higher antioxidative effects in conjunction with suitability to subsequent processing including Au wiring.
In accordance with example embodiments, an anti-oxide film may include the composition and a metal surface. In accordance with example embodiments, an electronic component may include the anti-oxide film.
In accordance with example embodiments, a method of forming an anti-oxide film may be provided, which may include coating a metal surface with a composition containing a fluorine-based polymer or a composition containing perfluoropolyether in conjunction with a PFPE-miscible polymer. When the PFPE-miscible polymer is a photosensitive polymer, the method may further include exposure of the coating film to UV irradiation, followed by development, after coating of the composition is complete. Hereinafter, the method of forming an anti-oxide film will be described in more detail.
Formation of the coating film may be carried out by a conventional method known in the art, e.g., spin coating, dip coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, spray coating, screen printing, flexographic printing, offset printing, and inkjet printing. Examples of the solvent used in formation of the coating film from the anti-oxide film-forming composition may include water, alcohol, toluene, xylene, chloroform, and tetrahydrofuran.
Formation of the coating film may be followed by drying, UV irradiation and development. Drying may be carried out by any conventional method known in the art. Exposure of the coating film may be carried out through a mask. There may be no particular limit to the light source for exposure of the coating film, as long as the light source may be capable of photosensitizing photosensitive functional group(s) of the photosensitive polymer used. For example, UV light, X-ray, E-beam, excimer laser (F2, ArF, or KrF laser), or a high-pressure mercury lamp may be used as a light source. Exposure energy may be appropriately determined by structures of the photosensitive functional groups of the photosensitive polymer and energy types of the light sources. For example, exposure of the coating film may be carried out by UV irradiation at a wavelength of about 340 to about 400 nm for about 10 to about 180 seconds, using a UV lamp with power of about 300 to about 500 W.
There may be no particular limit to the developing solution, as long as the solution imparts a sufficient difference in the solubility between the unexposed region and the exposed region. Water or a mixed solution of water with a water-compatible organic solvent may be used as a solvent for dissolution of the unexposed region of the photosensitive polymer. Non-limiting examples of the water-compatible organic solvent may include acetone, lower alcohol (e.g., methanol), acetonitrile and ketone (e.g., tetrahydrofuran). The developing solution may be a mixed solution.
When it is desired to use the anti-oxide film-forming composition containing the water-soluble photosensitive polymer, deionized water may be used in the development step after completion of UV irradiation. For example, the development of the film may be carried out at about room temperature for about 1 to about 5 minutes, using deionized water.
After completion of the development, baking of the coating film may be carried out, if necessary. There may be no particular limit to the baking conditions. For example, the baking process may be carried out on a hot plate at a temperature of about 50 to about 150° C. for about 0.5 to about 2 hours.
In accordance with example embodiments, there may be provided a method of manufacturing an electronic component including forming the anti-oxide film which includes coating of the above composition. Examples of the electronic component may include, but are not limited to, wiring pads of memory and processing microdevices, optical sensors, heat sinks for display devices, wirings and electrodes of Organic Thin Film Transistors, electrodes of display devices, and wirings and electrodes of battery devices.
A better understanding of example embodiments will be described in more detail with reference to the following examples. However, these examples may be given for the purpose of illustration merely and may be not to be construed as limiting the scope of example embodiments.
Polyvinyl alcohol (about 0.5 wt % in Di-water, Kanto Chemical Co., Ltd.) was mixed with ammonium dichromate (Sigma Aldrich) in a weight ratio of about 1:0.03, based on a content of solids. The resulting mixture and a perfluoropolyether-phosphate derivative (PT5045, Solvay Solexis) were mixed in a volume ratio of about 99:1 and stirred to prepare a composition.
A composition was prepared in the same manner as in Example 1, except that the mixture of polyvinyl alcohol (about 0.5 wt % in Di-water, Kanto Chemical Co., Ltd.) with ammonium dichromate (Sigma Aldrich) of Example 1 and a perfluoropolyether-phosphate derivative (PT5045, Solvay Solexis) were mixed in a volume ratio of about 97:3.
The anti-oxide film-forming composition synthesized in Example 1 was diluted to about 1/10 in water, coated on a copper metal substrate by spin coating at about 2000 rpm and dried at room temperature for about 15 minutes. A mask was placed on the dried surface of the coating film which was then irradiated with a 400 W/cm3 UV lamp at a wavelength of about 340 to about 400 nm for about 20 seconds and developed in deionized water at room temperature for about 3 minutes. As a result, only the UV-irradiated part remained in conjunction with dissolution of the unirradiated part to thereby result in the formation of patterns at the desired regions. Then, the coating was baked on a hot plate at a temperature of about 110° C. for about 30 minutes to form an anti-oxide film with a thickness of about 2,000 Å.
An anti-oxide film-forming composition synthesized in Example 1 was diluted to about ⅕ in water, coated on a copper metal substrate by spin coating at about 2000 rpm and dried at room temperature for about 15 minutes. A mask was placed on the dried surface of the copper metal which was then irradiated with a 400 W/cm3 UV lamp at a wavelength of about 340 to about 400 nm for about 20 seconds and developed in deionized water at room temperature for about 3 minutes. As a result, only the UV-irradiated part remained in conjunction with dissolution of the unirradiated part to thereby result in the formation of patterns at the desired region. Then, the coating was baked on a hot plate at a temperature of about 110° C. for about 30 minutes to form an anti-oxide film with a thickness of about 2000 Å.
Au wiring involving melt-adhesion of an Au wire by frictional heat was made on a substrate pad with formation of an anti-oxide film against copper oxidation prepared in Example 3.
Analogously to the procedure of Experimental Example 1, Au wiring was made on a substrate pad with formation of an anti-oxide film against copper oxidation prepared in Example 4.
Analogously to the procedure of Experimental Example 1, Au wiring was made on a substrate pad with no formation of an anti-oxide film. A rejection rate for adhesion completeness of the Au wiring over time in Experimental Examples 1 and 2 and Comparative Experimental Example 1 was measured by the naked eye and conductivity.
Although example embodiments have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions may be possible, without departing from the scope and spirit of the example embodiments as disclosed in the accompanying claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2008-0010651 | Feb 2008 | KR | national |
