This application claims the benefit of priority under 35 U.S.C. § 119 of Korean Patent Application Serial No. 10-2021-0023399 filed on Feb. 22, 2021, the content of which is relied upon and incorporated herein by reference in its entirety.
The present disclosure relates generally to a laminate and methods of making the same and, more particularly, to a laminate comprising an oxide layer and methods of making the same using sputtering.
Laminates comprising glass materials and/or ceramic materials can be used in photovoltaic applications or display applications, for example, liquid crystal displays (LCDs), electrophoretic displays (EPDs), organic light-emitting diode displays (OLEDs), and plasma display panels (PDPs). Glass sheets are commonly fabricated by a flowing glass-forming material to a forming device whereby a glass web may be formed by a variety of web forming processes, for example, slot draw, float, down-draw, fusion down-draw, rolling, tube drawing, or up-draw. The glass web may be periodically separated into individual glass sheets.
It is known to form laminates using a silicon wafer and an electrically conductive layer deposited thereon. Such laminates can be used as a printed circuit in electronic devices. However, forming such laminates with a substrate comprising a glass material and/or a ceramic material can have poor adhesion between the layers of the laminate, especially when the substrate is smooth (e.g., surface roughness (Ra) of about 3 nanometers (nm) or less, about 0.3 nm or less). Consequently, there is a need to provide a laminate with good adhesion between layers of the laminate when the substrate comprises a glass material and/or a ceramic material.
The following presents a simplified summary of the disclosure to provide a basic understanding of some embodiments described in the detailed description.
Embodiments of the disclosure can provide laminates with good adhesion between a substrate and an oxide layer. Providing an oxide layer comprising oxygen and a first element with a limited atomic ratio of oxygen to the first element (e.g., about 1.5 or less, about 1 or less, about 0.8 or less) can enable good adhesion. In some embodiments, providing a non-stoichiometric ratio of oxygen to the first element can further promote adhesion. Limiting the thickness of the oxide layer (e.g., about 40 nm or less, about 30 nm or less) can enable good adhesion, for example, by limiting the oxygen content of the oxide layer. In some embodiments, a substrate comprising glass and/or ceramic can have good adhesion with the oxide layer, for example, with covalent bonding or polar interactions. In further embodiments, the first element in the oxide layer can comprise at least one of titanium, tantalum, silicon, or aluminum, which can promote adhesion with the substrate comprising glass and/or ceramic.
In some embodiments, the laminate can comprise a metallic layer disposed over the oxide layer. Providing a metallic layer can enable good adhesion between the metallic layer and the oxide layer. In further embodiments, adhesion between the metallic layer and the oxide layer can be greater than the adhesion between the oxide layer and the substrate. For example, the metallic layer can comprise copper, which has negative mixing enthalpy with titanium in an oxide layer comprising titanium oxide, providing strong adhesion between the metallic layer and the oxide layer. In further embodiments, the metallic layer can be electrically conductive and patterned to form a discontinuous layer over a first major surface of the substrate, which can serve as wiring connections, for example, as part of the circuit board. In even further embodiments, the oxide layer can be electrically non-conductive, which can electrically isolate discontinuous portions of the metallic layer from one another.
Embodiments of the disclosure can provide methods of making a laminate comprising depositing an oxide layer over a substrate using reactive sputtering from an elemental target in an oxygen-containing environment, which can enable control of the oxygen content of the resulting oxide layer and promote adhesion between the substrate and the oxide layer. In some embodiments, a metallic layer (e.g., electrically conductive) can be disposed on the oxide layer (e.g., electrically non-conductive) and patterned to be discontinuous over a first major surface without removing corresponding portions of the discontinuous metallic layer, which can simplify processing of the laminate, for example, by reducing processing time and overall cost to make the laminate.
In some embodiments, a laminate can comprise a substrate comprising a first major surface. The laminate can comprise an oxide layer that can be disposed over the first major surface of the substrate. The oxide layer can comprise a thickness of about 40 nanometers (nm) or less. The oxide layer can comprise oxygen and a first element. The first element can comprise at least one of titanium, tantalum, silicon, or aluminum. The oxide layer can further comprise an atomic ratio of oxygen to the first element that can be about 1.5 or less. A peel strength of the laminate between the substrate and the oxide layer, measured at 20° C. in accordance with IPC-TM-650.2.4.8 Condition A, can be about 1.3 Newtons per centimeter (N/cm) or more.
In further embodiments, the laminate can further comprise a metallic layer disposed over the oxide layer.
In even further embodiments, the metallic layer can comprise copper.
In even further embodiments, the metallic layer comprises a thickness that can be in a range from about 100 nanometers to about 20 micrometers (μm).
In still further embodiments, a thickness of the metallic layer can be in a range from about 2 micrometers to about 15 micrometers.
In even further embodiments, the metallic layer can directly contact the oxide layer.
In even further embodiments, the metallic layer can be discontinuous over the first major surface of the substrate.
In still further embodiments, the oxide layer can be substantially continuous over the first major surface of the substrate.
In further embodiments, the atomic ratio of oxygen to the first element can be about 0.8 or less.
In further embodiments, the oxide layer can comprise titanium oxide. The first element can comprise titanium. An atomic ratio of oxygen to the titanium can be about 1.5 or less.
In even further embodiments, the atomic ratio of oxygen to the titanium of the titanium oxide can be about 0.8 or less.
In further embodiments, the oxide layer can consist essentially of titanium oxide.
In further embodiments, the oxide layer can be electrically non-conductive.
In further embodiments, the thickness of the oxide layer can be in a range from about 10 nanometers to about 30 nanometers.
In further embodiments, the oxide layer can directly contact the first major surface of the substrate.
In further embodiments, the peel strength of the laminate between the substrate and the oxide layer can be in a range from about 2.5 Newtons per centimeter to about 7 Newtons per centimeter.
In further embodiments, the peel strength of the laminate between the substrate and the oxide layer can be about 4 Newtons per centimeter or more.
In further embodiments, the substrate can comprise a glass material.
In further embodiments, the substrate can comprise a ceramic material.
In further embodiments, the substrate comprises a thickness that can be in a range from about 25 micrometers to about 2 millimeters.
In some embodiments, a method of making a laminate can comprise depositing an oxide layer over a first major surface of a substrate by sputtering from an elemental target comprising a first element in an oxygen-containing element. The oxide layer comprises a thickness that can be about 40 nanometers (nm) or less. The oxide layer can comprise oxygen and the first element. The first element can comprise at least one of titanium, tantalum, silicon, or aluminum. The oxide layer can further comprise an atomic ratio of the oxygen to the first element that can be about 1.5 or less. A peel strength of the laminate between the substrate and the oxide layer, measured at 20° C. in accordance with IPC-TM-650.2.4.8 Condition A, can be about 1.3 Newtons per centimeter (N/cm) or more.
In further embodiments, the method can further comprise depositing a metallic layer over the oxide layer.
In even further embodiments, the method can further comprise depositing a mask layer with a predetermined pattern on the metallic layer. The method can further comprise etching at least a portion of the metallic layer after depositing the mask layer. The method can further comprise removing the mask layer after the etching.
In still further embodiments, the metallic layer can be discontinuous over the first major surface of the substrate. The oxide layer can be substantially continuous over the first major surface of the substrate.
In even further embodiments, the metallic layer can comprise copper.
In even further embodiments, a thickness of the metallic layer can be in a range from about 2 micrometers (μm) to about 15 micrometers.
In even further embodiments, the metallic layer can directly contact the oxide layer.
In further embodiments, the method can further comprise heating the laminate at a temperature in a range from about 250° C. to about 400° C. for a time in a range from about 15 minutes to about 6 hours.
In further embodiments, the atomic ratio of the oxygen to the first element can be about 0.8 or less.
In further embodiments, the oxide layer can comprise titanium oxide. The first element can comprise titanium. An atomic ratio of the oxygen to the titanium can be about 1.5 or less.
In even further embodiments, the atomic ratio of the oxygen to the titanium of the titanium oxide can be about 0.8 or less.
In further embodiments, the oxide layer can consist essentially of titanium oxide.
In further embodiments, the oxide layer can be electrically non-conductive.
In further embodiments, the thickness of the oxide layer can be in a range from about 10 nanometers to about 30 nanometers.
In further embodiments, the oxide layer can directly contact the first major surface of the substrate.
In further embodiments, the peel strength of the laminate between the substrate and the oxide layer can be in a range from about 2.5 Newtons per centimeter to about 7 Newtons per centimeter.
In further embodiments, the peel strength of the laminate between the substrate and the oxide layer can be about 4 Newtons per centimeter or more.
In further embodiments, the substrate can comprise a glass material.
In further embodiments, the substrate can comprise a ceramic material.
In further embodiments, the substrate comprises a thickness that can be in a range from about 25 micrometers to about 2 millimeters.
Additional features and advantages of the embodiments disclosed herein will be set forth in the detailed description that follows, and in part will be clear to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows, the claims, as well as the appended drawings. It is to be understood that both the foregoing general description and the following detailed description present embodiments intended to provide an overview or framework for understanding the nature and character of the embodiments disclosed herein. The accompanying drawings are included to provide further understanding and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments of the disclosure, and together with the description explain the principles and operations thereof.
These and other features, aspects, and advantages are better understood when the following detailed description is read with reference to the accompanying drawings, in which:
Embodiments will now be described more fully hereinafter with reference to the accompanying drawings in which exemplary embodiments are shown. Whenever possible, the same reference numerals are used throughout the drawings to refer to the same or like parts. However, this disclosure may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Throughout the disclosure, with reference to
Laminates 101, 501, and 601 of the disclosure comprise the substrate 103. In some embodiments, the substrate 103 can comprise a substrate comprising a glass material and/or a ceramic material. In further embodiments, the substrate can comprise a pencil hardness of 8H or more, for example, 9H or more. As used herein, pencil hardness is measured using ASTM D 3363-20 with standard lead graded pencils. In further embodiments, the substrate 103 can consist essentially of a glass material or consist entirely of a glass material. In further embodiments, the substrate 103 can consist essentially of or consist entirely of a ceramic material. In some embodiments, the substrate 103 can comprise an oxide-containing material and/or a silicon-containing material.
In some embodiments, the substrate 103 can comprise a glass material. As used herein, “glass” refers to an amorphous material comprising at least 30 mole percent (mol %) of silica (SiO2). A substrate comprising glass (e.g., a glass material) includes both glasses and glass-ceramics, wherein glass-ceramics have one or more crystalline phases and an amorphous, residual glass phase. A substrate comprising glass comprises an amorphous material (e.g., glass) and optionally one or more crystalline materials (e.g., ceramic). Amorphous materials and glass may be strengthened. As used herein, the term “strengthened” may refer to a material that has been chemically strengthened, for example, through ion-exchange of larger ions for smaller ions in the surface of the substrate. However, other strengthening methods, for example, thermal tempering, or utilizing a mismatch of the coefficient of thermal expansion between portions of the substrate to create compressive stress and central tension regions, may be utilized to form strengthened substrates. Exemplary glass materials, which may be free of lithia or not, comprise soda-lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, alkali-containing aluminoborosilicate glass, alkali-containing phosphosilicate glass, and alkali-containing aluminophosphosilicate glass. Glass materials can comprise an alkali-containing glass or an alkali-free glass, either of which may be free of lithia or not. In one or more embodiments, glass materials may comprise, in mole percent (mol %). SiO2 in a range from about 40 mol % to about 80%, Al2O3 in a range from about 5 mol % to about 30 mol %, B2O3 in a range from 0 mol % to about 10 mol %, ZrO2 in a range from 0 mol % to about 5 mol %, P2O5 in a range from 0 mol % to about 15 mol %, TiO2 in a range from 0 mol % to about 2 mol %, R2O in a range from 0 mol % to about 20 mol %, and RO in a range from 0 mol % to about 15 mol %. As used herein, R2O can refer to an alkali metal oxide, for example, Li2O, Na2O, K2O, Rb2O, Cs2O, or combinations thereof. As used herein, RO can refer to MgO, CaO, SrO, BaO, ZnO, or combinations thereof. In some embodiments, glass materials may optionally further comprise in a range from 0 mol % to about 2 mol % of each of Na2SO4, NaCl, NaF, NaBr, K2SO4, KCl, KF, KBr, As2O3, Sb2O3, SnO2, Fe2O3, MnO, MnO2, MnO3, Mn2O3, Mn3O4, and/or Mn2O7. “Glass-ceramics” include materials produced through controlled crystallization of glass. In some embodiments, glass-ceramics can comprise about 1% to about 99% crystallinity. Examples of suitable glass-ceramics may include Li2O—Al2O3—SiO2 system (i.e., LAS-System) glass-ceramics, MgO—Al2O3—SiO2 system (i.e., MAS-System) glass-ceramics, ZnO×Al2O3×nSiO2 (i.e., ZAS system), and/or glass-ceramics that include a predominant crystal phase including β-quartz solid solution, β-spodumene, cordierite, petalite, and/or lithium disilicate. Glass-ceramic substrates may be strengthened using chemical strengthening processes. In one or more embodiments, MAS-System glass-ceramic substrates may be strengthened in a Li2SO4 molten salt, whereby an exchange of 2Li+ for Mg2+ can occur.
In some embodiments, the substrate 103 can comprise a ceramic material. As used herein, “ceramic” refers to a crystalline phase. A substrate comprising ceramic (e.g., a ceramic material) includes both ceramics and glass-ceramics, wherein glass-ceramics have one or more crystalline phases and an amorphous, residual glass phase. Ceramic materials may be strengthened (e.g., chemically strengthened). In some embodiments, a ceramic material can be formed by heating a substrate comprising a glass material to form ceramic (e.g., crystalline) portions. In further embodiments, ceramic materials may comprise one or more nucleating agents that can facilitate the formation of crystalline phase(s). In some embodiments, the ceramic materials can comprise one or more oxides, nitrides, oxynitrides, carbides, borides, and/or silicides. Example embodiments of ceramic oxides include zirconia (ZrO2), zircon (ZrSiO4), an alkali metal oxide (e.g., sodium oxide (Na2O)), an alkali earth metal oxide (e.g., magnesium oxide (MgO)), titania (TiO2), hafnium oxide (Hf2O), yttrium oxide (Y2O3), iron oxides, beryllium oxides, vanadium oxide (VO2), fused quartz, mullite (a mineral comprising a combination of aluminum oxide and silicon dioxide), and spinel (MgAl2O4). Example embodiments of ceramic nitrides include silicon nitride (Si3N4), aluminum nitride (AlN), gallium nitride (GaN), beryllium nitride (Be3N2), boron nitride (BN), tungsten nitride (WN), vanadium nitride, alkali earth metal nitrides (e.g., magnesium nitride (Mg3N2)), nickel nitride, and tantalum nitride. Example embodiments of oxynitride ceramics include silicon oxynitride, aluminum oxynitride, and a SiAlON (a combination of alumina and silicon nitride and can have a chemical formula, for example, Si12-m-nAlm+nOnNi6-n, Si6-nAlnOnN8-n, or Si2-nAlnO1+nN2-n, where m, n, and the resulting subscripts are all non-negative integers). Example embodiments of carbides and carbon-containing ceramics include silicon carbide (SiC), tungsten carbide (WC), an iron carbide, boron carbide (B4C), alkali metal carbides (e.g., lithium carbide (Li4C3)), alkali earth metal carbides (e.g., magnesium carbide (Mg2C3)), and graphite. Example embodiments of borides include chromium boride (CrB2), molybdenum boride (Mo2B5), tungsten boride (W2B5), iron boride, titanium boride, zirconium boride (ZrB2), hafnium boride (HfB2), vanadium boride (VB2), Niobium boride (NbB2), and lanthanum boride (LaB6). Example embodiments of silicides include molybdenum disilicide (MoSi2), tungsten disilicide (WSi2), titanium disilicide (TiSi2), nickel silicide (NiSi), alkali earth silicide (e.g., sodium silicide (NaSi)), alkali metal silicide (e.g., magnesium silicide (Mg2Si)), hafnium disilicide (HfSi2), and platinum silicide (PtSi).
As used herein, a silicon-containing material means a material comprising at least 30 mole percent (mol %) of silicon (Si). As described above, silicon can be found in both glass materials and ceramic materials in coordination with other elements, for example, oxygen, nitrogen, carbon, aluminum, hafnium, magnesium, molybdenum, nickel, platinum, sodium, titanium, tungsten, and/or zirconium. As used herein, an oxygen-containing material means a material comprising at least 15 mole percent (mol %) of oxygen (O). As described above, oxygen can be found in both glass materials and ceramic materials in coordination with other elements, for example, alkali metals, alkali earth metals, transition metals, aluminum, bismuth, carbon, gallium, lead, nitrogen, phosphorous, silicon, sulfur, selenium, and/or tin.
Throughout the disclosure, an elastic modulus (e.g., Young's modulus) of the substrate 103 (e.g., glass material, ceramic material, silicon-containing material, oxygen-containing material) and/or the oxide layer 113 is measured using indentation methods in accordance with ASTM E2546-15. In some embodiments, the substrate 103 can comprise an elastic modulus of about 10 GigaPascals (GPa) or more, about 50 GPa or more, about 60 GPa or more, about 70 GPa or more, about 100 GPa or less, or about 80 or less. In some embodiments, the substrate 103 can comprise an elastic modulus in a range from about 10 GPa to about 100 GPa, from about 50 GPa to about 100 GPa, from about 50 GPa to about 80 GPa, from about 60 GPa to about 80 GPa, from about 70 GPa ta about 80 GPa, or any range or subrange therebetween.
In some embodiments, the substrate 103 can be optically transparent. As used herein, “optically transparent” or “optically clear” means an average transmittance of 70% or more in the wavelength range of 400 nm to 700 nm through a 1.0 mm thick piece of a material. In some embodiments, an “optically transparent material” or an “optically clear material” may have an average transmittance of 75% or more, 80% or more, 85% or more, or 90% or more, 92% or more, 94% or more, 96% or more in the wavelength range of 400 nm to 700 nm through a 1.0 mm thick piece of the material. The average transmittance in the wavelength range of 400 nm to 700 nm is calculated by averaging transmittance measurements of whole number wavelengths from about 400 nm to about 700 nm.
As shown in
The first major surface 105 of the substrate 103 can comprise a surface roughness (Ra). Throughout the disclosure, all surface roughness values set forth in the disclosure are a surface roughness (Ra) calculated using an arithmetical mean of the absolute deviations of a surface profile from an average position in a direction normal to the surface of a test area of 10 μm by 10 μm as measured using atomic force microscopy (AFM). In some embodiments, the surface roughness (Ra) of the first major surface 105 and/or the second major surface 107 of the substrate 103 can be about 5 nm or less, about 3 nm or less, about 2 nm or less, about 1 nm or less, about 0.9 nm or less, about 0.5 nm or less, or about 0.3 nm or less. In some embodiments, the surface roughness (Ra) of the first major surface 105 and/or the second major surface 107 of the substrate 103 can be in a range from about 0.1 nm to about 5 nm, from about 0.1 nm to about 3 nm, from about 0.1 nm to about 2 nm, from about 0.1 nm to about 1 nm, from about 0.1 nm to about 0.9 nm, from about 0.1 nm to about 0.5 nm, from about 0.1 nm to about 0.3 nm, from about 0.15 nm to about 5 nm, from about 0.15 nm to about 3 nm, from about 0.15 nm to about 2 nm, from about 0.15 nm to about 1 nm, from about 0.15 nm to about 0.9 nm, from about 0.15 nm to about 0.5 nm, from about 0.15 nm to about 0.3 nm, from about 0.2 nm to about 5 nm, from about 0.2 nm to about 3 nm, from about 0.2 nm to about 2 nm, from about 0.2 nm to about 1 nm, from about 0.2 nm to about 0.9 nm, from about 0.2 nm to about 0.5 nm, from about 0.2 nm to about 0.3 nm, or any range or subrange therebetween.
As shown in
As shown in
The oxide layer 113 comprises an oxide comprising oxygen and a first element. In some embodiments, the first element comprises at least one of titanium, tantalum, silicon, or aluminum. For example, the oxide layer 113 can comprise titanium oxide, tantalum oxide, silicon oxide, and/or aluminum oxide. In further embodiments, the oxide layer 113 consists essentially of one or more oxides. In further embodiments, the oxide layer 113 can consist essentially of titanium oxide. In further embodiments, the oxide layer 113 can consist essentially of tantalum oxide. In further embodiments, the oxide layer 113 can consist essentially of silicon oxide. In further embodiments, the oxide layer 113 can consist essentially of aluminum oxide.
The oxide layer 113 can comprise an atomic ratio of oxygen to the first element. As used herein, the atomic ratio of an oxide layer refers to the amount of oxygen in the oxide layer in atomic percent (atomic %) divided by the amount of the first element in the oxide layer in atomic %. Likewise, the atomic ratio of a specific oxide comprising oxygen and the first element refers to the amount of oxygen in the specific oxide in atomic percent (atomic %) divided by the amount of the first element in the specific oxide in atomic %. Without wishing to be bound by theory, the oxide layer can comprise the oxide that can comprise a non-stoichiometric ratio of oxygen to the first element. As used herein, an oxide with a non-stoichiometric ratio refers to an oxide where the ratio between oxygen and the first element cannot be expressed using integers between 1 and 5. Without wishing to be bound by theory, the oxide layer can comprise an oxide (e.g., comprising a non-stoichiometric ratio of oxygen to the first element) that does not correspond to a naturally occurring oxide (e.g., titania, alumina, silica), for example, through a partial (e.g., incomplete) reaction between the first element and oxygen. Without wishing to be bound by theory, limiting the atomic ratio of oxygen to the first element can increase adhesion with a substrate comprising a glass material, a ceramic material, an oxygen-containing material, and/or a silicon-containing material by promoting bonding between the oxide and the substrate and/or intermolecular interactions between the oxide and the substrate. For example, an oxide with a limited atomic ratio of oxygen to the first element can comprise an energetically unstable or metastable configuration (e.g., coordination number), which may encourage interaction with material at the first major of the substrate.
In some embodiments, the atomic ratio of the oxide layer 113 can be about 1.5 or less, about 1.3 or less, about 1.1 or less, about 1.0 or less, about 0.9 or less, about 0.8 or less, about 0.6 or less, about 0.5 or less, or about 0.4 or less, about 0.1 or more, about 0.25 or more, about 0.35 or more, about 0.5 or more, about 0.7 or more, about 1.0 or more or about 1.1 or more. In some embodiments, the atomic ratio of the oxide layer 113 can be in a range from about 0.1 to about 1.5, from about 0.25 to about 1.5, from about 0.35 to about 1.5, from about 0.5 to about 1.5, from about 0.7 to about 1.5, from about 1.0 to about 1.5, from about 1.1 to about 1.5, from about 1.1 to about 1.3, or any range or subrange therebetween. In some embodiments, the atomic ratio of the oxide layer 113 can be in a range from about 0.1 to about 1.3, from about 0.25 to about 1.3, from about 0.35 to about 1.3, from about 0.5 to about 1.3, from about 0.5 to about 1.0, from about 0.5 to about 0.9, from about 0.7 to about 0.9, from about 0.7 to about 0.8, or any range or subrange therebetween. In some embodiments, the atomic ratio of the oxide layer 113 can be in a range from about 0.1 to about 1.1, from about 0.1 to about 1.0, from about 0.1 to about 0.9, from about 0.1 to about 0.8 from about 0.25 to about 0.8, from about 0.25 to about 0.6, from about 0.35 to about 0.6, from about 0.35 to about 0.5, from about 0.35 to about 0.4, or any range subrange therebetween.
In some embodiments, the oxide layer 113 can consist essentially of titanium oxide. In further embodiments, an atomic ratio of the titanium oxide can be about 1.5 or less. For example, titanium oxide can comprise titanium(II) oxide (TiO), titanium (III) oxide (Ti2O3), dititanium oxide (Ti2O), trititanium oxide (Ti3O), and/or a non-stoichiometric form of titanium oxide instead of titania (TiO2). In even further embodiments, the atomic ratio of the titanium oxide can be about 0.8 or less (e.g., Ti2O, Ti3O, or a non-stoichiometric form of titanium oxide).
In some embodiments, the oxide layer 113 can be electrically non-conductive. As used herein, “electrically non-conductive” refers to a material with an electrical conductivity of about 100 Siemens per meter (S/m) or less (i.e., an electrical resistivity of about 0.01 Ohm meters (Q m) or more). Unless otherwise specified, electrical conductivity is measured at 20° C. in accordance with ASTM 1004-17.
In further embodiments, the oxide layer can comprise an electrical conductivity of about 10 S/m or less, about 1 S/m or less, about 0.1 S/m or less, about 10−3 S/m or less, about 10−20 S/m or more, about 10−18 S/m or more, about 10−12 S/m or more, or about 10−6 S/m or more. In further embodiments, the oxide layer can comprise an electrical conductivity in a range from about 10−20 S/m to about 100 S/m, from about 10−18 S/m to about 10 S/m, from about 10−18 S/m to about 1 S/m, from about 10−12 S/m to about 1 S/m, from about 10−12 S/m to about 0.1 S/m, from about 10−6 S/m to about 0.1 S/m, from about 10−6 S/m to about 10−3 S/m, or any range or subrange therebetween.
In some embodiments, as shown in
In some embodiments, as shown in
In some embodiments, the metallic layer 123 can comprise a transition metal. In further embodiments, the metallic layer 123 can comprise copper, cobalt, cadmium, chromium, gold, iridium, iron, lead, molybdenum, nickel, platinum, palladium, rhodium, silver, and/or zinc. In even further embodiments, the metallic layer 123 can comprise copper. In still further embodiments, the metallic layer 123 can consist essentially of copper. In some embodiments, the metallic layer 123 can comprise aluminum, beryllium, magnesium, and/or copper. In some embodiments, mixing between the metallic layer 123 and the first element of the oxide layer 113 can be enthalpically favorable (e.g., between titanium as the first element of the oxide layer and copper and the metallic layer).
Metallic layer 123 can have an electrical conductivity of about 103 Siemens per meter (S/m) or more (i.e., an electrical resistivity of about 10−3 Ohm meters (Ω m) or less). In further embodiments, the metallic layer can comprise an electrical conductivity of about 105 S/m or more, about 106 S/m or more, about 107 S/m or more, about 1020 S/m or less, about 1015 S/m or less, about 1012 S/m or less, about 109 S/m or less, or about 107 S/m or less. In further embodiments, the metallic layer 123 can comprise an electrical conductivity in a range from about 103 S/m to about 1020 S/m, from about 103 S/m to about 1015 S/m, from about 105 S/m to about 1015 S/m, from about 106 S/m to about 1012 S/m, from about 107 S/m to about 1012 S/m, from about 107 S/m to about 109 S/m, or any range or subrange therebetween.
The laminate 101, 501, and/or 601 can comprise a peel strength. Throughout the disclosure, peel strength is measured at 20° C. in accordance with IPC-TM-650.2.4.8 “Peel Strength of Metallic Clad Laminates” condition A. As used herein, the peel strength of the laminate refers to the peel strength between the substrate (e.g., first major surface) and the oxide layer (e.g., fourth major surface). Without wishing to be bound by theory, the adhesion (e.g., measured as a peel strength) between the substrate and the oxide layer can be weaker than an adhesion between other layers of the laminate (e.g., between the oxide layer and the metallic layer), if provided. In some embodiments, the peel strength can be about 1.3 Newtons per centimeter (N/cm) or more, about 2.5 N/cm or more, about 4 N/cm or more, about 5 N/cm or more, about 12 N/cm or less, about 9 N/cm or less, about 7 N/cm or less, or about 6 N/cm or less. In some embodiments, the peel strength can be in a range from about 1.3 N/cm to about 12 N/cm, from about 1.3 N/cm to about 9 N/cm, from about 2.5 N/cm to about 9 N/cm, from about 2.5 N/cm to about 7 N/cm, from about 4 N/cm to about 7 N/cm, from about 4 N/cm to about 6 N/cm, from about 5 N/cm to about 6 N/cm, or any range or subrange therebetween.
In some embodiments, the laminate 101, 501, and/or 601 of the embodiments of the disclosure can be incorporated into an application (e.g., a display application, an electronic device). For example, the laminate can be used in a wide range of applications comprising liquid crystal displays (LCDs), electrophoretic displays (EPDs), organic light-emitting diode displays (OLEDs), plasma display panels (PDPs), touch sensors, photovoltaics, appliances, or the like. Such displays can be incorporated, for example, into mobile phones, tablets, laptops, watches, wearables, and/or touch-capable monitors or displays. For example, the laminate can be used as a circuit board in a wide range of applications comprising displays, wireless communication, and/or computations, for example, as a circuit board, a processor (e.g., application processor, microprocessor), and/or an antenna (e.g., millimeterWave).
An electronic product, for example a consumer electronic product, may include a housing comprising a front surface, a back surface, and side surfaces; electrical components at least partially within the housing, the electrical components comprising a controller, a memory, and a display, the display at or adjacent the front surface of the housing; and a cover substrate disposed over the display, wherein at least one of a portion of the housing or the cover substrate comprises the laminate described herein.
The laminate disclosed herein may be incorporated into another article, for example, an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches) and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), or appliance articles. An exemplary article incorporating any of the laminate disclosed herein is shown in
In some embodiments, methods of making an electronic product can comprise placing electrical components at least partially within a housing, the housing comprising a front surface, a back surface, and side surfaces, and the electrical components comprising a controller, a memory, and a display, wherein the display is placed at or adjacent the front surface of the housing. The methods can further comprise depositing a cover substrate over the display. At least one of a portion of the electrical components or the housing comprises the laminates manufactured by any of the methods of the disclosure.
Embodiments of methods of making a laminate in accordance with embodiments of the disclosure will be discussed with reference to the flow chart in
In a first step 301 of methods of the disclosure, methods can start with providing a substrate 103. In some embodiments, the substrate 103 may be provided by purchase or otherwise obtaining a substrate or by forming the substrate. In some embodiments, the substrate 103 can comprise a glass material and/or a ceramic substrate. In further embodiments, glass substrates and/or ceramic substrates can be provided by forming them with a variety of ribbon forming processes, for example, slot draw, down-draw, fusion down-draw, up-draw, press roll, redraw or float. In further embodiments, ceramic substrates can be provided by heating a glass substrate to crystallize one or more ceramic crystals. In further embodiments, the substrate 103 can comprise an oxygen-containing material and/or a silicon-containing material. The substrate 103 may comprise a second major surface 107 (see
After step 301, as shown in
In further embodiments, as shown, the sputtering chamber 403 can comprise an orifice 405a, 405b that can be used to control an environment in the sputtering chamber 403. In even further embodiments, the orifice 405a, 405b can be used to provide a reduced pressure (e.g., below atmospheric pressure, partial vacuum) within the sputtering chamber. In even further embodiments, the orifice 405a, 405b can be used to provide a continuous flow of gas through the sputtering chamber 403, for example, to maintain a predetermined partial pressure of oxygen within the sputtering chamber 403. In even further embodiments, the environment in the sputtering chamber can comprise oxygen. In still further embodiments, a partial pressure of oxygen in the environment in the sputtering chamber can be about 100 Pascals (Pa) or more, about 200 Pa or more, about 500 Pa or more, about 15,000 Pa or less, about 10,000 Pa or less, about 5,000 Pa or less, or about 2,000 Pa or less. In still further embodiments, a partial pressure of oxygen in the environment in the sputtering chamber can be in a range from about 100 Pa to about 15,000 Pa, from about 100 Pa to about 10,000 Pa, from about 200 Pa to about 10,000 Pa, from about 200 Pa to about 5,000 Pa, from about 500 Pa to about 5,000 Pa, from about 500 Pa to about 2,000 Pa, or any range or subrange therebetween. In still further embodiments, a partial pressure of oxygen in the environment in the sputtering chamber can be about 0.001 Pa or more, about 0.01 Pa or more, about 0.05 Pa or more, about 100 Pa or less, about 10 Pa or less, about 1 Pa or less, or about 0.1 Pa or less. In still further embodiments, a partial pressure of oxygen in the environment in the sputtering chamber can be in a range from about 0.001 Pa to about 100 Pa, from about 0.001 Pa to about 10 Pa, from about 0.01 Pa to about 10 Pa, from about 0.01 Pa to about 1 Pa, from about 0.05 Pa to about 1 Pa, from about 0.05 Pa to about 0.1 Pa, or any range or subrange therebetween. In still further embodiments, the environment (e.g., oxygen-containing environment) can contain one or more inert gases (e.g., argon, xenon, krypton). In yet further embodiments, the environment can consist essentially of oxygen and one or more of argon, xenon, or krypton.
In some embodiments, the sputtering can be conducted with the substrate 103 and/or the sputtering chamber 403 at a temperature of about 20° C. or more, about 30° C. or more, about 80° C. or more, about 400° C. or less, about 300° C. or less, about 200° C. or less, or about 100° C. In some embodiments, the sputtering can be conducted with the substrate 103 and/or the sputtering chamber 403 at a temperature in a range from about 20° C. to about 400° C., from about 30° C. to about 400° C., from about 30° C. to about 300° C., from about 80° C. to about 300° C., from about 80° C. to about 200° C., from about 80° to about 100° C., or any range or subrange therebetween.
In some embodiments, sputtering can comprise a magnetron using strong electric and magnetic fields to direct charged particles (e.g., plasma, ions of the materials comprising the environment (e.g., argon, krypton, xenon, oxygen)) at the sputtering surface 409a, 409b. In further embodiments, the magnetron can comprise a direct current (DC) power source. In even further embodiments, the DC magnetron sputtering may be pulsed (e.g., pulsed reactive sputtering). In even further embodiments, ejection of material from the elemental targets 407a and 407b can be alternated between the elemental targets 407a and 407b as the power to the magnetron (e.g., one or more magnetrons) is pulsed. In further embodiments, operating the magnetron can comprise alternating current (AC) between an anode and cathode that can comprise a frequency (e.g., radio frequency (RF)) of about 13.56 megahertz (MHz), although other frequencies are possible). In some embodiments, the elemental targets 407a, 407b can be rotated relative to the substrate 103. It is to be understood that the parameters such as the energy, the flow of charged particles, and/or the oxygen partial pressure can be based on, for example, the volume of the sputtering chamber 403, the pressure of the sputtering chamber 403, the size of the elemental targets 407a, 407b, the orientation of the elemental targets 407a, 407b, and/or the distance of the substrate from the elemental targets 407a, 407b. In addition to the above considerations, it is to be understood that the thickness of the deposited oxide layer can be controlled by the rate of material ejected from the elemental targets 407a, 407b and the duration of the sputtering process.
As discussed above, the oxide layer 113 deposited on the first major surface can comprise the thickness 119 of the oxide layer 113 and the atomic ratio of the oxygen to the first element. In some embodiments, the thickness 119 of the oxide layer 113 can be in one or more of the ranges discussed above for the thickness 119 of the oxide layer 113. In some embodiments, the atomic ratio of the oxygen to the first element of the oxide layer 113 can be within one or more of the ranges discussed above for the oxide layer 113. Without wishing to be bound by theory, the atomic ratio can increase as the thickness of the oxide layer increases. Consequently, in some embodiments, limiting the thickness of the oxide layer (e.g., about 40 μm or less, about 30 μm or less) can limit the atomic ratio of the oxide ratio, which can promote adhesion between the substrate 103 and the oxide layer 113. In some embodiments, another method (e.g., chemical vapor deposition (CVD) (e.g., low-pressure CVD, plasma-enhanced CVD), physical vapor deposition (PVD) (e.g., evaporation, sputtering, molecular beam epitaxy, ion plating), atomic layer deposition (ALD), spray pyrolysis, chemical bath deposition, sol-gel deposition) may be used to form the oxide layer 113.
After step 303, methods can proceed to step 305 comprising depositing a metallic layer 123 over the oxide layer 113 to produce the laminate 601 shown in
After step 305, the method can proceed to step 307 comprising depositing a mask layer over one or more portions of the metallic layer 123. In some embodiments, the mask can comprise a photoresist formed using photolithography. In some embodiments, as shown in
After step 307, as shown in
After step 309, as shown in
After step 303, 305, or 311, as shown in
After step 301, 311, or 313, methods of the disclosure can proceed to step 315. In some embodiments, step 315 may comprise the beginning of a subsequent process. In further embodiments, step 315 can comprise storing the laminate for future assembly in an application and/or further processing. In some embodiments, step 315 can comprise assembling the laminate in an application (e.g., a display application, an electronic device), as discussed above. In some embodiments, methods of the disclosure can be complete upon reaching step 315. In some embodiments, methods of the disclosure according to the flow chart in
In some embodiments, methods of making a foldable apparatus in accordance with embodiments of the disclosure can proceed along steps 301, 303, 305, 307, 309, 311, 313, and 315 of the flow chart in
Various embodiments will be further clarified by the following examples. The properties of the oxide layer and resulting peel strength of the laminate of Examples A-H are presented in Tables 1-2. Examples A-H comprise a substrate comprising a glass material (Composition 1 having a nominal composition in mol % of 63.6 SiO2; 15.7 Al2O3; 10.8 Na2O; 6.2 Li2O; 1.16 ZnO; 0.04 SnO2; and 2.5 P2O5), a substrate thickness of 150 μm, and a surface roughness (Ra) of 0.3 nm. For each example, 35 samples were prepared and measured to determine the reported peel strength and/or atomic ratio. In Examples A-H, the oxide layer consisted of titanium oxide with the thickness of the oxide layer presented in Tables 1-2 was deposited on the first major surface of the substrate. In Examples A-H, a metallic layer consisting of copper comprising a metallic thickness of 12 μm was deposited on the oxide layer by sputtering a 500 nm layer of copper followed by electroplating. Examples A-G did not comprise a heat treatment. In Examples A-G, the oxide layer was deposited using pulsed DC reactive sputtering with a magnetron pulsed at 10 kHz with a duty cycle of 50% to sputter titanium from an elemental target comprising a diameter of 100 millimeters (mm) at 100° C. with a partial pressure of oxygen maintained at 500 Pa. In Example H, the oxide layer was deposited using DC reactive sputtering with a magnetron pulsed at 10 kHz with a duty cycle of 50% to sputter titanium dioxide (TiO2) from a target consisting of TiO2 comprising a diameter of 100 mm at 100° C. in an inert environment comprising argon.
The peel strength for Examples A-E is presented in Table 1. For Examples A-C, the peel strength increases with thickness of the oxide layer going from 10 nm to 30 nm corresponding to peel strengths from 2.82 N/cm to 5.68 N/cm. Further increasing the thickness of the oxide layer beyond 30 nm (Examples D-E) is associated with a decrease in the peel strength from 5.68 N/cm at 30 nm to 1.68 N/cm at 40 nm and 1.62 N/cm at 1.36 N/cm. Increasing the thickness of the oxide layer to 100 nm produces a high variability of the peel strength.
The atomic ratios of Examples C and E-H and peel strengths are presented in Table 2. The atomic ratio of oxygen to titanium of the oxide layer was measured using transmission electron microscope (TEM) energy dispersive X-ray spectroscopy (EDS). Example H comprised an atomic ratio of 2.00 (formed by sputtering from a TiO2 target rather than an elemental titanium target) and peel strength of 0.20 N/cm. Decreasing the atomic ratio to 1.38 (Example E) is associated with an increase in the peel strength to 1.36 N/cm. Further decreasing the atomic ratio to 0.74 (Example C) is associated with a further increase in the peel strength to 5.68 N/cm. Consequently, decreasing the atomic ratio of oxygen to titanium increases, especially below about 1.50. Further, reactive sputtering from an elemental titanium target in an oxygen-containing environment can produce lower atomic ratios and greater adhesion than sputtering from a TiO2 target.
Of Examples A-F, Example C comprising a thickness of the oxide layer of 30 nm has the greatest peel strength (5.68 N/cm). Example H comprises the laminate of Example C that was further heat treated in an oven at 350° C. for 1 hour. The heat treatment decreased the atomic ratio from 0.74 (Example C) to 0.37 (Example G) while increasing the peel strength from 5.68 N/cm (Example C) to 6.80 N/cm (Example G). Consequently, heating the laminate can further decrease the atomic ratio of the oxide layer and increase the peel strength of the laminate.
Embodiments of the disclosure can provide laminates with good adhesion between a substrate and an oxide layer. Providing an oxide layer comprising oxygen and a first element with a limited atomic ratio of oxygen to the first element (e.g., about 1.5 or less, about 1 or less, about 0.8 or less) can enable good adhesion. In some embodiments, providing a non-stoichiometric ratio of oxygen to the first element can further promote adhesion. Limiting the thickness of the oxide layer (e.g., about 40 nm or less, about 30 nm or less) can enable good adhesion, for example, by limiting the oxygen content of the oxide layer. In some embodiments, a substrate comprising glass and/or ceramic can have good adhesion with the oxide layer, for example, with covalent bonding or polar interactions. In further embodiments, the first element in the oxide layer can comprise at least one of titanium, tantalum, silicon, or aluminum, which can promote adhesion with a substrate comprising glass and/or ceramic.
In some embodiments, the laminate can comprise a metallic layer disposed over the oxide layer. Providing a metallic layer can enable good adhesion between the metallic layer and the oxide layer. In further embodiments, adhesion between the metallic layer and the oxide layer can be greater than the adhesion between the oxide layer and the substrate. For example, the metallic layer can comprise copper, which has negative mixing enthalpy with titanium in an oxide layer comprising titanium oxide, providing strong adhesion between the metallic layer and the oxide layer. In further embodiments, the metallic layer can be electrically conductive and patterned to form a discontinuous layer over the first major surface of the substrate, which can serve as wiring connections, for example, as part of the circuit board. In even further embodiments, the oxide layer can be electrically non-conductive, which can electrically isolate discontinuous portions of the metallic layer from one another.
Embodiments of the disclosure can provide methods of making a laminate comprising depositing an oxide layer over a substrate using reactive sputtering from an elemental target in an oxygen-containing environment, which can enable control of the oxygen content of the resulting oxide layer and promote adhesion between the substrate and the oxide layer. In some embodiments, a metallic layer (e.g., electrically conductive) can be disposed on the oxide layer (e.g., electrically non-conductive) and patterned to be discontinuous over a first major surface without removing corresponding portions of the discontinuous metallic layer, which can simplify processing of the laminate, for example, by reducing processing time and overall cost to make the laminate.
As used herein, the terms “the,” “a,” or “an,” mean “at least one,” and should not be limited to “only one” unless explicitly indicated to the contrary. Thus, for example, reference to “a component” comprises embodiments having two or more such components unless the context clearly indicates otherwise.
As used herein, the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. When the term “about” is used in describing a value or an endpoint of a range, the disclosure should be understood to comprise the specific value or endpoint referred to. If a numerical value or endpoint of a range in the specification recites “about,” the numerical value or endpoint of a range is intended to comprise two embodiments: one modified by “about,” and one not modified by “about.” It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint and independently of the other endpoint.
The terms “substantial,” “substantially,” and variations thereof as used herein are intended to note that a described feature is equal or approximately equal to a value or description. For example, a “substantially planar” surface is intended to denote a surface that is planar or approximately planar. Moreover, as defined above, “substantially similar” is intended to denote that two values are equal or approximately equal. In some embodiments, “substantially similar” may denote values within about 10% of each other, for example within about 5% of each other, or within about 2% of each other.
As used herein, the terms “comprising” and “including,” and variations thereof, shall be construed as synonymous and open-ended, unless otherwise indicated. A list of elements following the transitional phrases comprising or including is a non-exclusive list, such that elements in addition to those specifically recited in the list may also be present.
While various embodiments have been described in detail with respect to certain illustrative and specific embodiments thereof, the present disclosure should not be considered limited to such, as numerous modifications and combinations of the disclosed features are possible without departing from the scope of the following claims.
Number | Date | Country | Kind |
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10-2021-0023399 | Feb 2021 | KR | national |
Filing Document | Filing Date | Country | Kind |
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PCT/US2022/015734 | 2/9/2022 | WO |