Articles of controllably bonded sheets and methods of making same

Abstract

The invention relates to a controllably bonded sheet article and a method of making the same. Described herein are articles and methods of making articles comprising a first sheet and a second sheet wherein the lamella and carrier are bonded together with a coating, preferably a hydrocarbon polymer coating, and related deposition methods and inert gas treatments, which can be applied to one or both sheets, van der Waals bonding, hydrogen bonding and covalent bonding between the sheets are controlled. The coating bonds the sheets together to prevent the formation of permanent bonds under high temperature processing while maintaining sufficient bonds to prevent delamination during high temperature processing.

Description

[0001] Cross-reference of related applications

[0002] This application claims priority to U.S. Provisional Application No. 62 / 381,731, filed August 31, 2016, pursuant to 35 USC § 119, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to articles comprising sheets on a carrier and methods of manufacturing sheets on a carrier, and more specifically, to articles comprising flexible glass sheets controllably bonded to a glass carrier and methods of manufacturing flexible glass sheets controllably bonded to a glass carrier. background

[0004] Flexible substrate materials offer the possibility of manufacturing cheaper devices using roll-to-roll processing, and the potential to produce thinner, lighter, more flexible, and durable displays. However, the technologies, equipment, and processes required for roll-to-roll processing of high-quality displays are not yet fully established. Because panel manufacturers have invested heavily in tooling for processing large glass sheets, laminating flexible substrates onto a carrier and fabricating display devices on flexible substrates through sheet-to-sheet processing offers a short-term solution for valuable initiatives to develop thinner, lighter, and more flexible displays. Displays on polymer sheets (e.g., polyethylene naphthalate (PEN)) have been validated, where device fabrication is a sheet-to-sheet form of PEN laminated onto a glass carrier. However, the temperature limits of PEN restrict device quality and the processes that can be used. Furthermore, the high permeability of polymer substrates leads to environmental degradation of organic light-emitting diode (OLED) devices, requiring near-hermetic encapsulation. Thin-film encapsulation offers the possibility of overcoming this limitation, but it has not yet been proven to provide acceptable yields at large volumes.

[0005] In a similar manner, display devices can be manufactured using glass carriers laminated onto one or more thin glass substrates. The low transmittance, improved temperature and chemical resistance of thin glass are expected to enable flexible displays with higher performance and longer lifespan.

[0006] In the fabrication of low-temperature polycrystalline silicon (LTPS) devices, vacuum and wet etching environments can be used, for example, at temperatures typically approaching 600°C or higher. These conditions limit the materials that can be used and place high demands on the carrier / sheet. Therefore, there is a need for a carrier method that utilizes the manufacturer's existing investment equipment to process thin glass (glass thickness ≤ 0.3 mm) without contamination or compromise of the bond strength between the thin glass and the carrier at higher processing temperatures, wherein, at the end of processing, the thin glass is easily detached from the carrier.

[0007] One commercial advantage is that manufacturers will be able to leverage their existing infrastructure investments in processing equipment while gaining access to thin glass sheets used in, for example, photovoltaic (PV) structures, OLEDs, liquid crystal displays (LCDs), and patterned thin-film transistor (TFT) electronics. Furthermore, this approach enables processing flexibility, including processes for cleaning and surface preparation of the glass sheets and carriers to facilitate bonding.

[0008] The challenge of known bonding methods lies in the high temperatures required for processing polycrystalline silicon TFTs. The demands for higher pixel density, higher resolution, and faster refresh rates in handheld, laptop, and desktop displays, along with the wider adoption of OLED displays, are driving panel manufacturers to shift from amorphous silicon TFT backplanes to oxide TFT or polycrystalline silicon TFT panels. This is because OLEDs are current-driven devices requiring high mobility. Polycrystalline silicon TFTs also offer the advantage of integrating driving and activation of other components. In polycrystalline silicon TFT processes, higher temperatures (ideally exceeding 600°C) are preferred for dopant activation. Summary of the Invention

[0009] Therefore, there is a need for a sheet-carrier article capable of withstanding the stringent conditions of TFT and flat panel display (FPD) processing, including high-temperature processing (without degassing incompatible with the semiconductor or display manufacturing process to which it will be used), and capable of removing the entire sheet area from the carrier (either all at once or in segments), thereby enabling the carrier to be reused for processing another sheet. This specification describes a method for controlling the adhesion between multiple sheet articles (e.g., carrier and sheet) and producing a temporary bond that is strong enough to withstand TFT and FPD processing (including processing at temperatures of about 300°C, about 400°C, about 500°C, and up to at least 600°C, including any range and subranges thereof), but weak enough to allow for the debonding of the sheet from the carrier, even after high-temperature processing. Such controlled bonding can be used to produce articles with reusable carriers, or articles with patterned areas of controlled bonding between the carrier and the sheet. More specifically, this disclosure provides coatings (including various materials and associated surface treatments) that can be applied to sheets and / or carriers to simultaneously control room-temperature van der Waals and / or hydrogen bonding as well as high-temperature covalent adhesion between the sheet and the carrier. Even more specifically, this disclosure describes coating deposition methods that can bond sheets to carriers, methods for preparing coatings for bonding, and methods for bonding coatings to both sheets and carriers. These methods produce adhesion between components such that the bond energy is not too high (which could make the components inseparable after electronic device processing) and not too low (which could lead to compromised bond quality, thus causing possible debonding or fluid ingress between the sheet and carrier during electronic device processing). These methods also produce glass articles that exhibit low degassing and withstand high-temperature processing (e.g., LTPS TFT processing and additional processing steps (e.g., wet cleaning and dry etching)). In alternative examples, coatings can be used to create a variety of controlled bonding regions (where the carrier and sheet maintain sufficient adhesion during various processing steps, including vacuum processing, wet processing, and / or ultrasonic cleaning) as well as covalently bonded regions to provide further processing options, such as maintaining hermeticity between the carrier and the sheet, even after the article has been cut into smaller pieces for additional device processing.

[0010] In the first aspect, it is an article comprising: The first sheet including the bonding surface of the first sheet, and A coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising a polymerized hydrogenated amorphous hydrocarbon compound, the coating having a refractive index higher than about 1.8.

[0011] In some examples of aspect 1, the refractive index of the coating is less than about 2.5.

[0012] In another example of aspect 1, the refractive index of the coating is about 1.9 to about 2.4.

[0013] In the second aspect, it is an article of manufacture comprising: The first sheet including the bonding surface of the first sheet, and A coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising a polymerized hydrogenated amorphous hydrocarbon compound, the coating having an optical band gap of less than 2 eV.

[0014] In some examples of aspect 2, the optical bandgap of the coating ranges from about 0.8 to about 2 eV.

[0015] In another example of aspect 2, the optical bandgap of the coating ranges from about 1.2 to about 1.8 eV.

[0016] In the third aspect, it is an article of manufacture comprising: The first sheet including the bonding surface of the first sheet, and A coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising a polymerized hydrogenated amorphous hydrocarbon compound, the coating having a Raman spectrum as follows: in the range of 1350 to 1400 cm⁻¹ -1 Peaks appearing within the range (D band) and 1530 to 1600 cm -1 The intensity ratio (D / G ratio) of the peaks (G bands) appearing within the range is approximately 0.5 to approximately 0.6.

[0017] In some examples of aspect 3, the intensity ratio (D / G ratio) can be in the range of about 0.52 to about 0.58.

[0018] In another example of aspect 3, for the Raman spectrum, the peak (D band) might be at approximately 1380 cm⁻¹. -1 And the peak (G band) is likely at approximately 1530 cm⁻¹. -1 .

[0019] In the fourth aspect, it is an article of manufacture comprising: A first sheet including the bonding surface of the first sheet; A coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising a polymerized hydrogenated amorphous hydrocarbon compound, the coating being formed by depositing a precursor compound having a hydrogen and carbon content greater than 90% by weight; and After holding the product in a nitrogen atmosphere at 600°C for 10 minutes, the adhesion energy between the first coating bonding surface and the first sheet bonding surface is less than 700 mJ / m. 2 .

[0020] In the fifth aspect, an article of any one of aspects 1-4 is provided, wherein a coating is formed by depositing a hydrocarbon compound having the chemical formula C. n H y , where n is 1 to 6 and y is 2 to 14.

[0021] In some examples of aspect 5, the surface energy of the first coating bonding surface is greater than about 50 mJ / m. 2 .

[0022] In another example of aspect 5, the surface energy of the first coating bonding surface is less than about 60 mJ / m. 2 .

[0023] In another example of aspect 5, the surface energy of the first coating bonding surface upon deposition is approximately 50 mJ / m. 2 Approximately 58 mJ / m 2 .

[0024] In another example of aspect 5, the hydrocarbon compound is an alkane selected from the group consisting of methane, ethane, propane, butane, pentane, and hexane.

[0025] In another example of aspect 5, the hydrocarbon compound is an olefin selected from the group consisting of ethylene, propylene, butene, pentene, and hexene.

[0026] In another example of aspect 5, the hydrocarbon compound is an alkyne selected from the group consisting of acetylene, propyne, butyne, pentyne, and hexyne.

[0027] In the sixth aspect, an article of any one of aspects 1-5 is provided, which further includes a second sheet comprising a second sheet bonding surface.

[0028] In some examples of aspect 6, the second coating bonding surface is bonded to the second sheet bonding surface.

[0029] In another example of aspect 6, the first sheet is a glass sheet.

[0030] In another example of aspect 6, the second sheet is a glass sheet.

[0031] In another example of aspect 6, the first sheet is a glass sheet, and the second sheet is a glass sheet.

[0032] In the seventh aspect, an article of any example of aspect 6 is provided, wherein the polymerized hydrocarbon compound is formed by depositing the hydrocarbon compound on the first sheet bonding surface or the second sheet bonding surface using low-pressure plasma chemical vapor deposition or atmospheric pressure plasma chemical vapor deposition.

[0033] In aspect 8, an article of any one of aspects 1-6 is provided, wherein the average thickness of the coating is less than 10 nm.

[0034] In aspect 9, an article of any one of aspects 1-6 is provided, wherein the average thickness of the coating is less than 5 nm.

[0035] In aspect 10, an article of any one of aspects 1-6 is provided, wherein the coating is a single layer.

[0036] In aspect 11, an article of any one of aspects 1-6 is provided, wherein the average thickness of the first sheet is greater than or equal to 200 μm.

[0037] In the 12th aspect, an article of any one of aspects 1-6 is provided, wherein after the article is held in a furnace at a temperature of 600°C in a nitrogen atmosphere for 10 minutes, the adhesion energy between the first coating bonding surface and the first sheet bonding surface is less than 600 mJ / m. 2 .

[0038] In aspect 13, an article of any one of aspects 1-6 is provided, wherein after the article is held in a furnace at a temperature of 500°C in a nitrogen atmosphere for 10 minutes, the adhesion energy between the first coating bonding surface and the first sheet bonding surface is less than 500 mJ / m. 2 .

[0039] In aspect 14, an article of any example of aspect 6 is provided, which, after being held in a furnace in a nitrogen atmosphere at a temperature of 600°C for 10 minutes, shows a change of less than 10% in the percentage bubble area of ​​the coating according to degassing test #1.

[0040] In aspect 15, an article of any one of aspects 1-6 is provided, wherein after the article is held in a furnace in a nitrogen atmosphere at a temperature of 500°C for 10 minutes, the percentage change in bubble area of ​​the coating is less than 10% according to degassing test #1.

[0041] In aspect 16, an article of any one of aspects 1-6 is provided, wherein after the article is held in a furnace in a nitrogen atmosphere at a temperature of 500°C for 10 minutes, the percentage change in bubble area of ​​the coating is less than 5% according to degassing test #1.

[0042] In the 17th aspect, an article of any one of aspects 12-16 is provided, wherein the first coating bonding surface is exposed to a nitrogen and oxygen atmosphere to increase the surface energy of the first coating bonding surface before the article is held in a furnace at a temperature of 500°C or higher in a nitrogen atmosphere for 10 minutes.

[0043] In the 18th aspect, there is a method for manufacturing an article of article, comprising: Plasma-chemical vapor deposition is used to form a coating containing polymerized hydrocarbon compounds on the bonding surface of a first sheet by depositing hydrocarbon compounds on the bonding surface of the first sheet. The coating includes a first coating bonding surface (bonded to the bonding surface of the first sheet) and a second coating bonding surface, and the hydrocarbon compound has the chemical formula C. n H y Where n is 1 to 6 and y is 2 to 14; and The second coating bonding surface is bonded to the second sheet bonding surface. After the product is held in a nitrogen atmosphere at 600°C for 10 minutes, the adhesion energy between the second coating bonding surface and the second sheet bonding surface is less than 700 mJ / m. 2 .

[0044] In some examples of aspect 18, the hydrocarbon compound is an alkane selected from the group consisting of methane, ethane, propane, butane, pentane, and hexane.

[0045] In another example of aspect 18, the hydrocarbon compound is an olefin selected from the group consisting of ethylene, propylene, butene, pentene, and hexene.

[0046] In another example of aspect 18, the hydrocarbon compound is an alkyne selected from the group consisting of acetylene, propyne, butyne, pentyne, and hexyne.

[0047] In another example of aspect 18, the polymerized hydrocarbon compound is a hydrogenated amorphous compound.

[0048] In another example of aspect 18, the first sheet is a glass sheet.

[0049] In another example of aspect 18, the second sheet is a glass sheet.

[0050] In another example of aspect 18, the first sheet is a glass sheet, and the second sheet is a glass sheet.

[0051] In the 19th aspect, an article of aspect 18 is provided, which further includes increasing the surface energy of the second coating bonding surface before bonding the second sheet bonding surface to the second coating bonding surface, wherein the surface energy is increased by exposing the second coating bonding surface to oxygen, nitrogen or a combination thereof.

[0052] In another example of aspect 19, the average thickness of the coating is less than 10 nm.

[0053] In another example of aspect 19, the average thickness of the coating is less than 5 nm.

[0054] In another example of aspect 19, the average thickness of the second sheet is less than or equal to 300 μm.

[0055] In another example of aspect 19, plasma chemical vapor deposition is either low-pressure plasma chemical vapor deposition or atmospheric-pressure plasma chemical vapor deposition.

[0056] In aspect 20, an article of aspect 19 is provided, wherein after the article is held in a furnace at a temperature of 500°C in a nitrogen atmosphere for 10 minutes, the adhesion energy between the second coating bonding surface and the second sheet bonding surface is less than 600 mJ / m. 2 .

[0057] In aspect 21, an article of aspect 19 is provided, wherein after the article is held in a furnace in a nitrogen atmosphere at a temperature of 600°C for 10 minutes, according to degassing test #1, the percentage change in bubble area of ​​the second coating is less than 10%.

[0058] In aspect 22, an article of aspect 19 is provided, wherein after the article is held in a furnace in a nitrogen atmosphere at a temperature of 500°C for 10 minutes, according to degassing test #1, the percentage change in bubble area of ​​the second coating is less than 10%.

[0059] In aspect 23, an article of aspect 19 is provided, wherein after the article is held in a furnace in a nitrogen atmosphere at a temperature of 500°C for 10 minutes, the percentage change in bubble area of ​​the second coating is less than 5% according to degassing test #1.

[0060] In aspect 24, an article of aspect 18 is provided, wherein the surface energy of the newly deposited adhesive surface of the second coating is greater than about 50 mJ / m 2 .

[0061] In aspect 25, an article of any one of aspects 18-23 is provided, wherein the coating has a refractive index higher than about 1.8 or 2.

[0062] In aspect 26, an article of any one of aspects 18-23 is provided, wherein the optical band gap of the coating is less than about 2 eV.

[0063] In aspect 27, an article of any one of aspects 18-23 is provided, wherein the Raman spectrum of the coating is in the range of 1350 to 1400 cm⁻¹. -1 Peaks appearing within the range (D band) and 1530 to 1600 cm -1 The intensity ratio (D / G ratio) of the peaks (G bands) appearing within the range is approximately 0.5 to approximately 0.6.

[0064] Any of the foregoing aspects (or examples of these aspects) may be provided alone or in combination with any one or more examples of the aspect described above; for example, the first aspect may be provided alone or in combination with any one or more examples of the first aspect described above; and the second aspect may be provided alone or in combination with any one or more examples of the second aspect described above, and so on.

[0065] The accompanying drawings are included to further understand the principles of this disclosure and are incorporated in and form part of this specification. The drawings illustrate examples and, together with the specification, serve to explain, for example, its principles and operation. It should be understood that the various features disclosed in this specification and the drawings can be used in any and all combinations. As a non-limiting example, the various features described above can be combined with each other as described in the following aspects. Attached Figure Description

[0066] Referring to the accompanying drawings and reading the following detailed description, a better understanding of the above and other features, examples, and advantages disclosed in this specification will be achieved, wherein: Figure 1 This is a side view of the article, which has a carrier bonded to a sheet, with a coating between them.

[0067] Figure 2 yes Figure 1 Exploded and partially sectional views of the product.

[0068] Figure 3 This is a graph showing the change in adhesion energy versus percentage bubble area for the bonding of a thin glass substrate with a hydrocarbon coating formed by hydrogenation amorphous plasma polymerization via methane precursors to a carrier.

[0069] Figure 4 This is a surface energy diagram before and after surface activation for hydrocarbon coatings formed by hydrogenated amorphous plasma polymerization via ethylene precursors.

[0070] Figure 5 This is a graph showing the change in adhesion energy versus percentage bubble area for the bonding of a thin glass substrate with a hydrocarbon coating formed by hydrogenation amorphous plasma polymerization via ethylene precursors to a carrier.

[0071] Figure 6 This is a graph showing the change in adhesion energy versus percentage bubble area for the bonding of a thin glass substrate with a hydrocarbon coating formed by hydrogenation amorphous plasma polymerization via ethylene precursors to a carrier.

[0072] Figure 7 This is a surface energy diagram of existing technology coatings formed using methane precursors.

[0073] Figure 8This is a Raman spectroscopy diagram of a hydrocarbon coating formed by hydrogenation amorphous plasma polymerization using ethylene precursors. Detailed Implementation

[0074] The examples will now be described in more complete detail with reference to the accompanying drawings. Whenever possible, the same reference numerals are used in all the drawings to denote the same or similar parts. However, the claimed subject matter can be implemented in many different ways and should not be construed as limited to the examples presented herein.

[0075] The directional terms used in this article (such as up, down, left, right, front, back, top, bottom) are only for reference to the accompanying drawings and are not used to indicate absolute orientation.

[0076] In this document, a range can be expressed as a range from "about" one specific value and / or to "about" another specific value. When representing such a range, another implementation includes a range from one specific value and / or to another specific value. Similarly, when the prefix "about" is used to indicate that a numerical value is an approximation, it should be understood that a specific numerical value forms another implementation. It should also be understood that the endpoint values ​​of each range are meaningful both in relation to and unrelated to another endpoint value.

[0077] A solution is provided for processing a second sheet on a first sheet, such that at least a portion (including at most all) of the second sheet (e.g., a thin film, such as a thin glass sheet) remains "unbonded," thereby allowing the device processed on the thin film to be removed from the first sheet (e.g., a carrier, such as a glass carrier). To maintain favorable surface shape characteristics, the carrier is typically a display-grade glass substrate. Therefore, in some cases, discarding the carrier after only one use is wasteful and costly. Consequently, to reduce display manufacturing costs, it is desirable to be able to reuse the carrier to process more than one thin film substrate. This document provides articles and methods that enable the wafer to be processed through the harsh environments of a processing line (e.g., TFTs, including high-temperature processing, wherein the high-temperature processing is carried out at temperatures ≥ 400°C and can vary depending on the type of device being manufactured, such as temperatures up to about 450°C in amorphous silicon or amorphous indium gallium zinc oxide (IGZO) backplane processing, up to about 500-550°C in crystalline IGZO processing, or up to about 600-650°C in typical LTPS and TFT processing), and still be able to easily remove the wafer from the carrier without damaging the wafer or the carrier (e.g., one of the carrier and the wafer breaks or fragments into two or more pieces), so that the carrier can be reused.

[0078] Glassware

[0079] like Figure 1 and 2As shown, article 2 (e.g., glass article) has a thickness of 8 and includes a first sheet 10 (e.g., a carrier having a thickness of 18), a second sheet 20 (e.g., a thin glass sheet having a thickness of 28), and a coating 30 (having a thickness of 38). The thickness 28 of the second sheet 20 may be, for example, equal to or less than about 300 micrometers (µm or μm), including but not limited to the following thicknesses, such as: about 10 to about 50 micrometers, about 50 to about 100 micrometers, about 100 to about 150 µm, about 150 to about 300 µm, about 300 µm, about 250 µm, about 200 µm, about 190 µm, about 180 µm, about 170 µm, about 160 µm, about 150 µm, about 140 µm, about 130 µm, about 120 µm, about 110 µm, about 100 µm, about 90 µm, about 80 µm, about 70 µm, about 60 µm, about 50 µm, about 40 µm, about 30 µm, about 20 µm, or about 10 µm, including any range and subranges therein.

[0080] The glass article 2 is arranged such that although the second sheet 20 itself is less than or equal to about 300 μm, it allows the second sheet 20 to be processed in equipment designed for thicker sheets (e.g., those about 0.4 mm or greater, such as 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm). The thickness 8, the sum of thicknesses 18, 28, and 38, can be equivalent to the thickness of a thicker sheet designed for processing with sheet processing equipment, for example, equipment designed for arranging electronic components on a substrate sheet. In some examples, if the processing equipment is designed for 700 μm sheets and the thickness 28 of the second sheet is 300 μm, then a thickness 18 of 400 μm would be chosen, assuming that the thickness 38 is negligible. That is, the coating 30 is not shown to scale; it is greatly enlarged merely for illustrative purposes. Furthermore, in Figure 2 The image shows a cross-sectional view of the coating. When a reusable carrier is provided, the coating is uniformly distributed on the bonding surface 14. Typically, the thickness 38 is in the nanometer range, for example, 2 nm to 250 nm, 5 nm to 100 nm, 8 nm to 80 nm, or 10 to 50 nm, or about 20, 30, or 40 nm. The presence of the coating can be detected by surface chemical analysis, such as by time-of-flight secondary ion mass spectrometry (ToF SIMS).

[0081] A first sheet 10, which can be used as, for example, a carrier, has a first surface 12, an adhesive surface 14, and a perimeter 16. The first sheet 10 can be any suitable material, including glass. The first sheet can be a non-glass material, such as ceramic, glass ceramic, silicon, or metal (because surface energy and / or adhesion can be controlled in a similar manner as described below with respect to glass carriers). If made of glass, the first sheet 10 can be of any suitable composition, including aluminosilicate, borosilicate, aluminoborosilicate, sodium calcium silicate, and depending on its end use, can be alkali-containing or alkali-free. Furthermore, in some examples, when made of glass, glass ceramic, or other materials, the adhesive surface of the first sheet can be formed as a coating or layer of metallic material disposed on the underlying bulk material of the first sheet. Thickness 18 can be from about 0.2 to about 3 mm or greater, for example, about 0.2 mm, about 0.3 mm, about 0.4 mm, about 0.5 mm, about 0.6 mm, about 0.65 mm, about 0.7 mm, about 1.0 mm, about 2.0 mm, or about 3.0 mm or greater, including any range and subranges therein, and will vary depending on thicknesses 28 and 38 (when thickness 38 is non-negligible), as described above. In some examples, the thickness 18 of the first sheet 10 can be greater than the thickness 28 of the second sheet 20. In some examples, thickness 18 can be less than thickness 28. In one embodiment, the first sheet 10 can be manufactured as a single layer (as shown) or as multiple layers (including multiple sheets) bonded together. In addition, the first sheet can be Gen 1 size or larger, such as Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or larger (e.g., sheet size is about 100 mm x 100 mm to about 3 m x 3 m, or larger).

[0082] The second sheet 20 has a first surface 22, an adhesive surface 24, and a perimeter 26. The perimeters 16 (first sheet 10) and 26 (second sheet 20) can be of any suitable shape, and can be identical or different from each other. Furthermore, the second sheet 20 can be any suitable material, including glass, ceramic, glass-ceramic, silicon, or metal. As described above with respect to the first sheet 10, when made of glass, the second sheet 20 can be of any suitable composition, including aluminosilicates, borosilicates, aluminoborosilicates, sodium-calcium silicates, and depending on its end use, can be alkali-containing or alkali-free. The coefficient of thermal expansion of the sheet can be matched substantially to the coefficient of thermal expansion of the first sheet to reduce any warping of the article during processing at elevated temperatures. The thickness 28 of the second sheet 20 is about 300 μm or less, for example, about 200 μm or about 100 μm, or the thickness described above. In addition, the second sheet 20 may be Gen 1 size or larger, such as Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or larger (e.g., sheet size is about 100 mm x 100 mm to about 3 m x 3 m, or larger).

[0083] Glass article 2 can have a thickness suitable for processing with existing equipment, and similarly, it can withstand the harsh environments in which it is processed. For example, flat panel display (FPD) processing can include wet ultrasonic processing, vacuum processing, and high-temperature processing (e.g., ≥ 400°C, ≥ 450°C, ≥ 500°C, ≥ 550°C, and up to at least 600°C), including any range and subranges therein.

[0084] To withstand the harsh environment in which article 2 will be processed, bonding surface 14 should bond to bonding surface 24 with sufficient strength to prevent the second sheet 20 from separating from the first sheet 10. This strength should be maintained throughout processing to prevent the second sheet 20 from separating from the first sheet 10 during processing. Furthermore, to allow the second sheet 20 to be removed from the first sheet 10 (so that the first sheet 10 can be reused, for example, as a carrier), the bond between bonding surface 14 and bonding surface 24 should not be too strong, in a manner that is achieved by the initially designed adhesive force and / or by adhesive forces that may arise due to modification of the initially designed adhesive force, for example, when the article is processed at high temperatures (e.g., temperatures ≥ about 400°C to about 500°C, ≥ 500°C to about 600°C, and at least 600°C, including any range and subranges therein). Coating 30 can be used to control the adhesive strength between bonding surface 14 and bonding surface 24, thereby achieving these objectives simultaneously. Controlled adhesive forces are achieved by controlling the contributions of van der Waals (and / or hydrogen bonding) and covalent attraction energies to the total adhesion energy, which is controlled by adjusting the polar and nonpolar surface energy components of the first sheet 10 and the second sheet 20. Alternatively, coating 30 may completely cover one bonding surface of a sheet (e.g., bonding surface 14) and present a coated bonding surface for coupling to another bonding surface of the other sheet (e.g., bonding surface 24) (whose properties are independent of those on said bonding surface). This controlled adhesion is strong enough to withstand FPD processing, including temperatures ≥ 400°C, and in some cases, processing temperatures ≥ 500°C, ≥ 550°C, and up to at least 600°C (inclusive of any range and subranges therein), and still remain detachable by applying forces sufficient to separate the sheets without causing significant damage to the first sheet 10 and / or the second sheet 20. For example, the applied force should not cause the first sheet 10 or the second sheet 20 to crack. This type of debonding enables the removal of the second sheet 20 and the device manufactured thereon, and also enables the reuse of the first sheet 10 as a carrier.

[0085] Although coating 30 is shown as a solid layer between sheet 20 and sheet 10, this is not necessarily the case. For example, the thickness of layer 30 can be approximately 0.1 nm to about 1 µm (e.g., about 1 nm to about 10 nm, about 10 nm to about 50 nm, about 50 nm to about 100 nm, about 250 nm, about 500 nm to about 1 µm), and may not completely cover the entire portion of bonding surface 14. For example, the coverage on bonding surface 14 can be ≤ about 100%, about 1% to about 100%, about 10% to about 100%, about 20% to about 90%, or about 50% to about 90%, including any range and subranges therein. In other examples, layer 30 can be up to about 50 nm thick, or in other examples, even up to about 100 nm to about 250 nm thick. Coating 30 can be considered to be disposed between sheet 10 and sheet 20, even if it may not be in contact with one or the other of sheet 10 and sheet 20. In other examples, coating 30 modifies the ability of bonding surfaces 14 and 24 to bond, thereby controlling the bond strength between sheet 10 and sheet 20. The material and thickness of coating 30, as well as the treatment of bonding surfaces 14 and 24 prior to bonding, can be used to control the bond strength (adhesive energy) between sheet 10 and sheet 20.

[0086] Coating composition

[0087] Examples of coatings include hydrocarbon polymers. Preferably, the hydrocarbon polymer is a hydrogenated amorphous hydrocarbon polymer. Such hydrocarbon polymers can be formed by depositing hydrocarbon precursor compounds on a first sheet (e.g., a carrier) or a second sheet (e.g., a thin film).

[0088] A group of hydrocarbon precursor compounds are those with the chemical formula C n H y The compound, wherein n is 1 to 6 and y is 2 to 14. In some examples, n is 1 to 4 and y is 2 to 10. The hydrocarbon compound may be straight-chain or branched. In some examples, the total carbon and hydrogen content of the coating formed by depositing the hydrocarbon precursor compound is at least 80% by weight, at least 85% by weight, at least 90% by weight, or at least 95% by weight. In some examples, the total carbon and hydrogen content of the precursor compound deposited to form the coating is at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99% by weight, or greater than 99.5% by weight.

[0089] Examples of hydrocarbon precursor compounds include alkanes. Alkanes can include methane, ethane, propane, butane, pentane, and hexane. In some examples, hydrocarbon precursor compounds include at least one carbon-carbon double bond, such as alkenes. Alkenes can include ethylene, propylene, butene, pentene, and hexene. The carbon-carbon double bond in an alkene can be present in various positions within the compound, for example, but-1-ene or but-2-ene. In other examples, hydrocarbon precursor compounds include at least one carbon-carbon triple bond, such as alkynes. Alkynes can include acetylene, propyne, butyne, pentyne, and hexyne. In some examples, the carbon-carbon triple bond in an alkyne can be present in various positions within the compound, for example, 1-butyne or 2-butyne.

[0090] The coating may comprise a single layer. Preferably, the coating thickness is less than 50 nm, for example, less than about 40 nm, less than about 30 nm, less than about 20 nm, less than about 15 nm, less than about 12 nm, less than about 10 nm, less than about 8 nm, or less than about 5 nm.

[0091] The coating is preferably a hydrogenated amorphous plasma-polymerized hydrocarbon compound possessing certain properties. The optical properties of the coating are obtained from spectral elliptic data using the Tauc-Lorentz model (J. Tauc, R. Grigorovici, A. Vancu, “Optical properties and electronic structure of amorphous germanium”, Phys. Status Solidi B, 15 (1996)). In some examples, the refractive index of the coating is about 1.8 to about 2.5, for example, about 1.9 to about 2.4, or equal to or greater than about 2, or equal to or greater than about 2.1, or equal to or greater than about 2.2, or equal to or greater than about 2.3. The refractive index of the hydrogenated amorphous plasma-polymerized hydrocarbon coating on the carrier sheet is determined using a Wollam variable-angle elliptic spectrophotometer. The refractive index is determined at 20°C for light with a wavelength of 632 nm. In another embodiment, the coating may possess one or more photoelectronic properties. These photoelectronic properties can originate from small band gaps ranging from about 0.8 eV to less than about 2 eV, for example, from about 1.2 eV to about 1.8 eV or from about 1.4 eV to about 1.6 eV. Photoelectronic properties can include, for example, absorption, transmission, or emission of light.

[0092] In some cases, Raman spectroscopy is used to characterize the coating. In amorphous diamond-like carbon films, Raman spectroscopy is a preferred method for determining film properties; for example, the Raman spectrum of the film may show two distinct peaks. The Raman spectrum can include a G-band peak and a defect band or D-band peak. For 532 nm excitation, the G-band peak can be from about 1530 to about 1600 cm⁻¹. -1 And the D-band peak can be from about 1350 to about 1400 cm⁻¹. -1 In one example, with excitation at 532 nm, the D-band peak 114 can be approximately 1375 cm⁻¹. -1 Approximately 1380cm -1 And the G-band peak can be approximately 1530 cm⁻¹ -1 Approximately 1535 cm -1 In another example, with excitation at 532 nm, the D-band peak can be around 1378 cm⁻¹. -1 And the G-band peak can be approximately 1533 cm⁻¹ -1 .

[0093] The parameters of the G-band and D-band peaks (e.g., position, width, and intensity ratio) can be used to characterize the coating compound. The G-band can have an intensity equal to that of the G-band peak (Ig). G The G-band amplitude, and the D-band can have an intensity equal to the D-band peak (I) D The D-band amplitude of the G-band can be determined. This allows us to determine the ratio (I) of the D-band amplitude to the G-band amplitude. D / I G The ratio (or D / G) is equal to the Raman graphitization ratio of the material. In some examples, the D / G ratio of the coating can be from about 0.5 to about 0.6, from about 0.52 to about 0.58, or from about 0.54 to about 0.56.

[0094] Deposition of coating

[0095] Examples of coating methods for providing coating 30 include chemical vapor deposition (CVD) techniques. Specific examples of CVD techniques include: CVD, low-pressure CVD, atmospheric pressure CVD, plasma-enhanced CVD (PECVD), atmospheric plasma CVD, atomic layer deposition (ALD), plasma ALD, and chemical beam epitaxy. In another example, the coating can be deposited using a pyrolytic torch at temperatures above 600°C, above 800°C, or above 1000°C (inclusive of any range and subranges therebetween).

[0096] The gas mixture used to form the coating (which contains hydrocarbon compounds) may also contain controlled amounts of another compound (e.g., a carrier gas or working gas). This other compound may include air, oxygen, nitrous oxide, carbon dioxide, water vapor, or hydrogen peroxide, and / or one or more inert gases, such as helium, neon, argon, krypton, or xenon.

[0097] Surface energy of coating

[0098] The coating can provide a surface energy of approximately 48 to approximately 75 mJ / m 2 The bonding surface, which is measured from a surface (including polar components and dispersion separation).

[0099] Typically, the surface energy of the coating can be measured during deposition and / or after further processing (e.g., activation with nitrogen or a mixture of nitrogen and oxygen). The surface energy of a freshly deposited coating before any further surface activation step is approximately 48 to approximately 60 mJ / m². 2 Or approximately 50 to approximately 58 mJ / m 2 or equal to or greater than approximately 50 mJ / m 2 or equal to or less than approximately 60 mJ / m 2 For example, after further processing, the surface energy can be increased to less than or equal to about 75 mJ / m². 2 This provides excellent self-propagating adhesion to the glass sheet, resulting in reasonable and cost-effective production times for the component. Two surface energy ranges (freshly deposited (meaning after layer deposition without any further treatment) and after further treatment) also effectively control high-temperature adhesion, preventing permanent bonding between the two components.

[0100] The surface energy of a solid surface is indirectly measured by measuring the static contact angles of three liquids (water, diiodomethane, and hexadecane) deposited individually in air onto the solid surface. The surface energy, as described herein, is determined according to the Wu model as described below. (See S. Wu, J. Polym. Sci. C, 34, 19, 1971) In the Wu model, the surface energy (including total surface energy, polar component, and dispersive component) is measured by fitting the three contact angles of the three test liquids (water, diiodomethane, and hexadecane) to the theoretical model. Regression analysis is performed from the contact angle values ​​of these three liquids to calculate the polar and dispersive components of the solid surface energy. The theoretical model used to calculate the surface energy values ​​comprises three independent equations relating to the three contact angle values ​​of the three liquids and the dispersive and polar components of the surface energy of the solid surface (denoted by the subscript "S") and the three test liquids:

[0101] In the formula, the subscripts "W", "D", and "H" refer to water, diiodomethane, and hexadecane, respectively, and the superscripts "d" and "p" represent the dispersive and polar components of the surface energy, respectively. Since diiodomethane and hexadecane are essentially nonpolar liquids, the above equation simplifies to:

[0102] For the three sets of equations (4-6) above, regression analysis can be used to calculate two unknown parameters: the dispersive surface energy component and the polar surface energy component of the solid surface, γ. S d and γ S p However, this method has a limiting maximum value, making it impossible to measure the surface energy of solid surfaces above this value. This limiting maximum value is the surface tension of water, approximately 73 mJ / m². 2 If the surface energy of a solid surface is significantly greater than the surface tension of water, the surface will be completely wetted by water, resulting in a contact angle close to zero. Therefore, beyond this surface energy value, regardless of the actual surface energy value, all calculated surface energy values ​​will correspond to approximately 73-75 mJ / m². 2 For example, if the actual surface energy of two solid surfaces is 75 mJ / m 2 and 150 mJ / m 2 The calculated liquid contact angle for both surfaces would then be approximately 75 mJ / m. 2 .

[0103] Therefore, all contact angles disclosed in this paper are measured by placing a droplet on a solid surface in air and measuring the angle between the solid surface and the liquid-air interface at the contact line. Thus, when the claimed surface energy value is 55 mJ / m... 2 Up to 75 mJ / m 2 It should be understood that these values ​​correspond to surface energy values ​​calculated using the method described above, not actual surface energy values ​​(when the calculated value is close to the actual surface energy value, the actual surface energy value may be greater than 75 mJ / m). 2 ).

[0104] Surface activation of coatings

[0105] The surface energy required for adhesion may not be achieved by the surface energy of the initially deposited hydrocarbon coating. Therefore, the deposited coating may optionally undergo further processing. For example, after coating 30 is deposited, one or more functional groups may optionally be added to increase the coating's additional adhesion capabilities. For example, adding functional groups may provide additional bonding sites between the coating and the second sheet 20. The functional groups may be added using plasma (e.g., atmospheric or low-pressure plasma). The functional groups are preferably polar and may be added using precursors (e.g., hydrogen, carbon dioxide, nitrogen, nitrous oxide, ammonia, acrylic acid, allylamine, allyl alcohol, or mixtures thereof).

[0106] The adhesion strength between the first or second sheet and the coating

[0107] Generally, the adhesive energy (i.e., bond strength) between two surfaces can be measured using the double cantilever beam method or the wedge test. The test quantitatively simulates the forces and effects of adhesive bonding at the coating / first sheet or second sheet interface. The wedge test is commonly used to measure bond strength. For example, ASTM D5041, Standard Test Method for Fracture Strength in Cleavage of Adhesives in Bonded Joints, and ASTM D3762, Standard Test Method for Adhesive-Bonded Surface Durability of Aluminum, are standard test methods for measuring substrate adhesion using wedges.

[0108] Based on the ASTM method described above, the outline of the test method for determining bond strength includes recording the temperature and relative humidity of the testing location (e.g., in a laboratory). Gently pre-crack or separate the second sheet at a corner of the glass article to disrupt the bond between the first and second sheets. A sharp blade can be used to pre-crack the second sheet from the first sheet, for example, a GEM brand blade with a thickness of 228 ± 20 micrometers. During pre-crack formation, momentary sustained pressure may be required to induce bond fatigue. Slowly insert a flat blade with the aluminum tag removed until crack tip propagation can be observed, thereby increasing cracking and separation. It is not necessary to explicitly insert the flat blade to induce cracking. Once a crack has formed, allow the glass article to stand for at least 5 minutes to allow for crack stabilization. For high humidity environments (e.g., greater than 50% relative humidity), a longer standing time may be required.

[0109] The glass article with the crack was evaluated under a microscope to record the crack length. The crack length was recorded from the separation point of the second sheet from the first sheet (i.e., the separation point farthest from the blade tip) and the closest non-conical portion of the blade. The recorded crack lengths were used to calculate the bond energy using the following equation.

[0110] (7)

[0111] Where γ represents the bonding energy, t b E1 represents the thickness of the blade, cutting edge, or wedge, and t represents the Young's modulus of the first sheet 10 (e.g., a glass carrier). w1 E2 represents the thickness of the first sheet, E2 represents the Young's modulus of the second sheet 20 (e.g., a thin glass sheet), and t w2 The thickness of the second sheet 20 is indicated by L, and L is the crack length between the first sheet 10 and the second sheet 20 after the sharp blade is inserted, as described above.

[0112] The bonding energy in silicon wafer bonding is considered to behave as follows: the initial hydrogen bond pairs of the wafer are heated to the point that many or all of the silanol-silanol hydrogen bonds are converted into Si-O-Si covalent bonds. Although the initial, room-temperature hydrogen bond formation is approximately 100-200 mJ / m², the bonding energy is still relatively low. 2 With a bonding energy of approximately 2000-3000 mJ / m², fully covalently bonded wafer pairs achieved during processing at approximately 400 to 800°C exhibit bonding energy (allowing for separation of the bonded surfaces). 2 The adhesive energy (which does not allow separation of the bonded surfaces); instead, the two wafers are as a whole. On the other hand, if both surfaces are perfectly coated with a low surface energy material (e.g., a fluoropolymer) of sufficient thickness to shield the influence of the underlying substrate, the adhesive energy will be the adhesive energy of the coating material and will be very low, resulting in low or no adhesion between the bonded surfaces. Therefore, it is impossible to process the second sheet 20 (e.g., a thin glass sheet) on the first sheet 10 (e.g., a carrier) without adhesive failure and potential damage to the second sheet. Consider two extreme cases: (a) two standard clean 1 (SC1, known in the art), cleaned glass surfaces filled with silanol groups are bonded together by hydrogen bonding at room temperature (adhesive energy is approximately 100-200 mJ / m). 2 Then, by heating to a high temperature, it converts the silanol groups into covalent Si-O-Si bonds (the bonding energy becomes 2000-3000 mJ / m). 2 The latter has an adhesion energy that is too high for the glass surfaces to be separated; and (b) a perfectly coated surface has a low adhesion energy (approximately 12-20 mJ / m). 2Two glass surfaces of a fluoropolymer (each surface) are bonded at room temperature and then heated to a high temperature. In the latter (b) case, not only do the surfaces not bond at a low temperature (because when the surfaces are placed together, the temperature is approximately 24-40 mJ / m²), but the bonding temperature is also significantly lower. 2 (The total adhesive energy is too low), and they also fail to bond at high temperatures because there are too few polar reactive groups. Between these two extremes, there exists, for example, 50-1000 mJ / m 2 The adhesive energy range allows for controlled bonding of the desired degree. Therefore, the inventors have discovered various methods for providing coatings with adhesive energy between these two extremes, thereby producing controlled bonding sufficient to maintain the bonded sheet pair (e.g., a glass carrier and a thin glass sheet) under the harsh conditions of FPD processing, but to a degree that (even after high-temperature processing, such as ≥ 400°C, ≥ 500°C, and at least 600°C) allows for separation of the first sheet (e.g., the carrier) from the second sheet (e.g., the sheet) after processing is complete. Furthermore, the separation of the first sheet from the second sheet can be performed by mechanical force in a manner that at least does not cause significant damage to the first sheet (preferably also to the second sheet).

[0113] Suitable bond energy can be achieved by using a selected surface modifier (i.e., surface heat treatment or nitrogen treatment prior to coating and / or bonding). Suitable bond energy can be obtained by selecting a chemical modifier for bonding surfaces 14 and / or 24 that simultaneously controls van der Waals (and / or hydrogen bonding, these terms are used interchangeably throughout this specification) bond energy as well as possible covalent bonding bond energy resulting from high-temperature processing (e.g., approximately ≥ 400°C, ≥ 500°C, and at least 600°C).

[0114] In some examples, after holding the article in an inert atmosphere (e.g., nitrogen atmosphere) at a temperature of 500°C, 550°C, 600°C, or 650°C (inclusive of any range and subranges therein) for 10 minutes, the coating may have an adhesive surface that bonds to the first or second sheet, with an adhesive energy equal to or less than 700 mJ / m 2 650 mJ / m 2 600 mJ / m 2 550 mJ / m 2 or equal to or less than 500 mJ / m 2(Including any range and subranges thereof). As used herein, the bond energy is measured by placing the article in an oven chamber, heating the oven to the test temperature (e.g., 600°C) at a rate of 9°C / min, holding the article at the test temperature for 10 minutes (preferably in an inert atmosphere, such as nitrogen), cooling the oven chamber to about 200°C over a period of about 1 minute, and then removing the article from the oven chamber and allowing it to cool to room temperature. This testing process for the article may also be referred to as subjecting the article to a thermal test cycle.

[0115] Production of products

[0116] For the production of articles (e.g., glass articles), a coating 30 is formed on one of the sheets (preferably the first sheet 10, such as a carrier). If desired, the coating 30 can be subjected to steps such as surface activation (optionally also annealing) to increase surface energy, reduce degassing during processing, and increase the adhesion of the coating 30, as described herein. For bonding with other sheets (e.g., the second sheet 20), the other sheets come into contact with the coating 30. If the coating 30 has a sufficiently high surface energy, introducing the other sheets into the coating 30 will cause the other sheets to undergo self-propagating bonding with the coating 30. Self-propagating bonding is advantageous for reducing assembly time and / or cost. However, if self-propagating bonding does not occur, additional techniques can be used to bond the other sheets to the coating 30, such as lamination, for example, pressing the sheets with rollers or bonding two sheets of material in contact using other techniques known in the field of lamination.

[0117] Degassing of coating

[0118] Polymer adhesives used in typical wafer bonding applications are typically 10-100 μm thick, losing about 5% of their mass at or near their temperature limits. For such materials derived from thick polymer films, mass loss or degassing can be readily quantified by mass spectrometry. On the other hand, measuring degassing of thin surface treatments with a thickness of less than or equal to about 10 to about 100 nm is more challenging, such as plasma-polymerized coatings and thin layers of pyrolytic silicone oils, as described above. For such materials, mass spectrometry is not sensitive enough. However, many other methods exist for measuring degassing.

[0119] Test #1 for measuring small amounts of degassing is based on an assembled article, i.e., a thin glass sheet is bonded to a glass carrier by the coating under test, and degassing is determined using the percentage change in bubbles or bubble area. Bubbles formed between the carrier and the sheet during the heating of the glass article indicate degassing of the coating. Degassing under the sheet may be limited by strong adhesion between the sheet and the carrier. However, layers ≤ 10 nm thick (e.g., plasma-polymerized materials) may still generate bubbles during heat treatment, even with small absolute mass losses. Furthermore, bubble formation between the sheet and the carrier can lead to problems with patterning, photolithography, and / or alignment issues during device fabrication onto the sheet. Additionally, blistering at the boundary of the bonded area between the sheet and the carrier can cause problems such as processing fluid from one process entering the bubbles in that process, leaving bubbles in downstream processes, thus contaminating downstream processes. A bubble area percentage change ≥ 10 or ≥ 5 is significant, indicating degassing and is undesirable. On the other hand, a bubble area percentage change ≤ 3 or ≤ 1 is not significant, indicating no degassing.

[0120] In a Class 1000 cleanroom for manual bonding, the average bubble area of ​​the bonded glass slides was approximately 1%. The percentage of bubbles in the bonded sheets is related to the cleanliness of the first sheet, the second sheet, and the surface preparation. Because these initial defects act as nucleation sites for bubble growth after heat treatment, any variation in bubble area of ​​less than approximately 1% after heat treatment falls within the variability of sample preparation. To perform this test, a commercially available desktop scanner with a transparent unit (Epson Expression 10000XL Photo) was used to obtain the first scanned image of the bonded area immediately following the bonding of the first and second sheets. Standard Epson software was used to scan the artifacts at 508 dpi (50 μm / pixel) and 24-bit RGB. If necessary, the image processing software first prepared the image by stitching images of different segments of the sample into a single image and removing scanner artifacts (using a calibration reference scanned without the sample in the scanner). The bonded areas were then analyzed using standard image processing techniques, such as thresholding, well filling, erosion / expansion, and stain analysis. A similar approach was taken using an Epson Rapid 11000XL radiograph. In transmission mode, bubbles in the bonded areas were visually visible in the scanned images, allowing for the determination of bubble area values. The bubble area was then compared to the total bonded area (i.e., the total overlap between the sheet and the carrier) to calculate the percentage area of ​​bubbles in the bonded areas relative to the total bonded area. The samples were then heat-treated in a N2 atmosphere at test limits of 300°C, 400°C, 500°C, and 600°C using an MPT-RTP600s rapid thermal processing system (purchased from Modular Process Technology, MPT, office in San Jose, CA) for up to 10 minutes. Specifically, the time-temperature cycle involved the following steps: inserting the article into a heating chamber at room temperature and atmospheric pressure; then heating the chamber to the test limit temperature at a rate of 9°C / min; holding the chamber at the test limit temperature for 10 minutes; then cooling the chamber to 200°C at a furnace rate in approximately 1 minute; removing the article from the chamber and cooling it to room temperature; and then scanning the article a second time using an optical scanner. The percentage bubble area of ​​the second scan was then calculated as described above and compared with the percentage bubble area of ​​the first scan to determine the change in percentage bubble area. As mentioned above, a change in bubble area of ​​≥10% is significant, indicating degassing. Due to the variability of the original percentage bubble area, the change in percentage bubble area was chosen as the measurement standard. That is, after the preparation of the sheet and carrier and before their bonding, due to processing and cleaning, most of the coating has approximately 2% bubble area in the first scan.However, variations may exist between materials.

[0121] The measured percentage bubble area (represented as a change in the percentage of bubble area) can also be characterized as the percentage of the total surface area of ​​the coating bonding surface that is not in contact with the first sheet. As described above, it is desirable that after the glass article undergoes the following temperature cycling, the percentage of the total surface area of ​​the coating bonding surface that is not in contact with the first sheet is less than 10%, less than 5%, less than 3%, less than 1%, and at most less than 0.5%. This temperature cycling involves heating the glass article in a chamber at a rate of 9°C / min from room temperature to 500°C, 600°C, 650°C, and at most 700°C (inclusive of any range and subranges therein), then holding the test temperature for 10 minutes, followed by allowing the chamber to cool to approximately 200°C in approximately 1 minute, and then removing the glass article from the chamber and allowing it to cool to room temperature. The coating described herein enables the glass article to separate from the second sheet after undergoing the temperature cycling and thermal testing described above, without causing the first sheet to break into two or more pieces.

[0122] glass processing

[0123] Controlled bonding regions can be achieved using coatings and suitable bonding surface preparations. These bonding regions provide room-temperature bonding between the first and second sheets, sufficient to allow the article to be processed using FPD-type processes (including vacuum and wet processes) and to control (even at elevated temperatures) the covalent bonding between the first and second sheets. This allows for the removal of the first sheet from the second sheet after high-temperature processing of the article (e.g., FPD-type processing or LTPS processing) without damaging the sheet. To evaluate possible bonding surface preparations and coatings with various bonding energies (which would provide a reusable carrier suitable for FPD processing), a series of tests were used to assess their respective suitability. Different FPD applications have different requirements, but LTPS and oxide TFT processes appear to be the most demanding. Therefore, representative steps in these processes were selected for testing, as they represent the applications required for article 2. In the oxide TFT process, annealing at 400°C was used, while in LTPS processing, crystallization and dopant activation steps exceeding 600°C were used. Therefore, the following tests are performed to evaluate the possibility that specific bonding surface preparation and coating will allow the sheet to remain bonded to the carrier throughout the FPD process, while allowing the sheet to be removed from the carrier (without damaging the sheet and / or the carrier) after such processing (including processing at temperatures ≥ 400°C and up to less than 700°C).

[0124] Example

[0125] Example 1

[0126] Methane precursor compounds were deposited as a coating on Corning® EAGLE XG® alkaline-free display glass with a thickness of approximately 0.7 mm. Deposition was performed using a linear atmospheric pressure plasma head at a power of 400 to 750 watts and a frequency of 13.56 MHz, at a rate of 50 to 100 sccm, and at room temperature, with a methane / helium carrier of approximately 1 wt%. The coating was deposited using a scan rate of 20 to 60 mm / s, and the plasma head was positioned at a distance of 10 to 30 mm from the display glass. The coated carrier was then bonded to a clean 100 μm thin glass sheet (made by Corning® Willow®). Prior to bonding, the Willow® glass was cleaned and well rinsed in 2% Semiclean KG at 65°C on a typical display cleaning line, cleaned in diluted SC1 (40:1:2 DI:JTB111:H2O2 (30%) 65°C / 10 min), and swirl-rinsed and dried.

[0127] Figure 3 This shows the bonding energy (mJ / m) between the first and second glass articles. 2 (Left Y-axis, solid diamond data points) and degassing (percentage change in bubble area, right Y-axis, solid square data points). The first glass article includes a first methane coating with a thickness of less than about 3 nm deposited at 25°C (1 scan), and the second glass article includes a second methane coating with a thickness of less than about 5 nm deposited at 25°C (2 scans). Both the first and second glass articles include a thin glass sheet (100 μm thick) attached to the carrier via the respective coating. Due to deposition, the first and second methane coatings generate approximately 577 mJ / m² between the thin glass sheet and the carrier, respectively. 2 and 439 mJ / m 2 The bonding energy was measured after the glass article was held in a furnace at 600°C in a nitrogen atmosphere for 10 minutes. The bonding energy was measured using the wedge insertion method as described above. Due to deposition, the first and second methane coatings exhibited bubble area changes of approximately 2.45% and 2.95%, respectively, after the glass article was held in a furnace at 600°C in a nitrogen atmosphere for 10 minutes, consistent with minimal to no degassing. The bubble area was determined using test #1. It can be seen that as the bonding energy decreases, the bubble area increases, indicating a decrease in the percentage of the thin glass sheet bonded to the coating surface. However, the bubble area is less than 5%, and this material is useful at temperatures up to at least approximately 600°C.

[0128] For the 1-scan coating, the measured surface energy immediately after deposition is 51.94 mJ / m². 2And for the 2-scan coating, it is 44.81 mJ / m 2 .

[0129] Figure 7 This shows a comparison of surface energies across the coating thickness range for methane deposition as disclosed in WO 2015 / 112958, where the surface energies are much lower than 49 mJ / m. 2 Furthermore, the effect decreases significantly with increasing thickness.

[0130] The optical bandgap of the coating in Example 1 was measured to be approximately 1.53 eV.

[0131] Comparative Example 2

[0132] Methane precursor compounds were deposited as a coating on Corning® EAGLE XG® alkali-free display glass with a thickness of approximately 0.7 mm. The coating was deposited in a Plasmatherm HDPCVD apparatus using a gas source of 20 standard cubic centimeters per minute (sccm) of C2H4 and 40 sccm of H2. The coating deposition time was 180 seconds, with a chamber pressure of 5 mT, a power of 1500 W, and frequencies applied to the coil at 2 kHz and to the stage at 13.56 MHz.

[0133] The coating was characterized by contact angle measurements using a Kruss goniometer (purchased from Kruss GmbH, Hamburg, Germany) with water, hexadecane, and diiodomethane fluids, and fitted with a Wu model. The coating thickness was measured using a Wollam spectroellipsometry spectrophotometer (purchased from JA Wollam Co., Lincoln, NE). The thickness of the freshly deposited coating was measured to be approximately 782 angstroms (approximately 78.2 nm). The measured surface energy of the freshly deposited coating was 46.7 mJ / m². 2 The measured surface energy was much lower than the 51.94 mJ / m² of the 1-scan coating in Example 1. 2 The surface energy of the coating was measured to be approximately 3.27 eV. This is significantly higher than the 1.53 eV optical band gap of the coating in Example 1.

[0134] Example 3

[0135] A plasma-polymerized ethylene coating was deposited on a 0.7 mm thick EAGLE XG® support using a Nextral NE5000 parallel-plate reactive ion etching (RIE) machine (purchased from Corial, headquartered in Benin, France) with an ethylene and hydrogen source. Deposition conditions were as follows: chamber pressure 30 mT, power 500 W, 8 standard cubic centimeters per minute (sccm) of C2H4 and 92 sccm of H2, and a stage temperature of 40°C. The freshly deposited coating was then surface-activated with a nitrogen and oxygen mixture of 25 sccm N2 and 25 sccm O2 at 10 mT and 500 W. The coated support was then bonded to a clean 100 μm thin glass slide (made by Corning® Willow®). Prior to bonding, Willow® glass is cleaned and well rinsed in 2% Semiclean KG at 65°C on a typical display cleaning line, cleaned in diluted SC1 (40:1:2 DI:JTB111:H2O2 (30%) 65°C / 10 min), and swirl-rinse and dried.

[0136] The coating was characterized by contact angle measurements using a Kruss goniometer (purchased from Kruss GmbH, Hamburg, Germany) with fluids of water, hexadecane, and diiodomethane, and fitted with a Wu model. Coating thickness was measured using a Wollam spectroellipsometry spectrophotometer (purchased from JA Wollam Co., Lincoln, Nebraska, NE), while roughness and dispersion were measured using the Tauc Lorentz model. Refractive index and thickness were also measured using an n&k analyzer with a single FK oscillator model included in the accompanying software. Bond energy was measured using the wedge insertion method as described above.

[0137] Figure 4 This figure shows the change in surface energy of the coating before bonding to the thin glass and during activation with a nitrogen and oxygen mixture. In this figure, solid diamond data points represent the thickness (in angstroms, "A") on the left Y-axis scale, and solid square data points represent the surface energy (in mJ / m²) on the right Y-axis scale. 2 The thickness of the freshly deposited coating is approximately 103 angstroms (approximately 10.3 nm), and the surface energy of the freshly deposited coating (at time 0) is approximately 54 mJ / m². 2 Activation with nitrogen and oxygen for 5 seconds ("s") increases the surface energy to approximately 72 mJ / m. 2The thickness is reduced to approximately 97 angstroms (approximately 9.7 nm). Therefore, the longer N2-O2 exposure time results in a reduced thickness and an increased surface energy.

[0138] Figure 5 The bonding energy (mJ / m²) of glass articles containing vinyl coatings with thicknesses of approximately 37 angstroms (approximately 3.7 nm), 44 angstroms (approximately 4.4 nm), and 46 angstroms (approximately 4.6 nm) is shown. 2 (Left Y-axis, solid diamond data points) and degassing (percentage change in bubble area, right Y-axis, solid square data points). The glass articles were held in a furnace at 500°C in a nitrogen atmosphere for 10 minutes. The furnace was heated to the test temperature of 500°C at a rate of 9°C / min, and after 10 minutes at the test temperature, the furnace was cooled to approximately 200°C in approximately 1 minute. The glass articles were then removed and allowed to cool to room temperature. The coating at a thickness of approximately 3.7 nm produced approximately 500 mJ / m². 2 The bonding energy generates approximately 325 mJ / m at a layer thickness of approximately 4.4 nm. 2 The bonding energy, and the generation of approximately 275 mJ / m at a layer thickness of approximately 4.6 nm. 2 The coating exhibits approximately 0% bubble area change at a layer thickness of approximately 3.7 nm, approximately 1% bubble area change at a layer thickness of approximately 4.4 nm, and approximately 8.5% bubble area change at a layer thickness of approximately 4.6 nm, all of which are consistent with no degassing. Coatings with thicknesses from approximately 3.5 nm to approximately 4.5 nm provide a favorable combination of adhesion energy (high enough to allow articles to be processed in display manufacturing processes without separation, but low enough after the required heat treatment to allow sheet separation without breakage) and low degassing (measured by bubble area change) to avoid processing contamination.

[0139] Figure 6 This displays the bonding energy (mJ / m²) of glass articles containing a vinyl coating over a temperature range. 2 (Left Y-axis, solid diamond data points) and degassing (percentage change in bubble area, right Y-axis, solid square data points). The glass was held at each specified temperature for 10 minutes (in a nitrogen atmosphere), and the coating had a thickness of approximately 44 angstroms (approximately 4.4 nm). The coating produced the following adhesion energy: approximately 250 mJ / m at approximately 25°C (room temperature). 2 Approximately 400 mJ / m after thermal testing cycles to approximately 300°C. 2 Approximately 515 mJ / m² after thermal testing cycles to approximately 400°C. 2 After thermal testing cycles to approximately 500°C, the efficiency is approximately 270 mJ / m. 2After thermal testing cycles to approximately 600°C, the value is approximately 320 mJ / m. 2 All of these bonding energies fall within the range that allows the sheet to separate without damage. The coating exhibits approximately 0% bubble area change at approximately 25°C, approximately 0% bubble area change at approximately 300°C, approximately 0% bubble area change at approximately 400°C, approximately 8.5% bubble area change at approximately 500°C, and approximately 7.5% bubble area change at approximately 600°C, all of which are consistent with no degassing.

[0140] Figure 8 The Raman spectra of the hydrocarbon coating formed by hydrogenated amorphous plasma polymerization using the ethylene precursor of this embodiment are shown. The coating composition exhibits a Raman spectral density of 1378 cm⁻¹ under 532 nm excitation. -1 D-band peak and 1533 cm -1 The G-band peak confirmed that the coating is a hydrogenated amorphous carbon material. The coating's I... D / I G The ratio is 0.55, which indicates the presence of diamond-like carbon (DLC) film.

[0141] It will be apparent to those skilled in the art that various modifications and variations can be made to the examples described herein without departing from the spirit and scope of the claimed subject matter. Changes and improvements can be made to the examples described above without manifestly departing from the spirit and principles described herein. All such changes and modifications are intended to be included within the scope of protection of this specification and the appended claims.

Claims

1. An article comprising: The first sheet including the bonding surface of the first sheet; and A coating disposed on a first sheet bonding surface, the coating comprising a first coating bonding surface, a second coating bonding surface opposite to the first coating bonding surface, and a refractive index greater than about 1.8, the first coating bonding surface being bonded to the first sheet bonding surface, the coating further comprising a polymerized hydrogenated amorphous hydrocarbon compound, and the coating having a Raman spectrum appearing in the 1350 to 1400 cm⁻¹ region. -1 The peak value is within the range of 1530 to 1600 cm. -1 The peak intensity ratio within the range is 0.5 to 0.6, and the precursor is a polar functional group selected from the group consisting of hydrogen, carbon dioxide, nitrogen, nitrous oxide, ammonia, acrylic acid, allylamine, allyl alcohol, or mixtures thereof.

2. The article of claim 1, wherein, The optical band gap of the coating is less than 2 eV.

3. The article of claim 1, further comprising a second sheet having a second sheet bonding surface, wherein the second sheet bonding surface is used for bonding.

4. The article of claim 3, wherein, At least one of the first sheet or the second sheet is a glass sheet.

5. The article of claim 1, wherein, The average thickness of the coating is less than 10 nm.

6. The article of claim 1, wherein, The coating is a single layer.

7. The article of claim 1, wherein, The average thickness of the first sheet is less than 200 μm.

8. The article of manufacture according to any one of claims 1-7, wherein, After holding the product in a nitrogen atmosphere at 600°C for 10 minutes, the adhesion energy between the first coated bonding surface and the first sheet bonding surface is equal to or less than 600 mJ / m. 2 .

9. The article of claim 1, wherein, After holding the product in a nitrogen atmosphere at 500°C for 10 minutes, the adhesion energy between the first coated bonding surface and the first sheet bonding surface is equal to or less than 500 mJ / m. 2 .

10. The article of claim 1, wherein, After the product was held in a nitrogen atmosphere at 600°C for 10 minutes, the percentage change in bubble area of ​​the coating according to degassing test #1 was less than or equal to 10%.

11. The article of claim 1, wherein, After the product was held in a nitrogen atmosphere at 500°C for 10 minutes, the percentage change in bubble area of ​​the coating according to degassing test #1 was less than 10%.

12. A method of manufacturing an article, comprising: A precursor compound is vapor-deposited onto the first sheet bonding surface to form a coating on the first sheet bonding surface, wherein the precursor compound contains more than 90% by weight of hydrogen and carbon. as well as The coating comprises a polymerized hydrogenated amorphous hydrocarbon compound, a first coating bonding surface, and a second coating bonding surface opposite to the first coating bonding surface.

13. The method of claim 12, wherein a coating is formed by depositing a hydrocarbon precursor compound, the hydrocarbon precursor compound having the chemical formula C n H y ,in, n is 1 to 6, and y is 2 to 14.

14. The method of claim 12, further comprising bonding the second coating bonding surface to the second sheet bonding surface of the second sheet.

15. The method of claim 12, wherein, Hydrocarbon precursor compounds are selected from the following group: alkanes, alkenes, and alkynes.

16. The method of claim 12, wherein, Hydrocarbon precursor compounds are alkanes selected from the group consisting of methane, ethane, propane, butane, pentane, and hexane.

17. The method of claim 12, wherein, Hydrocarbon precursor compounds are olefins selected from the group consisting of ethylene, propylene, butene, pentene, and hexene.

18. The method of claim 12, wherein, Hydrocarbon precursor compounds are alkynes selected from the group consisting of acetylene, propyne, butyne, pentyne, and hexyne.

19. The method of claim 14, wherein, At least one of the first sheet or the second sheet is a glass sheet.

20. The method of claim 12, further comprising increasing the surface energy of the second coating bonding surface by exposing the second coating bonding surface to oxygen, nitrogen, or a combination thereof before bonding the second sheet bonding surface to the second coating bonding surface.

21. The method of claim 12, wherein, The average thickness of the coating is less than 10 nm.

22. The method of claim 12, wherein, Vapor deposition includes low-pressure plasma chemical vapor deposition or atmospheric pressure plasma chemical vapor deposition.

23. The method of claim 12, wherein, The surface energy of the second coating bonding surface in its freshly deposited state is greater than 50 mJ / m². 2 .

24. The method of claim 12, wherein, The coating has a refractive index greater than 2.

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