Siloxane plasma polymers for sheet bonding

Abstract

Described herein are glass articles comprising a sheet and a carrier and methods of making glass articles wherein the sheet and carrier are bonded together using a coating, preferably an organosiloxane polymer coating, and associated deposition methods and inert gas treatments, the inert gas treatments may be applied on the sheet, on the carrier, or on the sheet and the carrier to control Van der Waals, hydrogen bonding, and covalent bonding between the sheet and the carrier. The coating bonds the sheet and the carrier together to prevent permanent bonding under high temperature processing, but while maintaining sufficient bonding to prevent peeling during high temperature processing.

Description

[0001] This invention patent application is a divisional application of the invention patent application with international application number PCT / US2017 / 049019, international application date August 29, 2017, application number 201780066372.6 entering the Chinese national phase, and invention name “Silicone plasma polymer for sheet bonding”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of priority under 35 U.S.C. §119 to U.S. Provisional Application Serial No. 62 / 381,124, filed on August 30, 2016, the contents of which are based upon and are incorporated herein by reference in their entirety. Technical Field

[0004] The present disclosure relates generally to articles and methods for processing sheets on carriers, and more particularly to articles and methods for processing flexible glass sheets on glass carriers. Background Art

[0005] Flexible substrates offer the prospect of cheaper devices using roll-to-roll processing, and it is possible to manufacture thinner, lighter, more flexible and more durable displays. However, the technology, equipment and processes required for roll-to-roll processing of high-quality displays have not yet been fully developed. Since panel manufacturers have invested heavily in tool sets for processing large glass sheets, laminating flexible substrates to carriers and manufacturing display devices by sheet-to-sheet processing provides a more short-term solution to develop the value proposition of thinner, lighter and more flexible displays. Displays have been shown on polymer sheets, such as polyethylene naphthalate (PEN), where the manufacture of the device is a sheet-to-sheet form using PEN laminated to a glass carrier. However, the upper temperature limit of PEN limits the quality of the device and the methods that can be used. In addition, the high permeability of polymer substrates leads to environmental degradation of organic light emitting diode (OLED) devices, in which nearly airtight packaging is required. Thin film encapsulation provides the hope of overcoming this limitation, but it has not yet been proven that it can provide acceptable yields at large volumes.

[0006] Similarly, display devices can be manufactured using a glass carrier laminated to one or more thin glass substrates. It is expected that the low permeability and improved temperature and chemical resistance of thin glass will enable higher performance and longer life flexible displays.

[0007] In the manufacture of low temperature polysilicon (LTPS) devices, for example, processes where temperatures approach 600°C or higher, vacuum and wet etching environments may be used. These conditions limit the materials that can be used and place high demands on the carrier / thin sheet. Therefore, what is desired is a carrier method that utilizes the existing capital infrastructure of the manufacturer, is capable of processing thin glass (e.g., glass with a thickness of ≤0.3 millimeters (mm)), without contaminating or losing the bond strength between the thin glass and the carrier at higher processing temperatures, and the thin glass is easily debonded from the carrier at the end of the process.

[0008] One commercial advantage is that manufacturers will be able to leverage the capital investments they have already made in processing equipment while reaping the benefits of thin glass sheets for use in, for example, photovoltaic (PV) structures, OLEDs, liquid crystal displays (LCDs), and patterned thin film transistor (TFT) electronics. Additionally, this approach enables process flexibility, including processes for cleaning and surface preparation of the thin glass sheet and carrier to facilitate bonding.

[0009] One challenge of the known bonding methods is the high temperatures used to process polysilicon TFTs. The demand for higher pixel density, higher resolution and faster refresh rates for handheld displays, notebook and desktop displays, and the wider use of OLED displays push panel manufacturers from amorphous silicon TFT backplanes to oxide TFT or polysilicon TFT backplanes. Since OLEDs are current driven devices, high mobility is desired. Polysilicon TFTs also offer the advantage of integrated driver and other component activation. For dopant activation, higher temperatures are preferred, ideally at temperatures above 600°C. Summary of the invention

[0010] In view of the above, there is a need for a thin sheet-carrier article that can withstand the rigors of TFT and flat panel display (FPD) processing (including high temperature processing) (without outgassing, which is incompatible with the semiconductor or display manufacturing process in which the thin sheet-carrier article will be used) and allows an entire area of ​​the thin sheet to be removed from the carrier (either all at once or in sections) to allow the carrier to be reused to process another thin sheet. The present specification describes a method for controlling the adhesion between the carrier and the thin sheet to produce a temporary bond that is strong enough to withstand TFT and FPD processing (including LTPS processing) and weak enough to allow the sheet to be debonded from the carrier even after high temperature processing. This controlled bonding can be used to manufacture articles with reusable carriers, or to manufacture articles with patterned areas of controlled bonding between the carrier and the sheet. More specifically, the present disclosure provides coatings (including various materials and related surface heating treatments) that can be provided on the thin sheet, the carrier, or both to control van der Waals forces and / or hydrogen bonding at room temperature, and covalent bonding at high temperatures between the thin sheet and the carrier. Even more specifically, the present disclosure describes methods of depositing coatings for bonding a thin sheet to a carrier; methods of preparing coatings for bonding; and methods for bonding the coatings to a thin sheet and a carrier. These methods produce bonding between the components so that the bonding energy is not too high but not too low, and too high a bonding energy may make the components inseparable after electronic device processing, and too low a bonding energy may impair the bonding quality, which may lead to debonding or fluid ingress between the thin sheet and the carrier during electronic device processing. These methods also produce a glass article that exhibits low outgassing and withstands high temperature processing, such as LTPS TFT processing, and additional processing steps, such as wet cleaning and dry etching. In some alternative embodiments, the coating can be used to form various controlled bonding areas (where the carrier and the thin sheet remain fully bonded together after various processes, including vacuum processing, wet processing and / or ultrasonic cleaning processing), and can also be used to form covalent bonding areas to provide additional processing options, such as maintaining airtightness between the carrier and the sheet even after the article is divided into smaller pieces for additional device processing.

[0011] In a first aspect, there is provided an article comprising:

[0012] a first sheet material comprising a first sheet material bonding surface;

[0013] a second sheet material comprising a second sheet material bonding surface; and

[0014] a coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising a plasma polymerized organosiloxane compound;

[0015] The first coating bonding surface is bonded to the first sheet bonding surface, and the second coating bonding surface is bonded to the second sheet bonding surface.

[0016] In one example of aspect 1, the coating comprises poly(diphenylsiloxane).

[0017] In another example of aspect 1, the surface energy of the first coating bonding surface is 40 mJ / m 2 Up to 75mJ / m 2 between.

[0018] In another example of aspect 1, the thickness of the first coating layer is less than 100 nm.

[0019] In another example of aspect 1, the coating is a single layer.

[0020] In another example of aspect 1, the thickness of the first sheet is less than 200 μm.

[0021] In another example of aspect 1, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the first coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 600 mJ / m 2 .

[0022] In another example of aspect 1, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the first coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 700 mJ / m 2 , wherein the first coating bonding surface is annealed at a temperature of 400° C. in a nitrogen atmosphere before the first coating bonding surface is bonded to the first sheet bonding surface after subjecting the article to a temperature of 600° C.

[0023] In another example of aspect 1, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the first coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 600 mJ / m 2 , wherein the first coating bonding surface is annealed at a temperature of 400° C. in a nitrogen atmosphere before the first coating bonding surface is bonded to the first sheet bonding surface after subjecting the article to a temperature of 600° C.

[0024] In another example of aspect 1, after the first coating bonding surface has been annealed at 400°C in a nitrogen atmosphere before the first coating bonding surface is bonded to the first sheet bonding surface, the bubble area percentage changes by less than 10% when the article is subjected to a temperature of 600°C in a nitrogen atmosphere for 10 minutes.

[0025] In another example of aspect 1, after the first coating bonding surface has been annealed at 400°C in a nitrogen atmosphere before the first coating bonding surface is bonded to the first sheet bonding surface, the bubble area percentage changes by less than 5% when the article is subjected to a temperature of 600°C in a nitrogen atmosphere for 10 minutes.

[0026] In another example of aspect 1, the first sheet is a glass sheet.

[0027] In another example of aspect 1, the second sheet is a glass sheet.

[0028] In another example of aspect 1, the first sheet is a glass sheet and the second sheet is a glass sheet.

[0029] In a second aspect, there is provided an article as described in aspect 1, the plasma-polymerized organosiloxane compound being formed by depositing a monomer on at least one of the first sheet bonding surface and the second sheet bonding surface.

[0030] In one example of aspect 2, the monomer is deposited on at least one of the first sheet bonding surface and the second sheet bonding surface using low-pressure plasma chemical vapor deposition (CVD) or atmospheric-pressure plasma CVD.

[0031] In a third aspect, there is provided an article as described in aspect 2, wherein the monomer comprises a compound of formula (R 1 ) m Si(X 1 ) n A compound wherein each R 1 are independently aryl, alkyl, alkenyl, alkynyl or a combination thereof; m is 1, 2 or 3; each X 1 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl, or a combination thereof; and n is 1, 2 or 3.

[0032] In one example of aspect 3, R 1 It is an aromatic group.

[0033] In another example of aspect 3, X 1 It is an alkoxy group.

[0034] In another example of Aspect 3, R 1 is an aryl group and X 1 It is an alkoxy group.

[0035] In another example of aspect 3, the monomer is phenyltrimethoxysilane, phenyltriethoxysilane, phenyltribromosilane, phenyltrichlorosilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dibromodiphenylsilane, dichlorodiphenylsilane, bis(dimethylamino)diphenylsilane, bis(diethylamino)diphenylsilane, phenylsilane or diphenylsilane.

[0036] In a fourth aspect, the article of aspect 2 is provided, wherein the monomer comprises a disiloxane compound having the following structure, wherein R 2 -R 7 Each is independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl or a combination thereof.

[0037]

[0038] In one example of aspect 4, the monomer is hexamethyldisiloxane.

[0039] In a fifth aspect, there is provided the article of aspect 1, wherein the coating comprises a bottom coating and a top coating, the bottom coating being between the top coating and the second sheet.

[0040] In one example of aspect 5, the thickness of the bottom coating layer is between 10 nm and 80 nm, and the thickness of the top coating layer is between 10 nm and 50 nm.

[0041] In a sixth aspect, there is provided a method of manufacturing an article, the method comprising:

[0042] forming a coating comprising a plasma-polymerized organosiloxane compound on the bonding surface of the second sheet by depositing a monomer on the bonding surface of the second sheet using plasma CVD, the coating comprising the coating bonding surface; and

[0043] The coating bonding surface is bonded to the bonding surface of the first sheet.

[0044] In one example of aspect 6, the monomer is deposited on the bonding surface of the second sheet using low-pressure plasma CVD or atmospheric-pressure plasma CVD.

[0045] In one example of aspect 6, the coating comprises poly(diphenylsiloxane).

[0046] In another example of aspect 6, the coating has a thickness of less than 100 nm.

[0047] In another example of aspect 6, the coating is a single layer.

[0048] In another example of aspect 6, the first sheet has a thickness of less than 200 μm.

[0049] In another example of aspect 6, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 600 mJ / m 2 .

[0050] In another example of aspect 6, the first sheet is a glass sheet.

[0051] In another example of aspect 6, the second sheet is a glass sheet.

[0052] In another example of aspect 6, the first sheet is a glass sheet and the second sheet is a glass sheet.

[0053] In a seventh aspect, there is provided a method as in aspect 6, further comprising increasing the surface energy of the coating bonding surface before bonding the bonding surface of the first sheet to the coating bonding surface.

[0054] In one example of aspect 7, the surface energy of the coating bonding surface is increased by exposing the bonding surface to oxygen, nitrogen, or a combination thereof.

[0055] In another embodiment of aspect 7, the surface energy of the coating bonding surface is increased to 40 mJ / m 2 Up to 75mJ / m 2 between.

[0056] In the eighth aspect, the method according to aspect 6 is provided, wherein the monomer comprises a compound of formula (R 1 ) m Si(X 1 ) n A compound wherein each R 1 are independently aryl, alkyl, alkenyl, alkynyl or a combination thereof; m is 1, 2 or 3; each X 1 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl, or a combination thereof; and n is 1, 2 or 3.

[0057] In one example of aspect 8, R 1 It is an aromatic group.

[0058] In another example of aspect 8, X 1 It is an alkoxy group.

[0059] In another example of aspect 8, R 1 is an aryl group and X 1 It is an alkoxy group.

[0060] In another example of aspect 8, the monomer is phenyltrimethoxysilane, phenyltriethoxysilane, phenyltribromosilane, phenyltrichlorosilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dibromodiphenylsilane, dichlorodiphenylsilane, bis(dimethylamino)diphenylsilane, bis(diethylamino)diphenylsilane, phenylsilane or diphenylsilane.

[0061] In a ninth aspect, the method according to aspect 6 is provided, wherein the monomer comprises a disiloxane compound having the following structure, wherein R 2 -R 7 Each is independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl or a combination thereof.

[0062]

[0063] In one example of Aspect 9, the monomer is hexamethyldisiloxane.

[0064] In a tenth aspect, the method of aspect 6 is provided, wherein the coating comprises a bottom coating and a top coating, the bottom coating being between the top coating and the second sheet.

[0065] In another example of aspect 10, the thickness of the bottom coating layer is between 10 nm and 80 nm, and the thickness of the top coating layer is between 10 nm and 50 nm.

[0066] In an eleventh aspect, there is provided a method as in aspect 6, further comprising subjecting the coating to thermal annealing before bonding the first sheet to the coating.

[0067] In one example of aspect 11, the coating is subjected to thermal annealing in a nitrogen atmosphere.

[0068] In another example of aspect 11, the coating is subjected to thermal annealing at a temperature of at least 300°C.

[0069] In another example of aspect 11, the coating is subjected to thermal annealing at a temperature of at least 400°C.

[0070] In another example of aspect 11, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 700 mJ / m 2 .

[0071] In another example of aspect 11, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 600 mJ / m 2 .

[0072] In another example of aspect 11, when the article is subjected to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the bubble area percentage changes by less than 10%.

[0073] In another example of aspect 11, when the article is subjected to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the bubble area percentage changes by less than 5%.

[0074] In a twelfth aspect, there is provided an article comprising:

[0075] a first sheet material comprising a first sheet material bonding surface;

[0076] a second sheet material comprising a second sheet material bonding surface; and

[0077] a coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising poly(diphenylsiloxane);

[0078] The first coating bonding surface is bonded to the first sheet bonding surface, and the second coating bonding surface is bonded to the second sheet bonding surface.

[0079] In one example of aspect 12, the surface energy of the first coating bonding surface is 40 mJ / m 2 Up to 75mJ / m 2 between.

[0080] In another example of aspect 12, the coating has a thickness of less than 100 nm.

[0081] In another example of aspect 12, the coating is a single layer formed by depositing a monomer.

[0082] In another example of aspect 12, the first sheet has a thickness of less than 200 μm.

[0083] In another example of aspect 12, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the first coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 700 mJ / m 2 , wherein the first coating bonding surface is annealed at a temperature of 400° C. in a nitrogen atmosphere before the first coating bonding surface is bonded to the first sheet bonding surface after subjecting the article to a temperature of 600° C.

[0084] In another example of aspect 12, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the first coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 600 mJ / m 2, wherein the first coating bonding surface is annealed at a temperature of 400° C. in a nitrogen atmosphere before the first coating bonding surface is bonded to the first sheet bonding surface after subjecting the article to a temperature of 600° C.

[0085] In another example of aspect 12, after the first coating bonding surface has been annealed at 400°C in a nitrogen atmosphere before the first coating bonding surface is bonded to the first sheet bonding surface, the bubble area percentage changes by less than 10% when the article is subjected to a temperature of 600°C in a nitrogen atmosphere for 10 minutes.

[0086] In another example of aspect 12, after the first coating bonding surface has been annealed at 400°C in a nitrogen atmosphere before the first coating bonding surface is bonded to the first sheet bonding surface, the bubble area percentage changes by less than 5% when the article is subjected to a temperature of 600°C in a nitrogen atmosphere for 10 minutes.

[0087] In another example of aspect 12, the first sheet is a glass sheet.

[0088] In another example of aspect 12, the second sheet is a glass sheet.

[0089] In another example of aspect 12, the first sheet is a glass sheet and the second sheet is a glass sheet.

[0090] In a thirteenth aspect, the article of aspect 12 is provided, the poly(diphenylsiloxane) coating being formed by depositing a monomer on at least one of the first sheet bonding surface and the second sheet bonding surface.

[0091] In one example of aspect 13, the monomer is deposited on at least one of the first sheet bonding surface and the second sheet bonding surface using low-pressure plasma CVD or atmospheric-pressure plasma CVD.

[0092] In another example of aspect 13, the monomer comprises a diphenylsilane compound having the following structure, wherein X 2 and X 3 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl, or a combination thereof.

[0093]

[0094] In a fourteenth aspect, the article of aspect 12 is provided, the coating comprising a bottom coating and a top coating, the bottom coating being between the top coating and the second sheet.

[0095] In another example of aspect 14, the thickness of the bottom coating layer is between 10 nm and 80 nm, and the thickness of the top coating layer is between 10 nm and 50 nm.

[0096] In a 15th aspect, there is provided a method of manufacturing an article, the method comprising:

[0097] forming a coating comprising poly(diphenylsiloxane) on the bonding surface of the second sheet by depositing a monomer on the bonding surface of the second sheet, the coating comprising the coating bonding surface; and

[0098] The coating bonding surface is bonded to the bonding surface of the first sheet.

[0099] In one example of aspect 15, the monomer is deposited on the bonding surface of the second sheet using low-pressure plasma CVD or atmospheric-pressure plasma CVD.

[0100] In another example of aspect 15, the monomer comprises a diphenylsilane compound having the following structure, wherein X 2 and X 3 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl, or a combination thereof.

[0101]

[0102] In another example of aspect 15, the coating has a thickness of less than 100 nm.

[0103] In another example of aspect 15, the coating is a single layer.

[0104] In another example of aspect 15, the first sheet has a thickness of less than 200 μm.

[0105] In another example of aspect 15, the first sheet is a glass sheet.

[0106] In another example of aspect 15, the second sheet is a glass sheet.

[0107] In another example of aspect 15, the first sheet is a glass sheet and the second sheet is a glass sheet.

[0108] In a sixteenth aspect, the method of aspect 15 is provided, wherein the coating comprises a bottom coating and a top coating, the bottom coating being between the top coating and the second sheet.

[0109] In another example of aspect 16, the thickness of the bottom coating layer is between 10 nm and 80 nm, and the thickness of the top coating layer is between 10 nm and 50 nm.

[0110] In a seventeenth aspect, there is provided a method as in aspect 15, further comprising subjecting the coating to a thermal anneal before bonding the first sheet to the coating.

[0111] In one example of aspect 17, the coating is subjected to thermal annealing in a nitrogen atmosphere.

[0112] In another example of aspect 17, the coating is subjected to thermal annealing at a temperature of at least 300°C.

[0113] In another example of aspect 17, the coating is subjected to thermal annealing at a temperature of at least 400°C.

[0114] In another example of aspect 17, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 700 mJ / m 2 .

[0115] In another example of aspect 17, after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 600 mJ / m 2 .

[0116] In another example of aspect 17, when the article is subjected to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the bubble area percentage changes by less than 10%.

[0117] In another example of aspect 17, when the article is subjected to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the bubble area percentage changes by less than 5%.

[0118] Any one of the above aspects may be provided alone or in combination with any one or more instances of that aspect discussed above; that is, the first aspect may be provided alone or in combination with any one or more instances of the first aspect discussed above; the second aspect may be provided alone or in combination with any one or more instances of the second aspect discussed above; and so on.

[0119] The included drawings provide a further understanding of the principles of the present disclosure, and the drawings are incorporated into and constitute a part of the present specification. The drawings illustrate one or more embodiments and, together with the specification, serve to explain the principles and operation thereof by way of example. It should be understood that the various features disclosed in the present specification and the drawings may be used in any combination. As non-limiting examples, the various features may be combined with each other as described as aspects in the above specification. BRIEF DESCRIPTION OF THE DRAWINGS

[0120] The above features, aspects and advantages and other features, aspects and advantages of the embodiments disclosed in this specification may be better understood by reading the following detailed description with reference to the accompanying drawings, in which:

[0121] Figure 1 is a schematic side view of an article having a carrier bonded to a sheet and having a coating between the carrier and the sheet.

[0122] Figure 2 yes Figure 1 Exploded and partial cross-sectional views of the product.

[0123] Figure 3 is a graph of the thickness of plasma polymerized phenyl silicone and diphenyl silicone coatings as deposited and while undergoing processing.

[0124] Figure 4 is a graph of the surface energies of plasma polymerized phenyl silicone and diphenyl silicone coatings on a carrier and the corresponding cover wafer.

[0125] Figure 5 is a graph of the change in binding energy and bubble area percentage for thin glass bonded to a support by plasma polymerized phenyl silicone and diphenyl silicone coatings treated with N2-O2 plasma.

[0126] Figure 6 is a graph of the surface energy of plasma polymerized diphenylsilicone coatings on a carrier and corresponding cover wafer, measured as deposited and after annealing in flowing nitrogen for 10 minutes.

[0127] Figure 7 is a graph of the change in binding energy and percent bubble area for thin glass bonded to a support by plasma polymerized phenyl silicone and diphenyl silicone treated with N2-O2 plasma, which were annealed in flowing nitrogen for 10 minutes prior to surface activation and bonding. DETAILED DESCRIPTION

[0128] Exemplary embodiments will be described in more detail below with reference to the accompanying drawings. Whenever possible, the same reference numerals are used in all drawings to represent the same or similar parts. However, the claimed subject matter can be implemented in many different forms and should not be interpreted as being limited to the embodiments listed herein.

[0129] The directional terms used herein (eg, up, down, left, right, front, back, top, bottom) are only used with reference to the drawings in which they are drawn and are not intended to imply an absolute orientation.

[0130] Herein, ranges may be expressed as starting from "about" one specific value and / or ending at "about" another specific value. When such a range is expressed, another embodiment includes starting from the one specific value and / or ending at the other specific value. Similarly, when a value is expressed as an approximation using the antecedent "about", it is understood that the specific value constitutes another embodiment. It is also understood that the endpoint values ​​of each range are meaningful both in relation to the other endpoint value and independently of the other endpoint value.

[0131] Solutions are provided that enable processing of a first sheet on a second sheet, whereby at least a portion (including up to all) of the first sheet (e.g., a thin sheet of glass) remains "unbonded" so that the device processed on the sheet can be removed from the second sheet (e.g., a carrier). In order to maintain the beneficial characteristics of the surface shape, the carrier is typically a display-grade glass substrate. Therefore, in some cases, it may be wasteful and expensive to discard the carrier after only one use. Therefore, in order to reduce display manufacturing costs, it is desirable to be able to reuse the carrier to process more than one thin sheet substrate. The present disclosure describes products and methods that enable a thin film to be processed through the harsh environment of a processing line (such as a TFT), including high temperature processing, and also allow the thin film to be easily removed from the carrier without damaging the thin film or the carrier (such as breaking or cracking one of the carrier and the thin film into two or more pieces), thereby allowing the carrier to be reused, wherein high temperature processing is processing at a temperature ≥400°C, and the temperature can vary with the type of device being manufactured, for example, a temperature of up to about 450°C when processing amorphous silicon or amorphous indium gallium zinc oxide (IGZO) backplanes, a temperature of up to about 500-550°C when processing crystalline IGZO, or a typical temperature of up to about 600-650°C in LTPS and TFT processes.

[0132] Glass products

[0133] like Figure 1 and 2 As shown, the glass article 2 has a thickness 8 and includes a first sheet 20 having a thickness 28 (e.g., a thin glass sheet, such as a thin glass sheet having a thickness equal to or less than about 300 μm, including but not limited to, for example, 10-50 μm, 50-100 μm, 100-150 μm, 150-300 μm, 300, 250, 200, 190, 180, 170, 160, 150140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20 or 10 μm), a coating 30 having a thickness 38 and a second sheet 10 having a thickness 18 (e.g., a carrier).

[0134] The glass article 2 is arranged to allow processing of the first sheet 20 in an apparatus designed for thicker sheets, such as approximately greater than or equal to about 0.4 mm, such as 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1.0 mm, but the first sheet 20 itself is equal to or less than about 300 μm. Thickness 8 is the sum of thicknesses 18, 28 and 38, which thickness 8 can be equal to the thickness of the thicker sheet, and the apparatus (such as an apparatus designed to place components of an electronic device on a substrate sheet) is designed for processing the thicker sheet. In one example, if the processing equipment is designed for 700 μm sheets and the thickness 28 of the first sheet is 300 μm, the thickness 18 is selected to be 400 μm, while assuming that the thickness 38 is negligible. That is, the coating 30 is not shown to scale, but is exaggerated for illustration purposes only. In addition, in Figure 2 In the embodiment of the present invention, the coating is shown in cross-section. When a reusable carrier is provided, the coating can be uniformly disposed above the binding surface 14. Typically, the thickness 38 will be nanometer-scale, such as 2nm to 1 μm, 5nm to 250nm, 10 to 50nm or 20 to 100nm, or about 30, 40, 50, 60, 70, 80 or 90nm. The presence of the coating can be detected by surface chemical analysis, such as by time-of-flight secondary ion mass spectrometry (ToF Sims).

[0135] The second sheet 10 has a first surface 12, a bonding surface 14 and a perimeter 16. The second sheet 10 can be any suitable material, including glass. In other examples, the second sheet can be a non-glass material, such as ceramic, glass ceramic, silicon wafer or metal (because its surface energy and / or bonding can be controlled in a manner similar to that described below in conjunction with a glass carrier). If the second sheet 10 is made of glass, it can have any suitable composition, including aluminosilicate, borosilicate, aluminoborosilicate, sodium calcium silicate, and can be alkali-containing or alkali-free depending on its final application. The thickness 18 can be about 0.2mm to 3mm or more, such as 0.2, 0.3, 0.4, 0.5, 0.6, 0.65, 0.7, 1.0, 2.0 or 3mm or more, and as described above, the thickness 18 will depend on the thickness 28 and the thickness 38 (when the thickness 38 is not negligible). In one embodiment, the second sheet 10 can be made of a layer as shown in the figure, or made of multiple layers combined together (including multiple sheets). Furthermore, the carrier may be of Gen 1 size or larger, such as Gen 2, 3, 4, 5, 8 or larger (eg, sheet sizes ranging from 100 mm x 100 mm to 3 m x 3 m or larger).

[0136] The first sheet 20 has a first surface 22, a bonding surface 24 and a perimeter 26. The perimeters 16 (second sheet) and 26 can have any suitable shape, can be the same as each other or can be different from each other. In addition, the first sheet 20 can be any suitable material, including glass, ceramic, silicon wafer, glass ceramic or metal. As described above with respect to the second sheet 10, when the first sheet 20 is made of glass, it can have any suitable composition, including aluminosilicate, borosilicate, aluminoborosilicate, sodium lime silicate, and can be alkali-containing or alkali-free depending on its final application. The thermal expansion coefficient of the sheet can be substantially the same as that of the carrier, thereby reducing any warping of the article during high temperature processing. As described above, the thickness 28 of the first sheet 20 is 300μm or less. In addition, the first sheet can be 1 generation (Gen 1) size or larger, such as 2 generations, 3 generations, 4 generations, 5 generations, 8 generations or larger (for example, the sheet size is 100mm×100mm to 3 meters×3 meters or larger).

[0137] The thickness of the glass article 2 can be adapted to processing using existing equipment, and the thickness can also withstand the harsh environment in which processing occurs. For example, processing of flat panel displays (FPDs) can include wet ultrasonic, vacuum, and high temperature (e.g., ≥400° C.) processing. For some processes, as described above, the temperature can be ≥500° C., ≥550° C., ≥600° C., ≥650° C., and ≥700° C.

[0138] In order to withstand the harsh environment in which the article 2 is to be processed, the bonding surface 14 should be bonded to the bonding surface 24 with sufficient strength so that the first sheet 20 does not separate from the second sheet 10. And this strength needs to be maintained throughout the processing process so that the first sheet 20 does not separate from the second sheet 10 during processing. In addition, in order to allow the first sheet 20 to be removed from the second sheet 10 (for example, so that the second sheet 10 can be reused), the bonding surface 14 should not be bonded to the bonding surface 24 too firmly by the bonding force of the initial design and / or the bonding force that may be caused by changing the bonding force of the initial design, which may occur when the article is subjected to processing at high temperatures, such as ≥400° C. to ≥750° C. The coating 30 can be used to control the bonding strength between the bonding surface 14 and the bonding surface 24 to achieve these two purposes at the same time. A controlled bonding force is obtained by controlling the contribution of van der Waals forces (and / or hydrogen bonding) and covalent attraction energy to the total adhesion energy, which is controlled by adjusting the polar and non-polar surface energy components of the first sheet 20 and the second sheet 10. The controlled bond is strong enough to withstand FPD processing, for example, including temperatures of ≥400°C, in some cases, processing temperatures of ≥500°C, ≥550°C, ≥600°C, ≥650°C, and ≥700°C, and remains debondable by applying a force sufficient to separate the sheets without causing significant damage to the first sheet 20 and / or the second sheet 10. For example, the force should not break either the first sheet 20 or the second sheet 10. The debonding allows the removal of the first sheet 20 and the device fabricated thereon, and also allows the second sheet 10 to be reused as a carrier.

[0139] Although coating 30 is shown as a solid layer between first sheet 20 and second sheet 10, this need not be the case. For example, coating 30 may be approximately 0.1 nm to 1 μm thick (e.g., 1 nm to 10 nm, 10 nm to 50 nm, 100 nm, 250 nm, 500 nm to 1 μm), and may not completely cover all portions of bonding surface 14. For example, coverage may be ≤ 100%, 1% to 100%, 10% to 100%, 20% to 90%, or 50% to 90% of bonding surface 14. In other embodiments, coating 30 may be up to 50 nm thick, or even up to 100 nm to 250 nm thick in other embodiments. It may be considered that coating 30 is disposed between second sheet 10 and first sheet 20, even though it may not be in contact with one or the other of second sheet 10 and first sheet 20. In another aspect of the coating 30, the coating changes the ability of the bonding surface 14 to bond to the bonding surface 24, thereby controlling the bonding strength between the second sheet 10 and the first sheet 20. The material and thickness of the coating 30 and the treatment of the bonding surfaces 14, 24 prior to bonding can be used to control the bonding strength (adhesion energy) between the second sheet 10 and the first sheet 20.

[0140] Coating composition

[0141] Examples of coatings include organosiloxanes, particularly organosiloxane polymers. Such organosiloxane polymers can be formed by depositing monomers containing oxygen-silicon bonds on at least one of the sheet or the support, or by depositing silicon-containing monomers in the presence of an oxidant. When depositing monomers containing oxygen-silicon bonds, an oxidant may also be used.

[0142] One group of monomers suitable for forming organosiloxane polymers is the following formula (R 1 ) m Si(X 1 ) n wherein each R1 is independently aryl, alkyl, alkenyl, alkynyl or a combination thereof (i.e., aralkyl); m is 1, 2 or 3; each X 1 is independently a precursor group or a leaving group; and n is 1, 2 or 3. Examples of precursor groups include hydroxyl and alkoxy. Examples of leaving groups include hydrogen, halogen, amino, aryl, alkyl, alkenyl, alkynyl and combinations thereof (i.e., aralkyl). 1When being a leaving group, for example when the compound is phenylsilane or diphenylsilane, the organosiloxane polymer can be prepared by reacting these monomers with an oxidant, such as air, oxygen, nitrous oxide, carbon dioxide, water vapor or hydrogen peroxide. Can first carry out the reaction in plasma, then deposit. According to the preferred compound example described in this group of monomers, be phenyltrimethoxysilane, phenyltriethoxysilane, phenyltribromosilane, phenyltrichlorosilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dibromodiphenylsilane, dichlorodiphenylsilane, bis (dimethylamino) diphenylsilane, bis (diethylamino) diphenylsilane, phenylsilane or diphenylsilane.

[0143] In a preferred embodiment, R 1 In another preferred embodiment, X 1 In another preferred embodiment, R 1 is an aryl group and X 1 In another preferred embodiment, the monomer is a diphenylsilicone compound having the following structure, wherein X 2 and X 3 is independently hydrogen, halogen, hydroxyl, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl or a combination thereof (i.e., aralkyl). Preferably, the monomer is dimethoxydiphenylsilane or diethoxydiphenylsilane (equivalent to X 2 and X 3 Deposition of such monomers preferably results in an organosiloxane polymer that is a poly(diphenylsiloxane).

[0144]

[0145] Another group of monomers suitable for forming organosiloxane polymers are disiloxane compounds having the following structure, wherein R 2 -R 7 Independently selected from hydrogen, halogen, hydroxyl, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl or combinations thereof (ie, aralkyl). In a preferred embodiment, the monomer is hexamethyldisiloxane.

[0146]

[0147] The coating may comprise a monolayer. Preferably, the coating has a thickness of less than 100 nm, such as less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, less than 40 nm, less than 30 nm, less than 20 nm or less than 10 nm.

[0148] The coating may also comprise more than one layer, for example two layers. The coating may comprise a bottom coating and a top coating, wherein the bottom coating is suitable for bonding to a carrier and the top coating is suitable for bonding to a sheet. Preferably, the bottom coating is less than 50 nm, for example less than 40 nm, less than 30 nm, less than 20 nm or less than 10 nm. Preferably, the top coating is less than 30 nm, for example less than 20 nm or less than 10 nm. The bottom coating preferably has more elastic silicone, while the top coating preferably has more siloxane.

[0149] Deposition of coating

[0150] Examples of coating methods for providing the coating include chemical vapor deposition (CVD) techniques and similar methods. Specific examples of CVD techniques include CVD, low pressure CVD, atmospheric pressure CVD, plasma enhanced CVD (PECVD), atmospheric pressure plasma CVD, atomic layer deposition (ALD), plasma ALD, and chemical beam epitaxy. Another example of a coating method is to utilize wet chemistry, which can be used in some examples.

[0151] The reactive gas mixture containing the organosilane or organosiloxane monomer may also contain controlled amounts of an oxidant such as air, oxygen, nitrous oxide, carbon dioxide, water vapor or hydrogen peroxide and / or an inert gas such as helium, neon, argon, krypton, xenon.

[0152] Surface energy of coating

[0153] The coating can provide a surface energy of about 40mJ / m 2 About 75mJ / m 2 The surface energy (including polar and dispersive components) measured for a surface is within the binding surface range, whereby the surface only provides weak binding.

[0154] In general, the surface energy of the coating can be measured when the coating is deposited and / or further treated, such as by activating with nitrogen. The surface energy of the solid surface is indirectly measured by measuring the static contact angles of three liquids, water, diiodomethane and hexadecane, deposited separately on the solid surface in air. The surface energy disclosed herein is determined according to the Wu model. (See: S. Wu, J. Polym. Sci. C, 34, 19, 1971). In the Wu model, the surface energy, including the total surface energy, the polar component and the dispersion component, is measured by fitting the theoretical model to the three contact angles of the three test liquids (water, diiodomethane and hexadecane). According to the contact angle values ​​of the three liquids, regression analysis is performed to calculate the polar component and the dispersion component of the solid surface energy. The theoretical model for calculating the surface energy value includes the following three independent equations, which are related to the three contact angle values ​​of the three liquids and the solid surface (represented by the subscript "S") and the dispersion component and the polar component of the surface energy of the three test liquids:

[0155]

[0156] Among them, the subscripts "W", "D" and "H" represent water, diiodomethane and hexadecane, respectively, and the superscripts "d" and "p" represent the dispersion component and polar component of the surface energy, respectively. Since diiodomethane and hexadecane are actually non-polar liquids, the above equations are simplified to:

[0157]

[0158] According to the above three equations (4-6), the two unknown parameters, the dispersion surface energy components of the solid surface, are calculated by regression analysis. and polar surface energy component However, there is a maximum value of the surface energy of a solid surface that can be measured using this method. This maximum value is the surface tension of water, which is 73 mJ / m 2 If the surface energy of a solid surface is significantly greater than the surface tension of water, the surface can be completely wetted by water, resulting in a contact angle close to zero. Therefore, when this surface energy value is exceeded, all calculated surface energy values ​​will correspond to about 73-75 mJ / m, regardless of the actual surface energy value. 2 For example, if the actual surface energy of two solid surfaces is 75 mJ / m 2 and 150mJ / m 2 , then for these two surfaces, the calculated value using the liquid contact angle would be about 75 mJ / m 2 .

[0159] Therefore, all contact angles disclosed herein are measured by placing a droplet of liquid on a solid surface in air and measuring the angle between the solid surface and the liquid-air interface at the contact line. 2 Up to 75mJ / m 2 It should be understood that these values ​​correspond to the calculated surface energy values ​​obtained based on the above method, rather than the actual surface energy values. When the calculated values ​​are close to the actual surface energy values, the actual surface energy values ​​may be greater than 75 mJ / m 2 .

[0160] Annealing of coating

[0161] After the coating is deposited, annealing may be optionally performed. Annealing may be used to partially remove polymeric materials from the coating. Such removal may significantly reduce the outgassing of the coating, for example, outgassing during processing of the first sheet and the second sheet at high temperatures. The reduction in outgassing may make the bonding at high temperatures more secure, which makes the processing of the sheet more successful. Annealing may be performed in a rapid thermal processing system (RTP). Annealing may be performed at a temperature above 100°C, for example, at a temperature above 200°C, above 300°C, above 400°C, above 500°C, or above 600°C. Annealing may occur in an atmosphere containing, for example, nitrogen, oxygen, or air. Annealing may be performed for at least 15 seconds, for example, at least 30 seconds, at least 45 seconds, at least 1 minute, at least 2 minutes, at least 3 minutes, at least 4 minutes, at least 5 minutes, at least 6 minutes, at least 7 minutes, at least 8 minutes, at least 9 minutes, or at least 10 minutes. The time and temperature of annealing may vary depending on the composition of the coating. Whether a specific annealing time and temperature is sufficient for a specific composition may be determined using Outgassing Test #1. That is, for a particular coating composition, a time-temperature annealing cycle can be performed followed by Outgassing Test #1 (described below). If (in Outgassing Test #1) the surface energy change of the overburden is <10 mJ / m 2, then the time-temperature annealing cycle is sufficient to minimize exhaust. Alternatively, the adequacy of a specific annealing time and temperature (for minimizing exhaust) can be analyzed by the observed coating thickness change when the coating is subjected to a specific test temperature during the test time. More specifically, the substrate in which the coating is deposited is subjected to a specific time-temperature annealing process to be used for testing adequacy. After undergoing the time-temperature annealing process, the substrate and the coating (without another substrate combined with the coating to cover the coating) are subjected to the required time-temperature device processing cycle. If the thickness change of the coating has a minimum value after the required time-temperature device processing cycle, the annealing process is sufficient to minimize exhaust. In order to find the approximate starting point of the annealing time-temperature cycle, the thermogravimetric analysis of the material to be used as the coating can be observed. A good starting temperature is a temperature around the desired device processing temperature and at which the material thickness reduction (or material loss) occurs the most. Subsequently, the time and temperature can be changed to observe what will provide the most effective combination to minimize exhaust. In general, as the annealing temperature increases, the time to provide a sufficient annealing effect decreases. Similarly, as the annealing temperature decreases, the time to provide a sufficient annealing effect increases.

[0162] Surface activation of coatings

[0163] The surface energy required for binding may not be available through the surface energy of the initially deposited organosiloxane coating. Therefore, the deposited layer may be further processed. For example, after the coating is deposited, one or more functional groups may be optionally added to increase the coating's additional binding capacity. For example, the addition of functional groups may provide additional binding sites between the coating and the sheet. Plasma (e.g., atmospheric or low pressure plasma) may be used to add the functional groups. The functional groups are preferably polar and may be added using precursors such as hydrogen, carbon dioxide, nitrogen, nitrous oxide, ammonia, acrylic acid, allylamine, allyl alcohol, or a mixture thereof.

[0164] The binding energy of the first sheet or the second sheet to the coating

[0165] In general, the adhesion energy (i.e., bonding energy) between two surfaces can be measured by the double cantilever beam method or the wedge penetration test. The test simulates in a qualitative manner the forces and actions at an adhesive bonded joint at the coating / first sheet or second sheet interface. The wedge penetration test is commonly used to measure bonding energy. For example, ASTM D5041, Standard Test Method for Fracture Strength at Adhesive Cracking in Bonded Joints, and ASTM D3762, Standard Test Method for Durability of Aluminum Surfaces Bonded with Adhesives, are standard test methods for measuring bonding of substrates using a wedge.

[0166] For example, the overview of the test method includes recording the temperature and relative humidity for testing, such as the temperature and relative humidity in the laboratory. The first sheet is slightly preliminarily debonded or separated at the corner of the glass product to destroy the bond between the first sheet and the second sheet, that is, debonding is initiated. A sharp razor blade can be used, such as a GEM brand razor blade with a thickness of about 228 ± 20 microns, for initiating the debonding of the first sheet and the second sheet. When the debonding is formed, it may be necessary to have an instantaneous continuous pressure to fatigue the bond. The flat razor blade having the aluminum label removed is slowly inserted until the front edge of the debonding is observed to expand, thereby increasing the separation between the debonding portion and each sheet. Debonding can be induced without significantly inserting a flat razor blade. Once debonding is formed, the glass product is allowed to stand for at least 5 minutes to stabilize the debonding area. For high humidity environments, such as environments where the relative humidity is higher than 50%, a longer standing time may be required.

[0167] The debonding length was recorded with a microscope to evaluate the formation of the debonding initiated glass article. The debonding length was measured based on the final separation point of the first sheet from the second sheet (i.e., the separation point farthest from the razor blade tip) and the nearest non-tapered portion of the razor blade. The debonding length was recorded and used in the following equation to calculate the bonding energy.

[0168] γ=3t b 2 E1t w1 3 E2t w2 3 / 16L 4 (E1t w1 3 +E2t w2 3 ) (7)

[0169] Where γ represents the binding energy, t b represents the thickness of the blade, razor blade or wedge, E1 represents the Young's modulus of the first sheet (e.g., a thin glass sheet), t w1 represents the thickness of the first sheet, E2 represents the Young's modulus of the second sheet (such as a glass carrier), t w2 represents the thickness of the second sheet, and L represents the debonding length between the first sheet and the second sheet after the blade, razor blade or wedge is inserted as described above.

[0170] The bonding energy is understood to be representative of silicon wafer bonding, in which a pair of wafers initially bonded by hydrogen bonding are heated to convert a large number or all of the silanol-silanol hydrogen bonds to Si-O-Si covalent bonds. Although the initial room temperature hydrogen bonding produces approximately 100-200 mJ / m 2The bonding energy, which allows the separation of the bonding surfaces, is about 2000 to 3000 mJ / m during high temperature (about 400 to 800 °C) processing for a fully covalently bonded wafer pair. 2 , which does not allow separation of the bonded surfaces; instead, the two wafers function as a whole. On the other hand, if both surfaces are completely coated with a low surface energy material (such as a fluoropolymer) and the thickness is large enough to shield the influence of the underlying substrate, the adhesion energy will be that of the coating material and will be extremely low, resulting in low or no adhesion between the bonded surfaces. Therefore, it will not be possible to process the wafer on the carrier. Consider two extreme cases: (a) two glass surfaces saturated with silanol groups and cleaned by standard clean 1 (SC1, known in the art) are bonded together at room temperature by hydrogen bonding (so that the adhesion energy is about 100-200 mJ / m 2 ), which is then heated to a temperature that converts the silanol groups into covalent Si--O--Si bonds (thus converting the adhesion energy to 2000-3000 mJ / m 2 ). The 2000-3000mJ / m 2 The adhesion energy is too high to separate the glass surfaces; and (b) at room temperature, the fluorinated polymer is completely coated with a low surface adhesion energy (about 12-20 mJ / m per surface) 2 ) and heat them to a high temperature. In the latter case (b), not only do the surfaces not bond at low temperatures (because when the surfaces are brought together, about 24-40 mJ / m 2 The total adhesion energy of the adhesive is too low), and they do not bind at high temperatures because there are too few polar reactive groups. Between these two extremes, there is a range of adhesion energies, for example between 50 mJ / m 2 -1000mJ / m 2 , which range can produce a desired degree of controlled bonding. Therefore, the inventors have discovered various methods of providing coatings that can result in bonding energies that are between these two extremes and can form a controlled bond that is sufficient to keep a pair of glass substrates (e.g., a glass carrier and a thin glass sheet) bonded to each other after being subjected to the rigors of FPD processing, and the degree of bonding allows the first sheet (e.g., a thin sheet) to be separated from the second sheet (e.g., a carrier) after processing is completed (even after high temperature processing, such as ≥400°C to 700°C). In addition, the separation of the first sheet from the second sheet can be performed by mechanical force, and in a manner that does not significantly damage at least the first sheet, and preferably the second sheet.

[0171] Appropriate bonding energies may be achieved by using selected surface modifiers (i.e., coatings) and / or by heat treating or nitrogen treating the surfaces prior to bonding. Appropriate bonding energies may be achieved by selecting chemical modifiers for one or both of bonding surfaces 14 and 24 that control Van der Waals (and / or hydrogen bonding, these terms are used interchangeably throughout the specification) adhesion energies as well as covalent bonding adhesion energies that may result from high temperature processing (e.g., about ≥400° C. to 700° C.).

[0172] The modified layer is tested for its binding energy to a thin sheet (e.g., a thin glass sheet) after specific heating conditions. In order to observe whether a specific surface modification layer will keep the thin sheet bonded to the carrier, but still allow the thin sheet to debond from the carrier after processing, the following test is performed. The article (a thin sheet bonded to the carrier via the surface modification layer) is placed in an oven that is heated to the desired processing test temperature at a rate of 4°C / second. The article is then kept in the oven (maintained at the desired processing test temperature) for 10 minutes. The oven is then cooled to about 150°C over 45 minutes, and the sample is pulled out. The article is then tested for binding energy according to the binding energy test described herein.

[0173] Production of glass products

[0174] To produce the glass article, one of the glass sheets, preferably the second sheet, is contacted with the coating. If necessary, the coating may be subjected to steps such as surface activation and annealing to increase the surface energy and improve the bonding ability of the coating. To bond the other sheet, preferably the first sheet, the other sheet is contacted with the coating. If the coating has a sufficiently high surface energy, contacting the other glass sheet with the coating will cause the glass sheet to bond to the coating by self-propagating bonding. Self-propagating bonding is advantageous for reducing assembly time and / or saving assembly costs. However, if self-propagating bonding is not achieved, another technique may be used to bond the thin glass sheet to the coating, such as lamination, for example by pressing the sheets together using rollers, or by bringing the two sheets of material together for bonding by other techniques known in the art of lamination.

[0175] Exhaust of coating

[0176] Polymer adhesives used in typical wafer bonding applications are typically 10-100 μm thick and lose about 5% of their mass at or near their temperature extremes. For these materials escaping from thick polymer films, the amount of mass loss or outgassing can be easily quantified using mass spectrometry. On the other hand, outgassing from thin surface treatments with a thickness of about 10nm to 100nm or less is much more difficult, such as outgassing from the plasma polymerized coatings mentioned above, and outgassing from thin layers of pyrolyzed silicone oil. For these materials, mass spectrometry is not sensitive enough. However, there are many other ways to measure outgassing.

[0177] Outgassing as described in the present disclosure is measured by the following outgassing test. According to this test, a small amount of outgassing is measured based on an assembled article (i.e., an assembled article in which a thin glass sheet is bonded to a glass carrier via a coating to be tested), and outgassing is determined using a percentage change in bubble area. During heating of the glass article, bubbles are formed between the carrier and the thin sheet, which indicate outgassing of the coating. Outgassing beneath the thin sheet can be limited by the strong adhesion between the thin sheet and the carrier. However, layers ≤10 nm thick (e.g., plasma-polymerized materials, self-assembled monolayers (SAMs), and pyrolyzed silicone oil surface treatments) can still form bubbles during thermal treatment, although their absolute mass loss is small. Moreover, the formation of bubbles between the thin sheet and the carrier can lead to problems related to the arrangement of patterns during generation, photolithography processing, and / or processing of the device onto the thin sheet. In addition, bubbling at the boundary of the bonding area between the thin sheet and the carrier can cause problems with process fluids from one process contaminating downstream processes. A percentage change in bubble area of ​​≥5% is significant, indicating that outgassing has occurred, which is undesirable. On the other hand, a change in bubble area percentage of ≤ about 1% is not significant, indicating that no degassing has occurred.

[0178] The average bubble area of ​​the bonded thin glass by artificial bonding in a Class 1000 clean room is about 1%. The percentage of bubbles in the bonded carrier varies depending on the cleanliness of the carrier, the thin glass sheet, and the surface preparation. Because these initial defects act as nucleation sites for bubble growth after heat treatment, any bubble area change less than 1% during heat treatment is within the variability of sample preparation. In order to perform this test, a commercial desktop scanner [Epson Expression 10000XL Photo Scanner (Photo)] with a transparent unit was used immediately after bonding to make the first scanned image of the area where the thin sheet is bonded to the carrier. Using standard Epson software, each part was scanned using 508dpi (50 microns / pixel) and 24-bit RGB. The image processing software first prepares the image by: stitching together images of different parts of the sample to form a single image when necessary, and removing scanner artifacts (by using a calibration reference scan performed without a sample in the scanner). Standard image processing techniques, such as thresholding, hole filling, erosion / expansion, and Blob analysis, are then used to analyze the bonded area. In addition to using an Epson Expression 10000XL photo printer, an Epson Expression 11000XL photo scanner can also be used in a similar manner. In transmission mode, bubbles in the bonding area are visible in the scanned image, and the bubble area value can be determined. Then, the bubble area is compared with the total bonding area (i.e., the total overlapping area between the thin sheet and the carrier) to calculate the percentage of the bubble area in the bonding area relative to the total bonding area. Subsequently, the sample was heat treated in an MPT-RTP600s rapid thermal processing system [purchased from Modular Process Technology (MPT, with offices in San Jose, California)]) at test limit temperatures of 300°C, 400°C, 500°C and 600°C under a N2 atmosphere for 10 minutes. Specifically, the time-temperature cycle performed includes: placing the article in a heating chamber at room temperature and atmospheric pressure; then heating the heating chamber to the test limit temperature at a rate of 9°C / minute; maintaining the heating chamber at the test limit temperature for 10 minutes; then cooling the heating chamber to 200°C at the rate of the furnace; removing the article from the heating chamber and allowing the article to cool to room temperature; and then scanning the article a second time with an optical scanner. Subsequently, the bubble area percentage from the second scan can be calculated according to the above and compared with the bubble area percentage from the first scan to determine the change in bubble area percentage. As described above, a bubble area change of ≥5% is significant and indicates the presence of outgassing. Due to the variability of the original bubble area percentage, the change in bubble area percentage was selected as the measurement criterion. That is, due to the processing and cleanliness after the thin sheet and carrier are prepared and before they are combined, most coatings have a bubble area of ​​about 2% in the first scan.However, there may be variations between materials.

[0179] The percentage of bubble area measured, such as illustrated by the change in bubble area percentage, can also be characterized as the percentage of the total surface area of ​​the coating bonding surface that is not in contact with the bonding surface of the first sheet. As described above, the percentage of the total surface area of ​​the coating bonding surface that is not in contact with the first sheet is advantageously less than 5%, less than 3%, less than 1%, and up to less than 0.5% after the glass article is subjected to temperature cycling by heating from room temperature to 500°C, 600°C, 650°C, and up to 700°C in a chamber at a rate of about 400°C / minute to about 600°C / minute, then holding at the test temperature for 10 minutes, and then cooling the glass article to room temperature. The coatings described herein allow the first sheet to be separated from the second sheet without breaking the first sheet into two or more pieces after the glass article is subjected to the above-mentioned temperature cycling and thermal testing.

[0180] Glass products processing

[0181] The use of the coating together with the appropriate bonding surface preparation can achieve a controlled bonding area, that is, a bonding area that meets the following requirements: it can provide room temperature bonding between the first sheet and the second sheet, which is sufficient to enable the article to be processed in FPD-type processes (including vacuum processes and wet processes), but the bonding area controls the covalent bonding between the first sheet and the second sheet (even at high temperatures) so as to allow the first sheet to be removed from the second sheet (without damaging each sheet) after high temperature processing of the article, such as after FPD-type processing or LTPS processing. In order to evaluate potential bonding surface preparations, as well as coatings with various bonding energies that can provide a reusable carrier suitable for FPD processing, a series of tests were used to evaluate the suitability of each. Different FPD applications have different requirements, but currently LTPS and oxide TFT processes appear to be the most stringent. Therefore, tests representing steps in these processes were selected because these are the expected applications of Article 2. Annealing at 400°C is utilized in the oxide TFT process, while crystallization and doping activation steps in excess of 600°C are used in the LTPS process. Therefore, the following tests were conducted to evaluate the potential of specific bonding surface preparations and coatings to enable the flakes to remain bonded to the carrier throughout FPD processing, yet allow the flakes to be removed from the carrier (without damaging the flakes and / or the carrier) after said processing (including processing at temperatures ≥400°C to 700°C).

[0182] Example

[0183] Example 1

[0184] A plasma polymer coating of diphenylsilicone (also known as poly(diphenylsiloxane)) was deposited on a 0.7 mm support (the support was purchased from Corning Incorporated in Corning, New York) under a low pressure plasma discharge from oxygen and dimethoxydiphenylsilane. Alkali-free display glass manufacturing). The deposition was carried out in a Plasma-Treat PTS150 system (a low pressure hot wall CVD reactor purchased from Plasmatreat, Belmont, California), and the wall was heated to 150°C, dimethoxydiphenylsilane was flowed into the evaporator at 150°C at 0.1 ml / min, the chamber pressure was 50 mTorr (mT), O2 was 40 standard cubic centimeters / minute (sccm), and there were two RF powered electrodes, which applied a bias of 25-50 watts (W) at a 13.56 MHz RF frequency. In this system, a pair of electrodes in the chamber are RF driven, and the substrate is at a floating potential in the discharge between the electrodes.

[0185] Comparative Example 1

[0186] A phenyl silicone plasma polymer coating (also known as poly(phenylsiloxane)) was deposited on a support consisting of a 0.7 mm thick layer of Alkali-free display glass manufacturing). The deposition was carried out in a PTS150 system from Plasma-Treat at 150°C, starting with phenyltriethoxysilane flow at 0.1 ml / min, pressure of 50 mT, 40 sccm O2 flow, and bias of 25-50 Watt at 13.56 MHz RF frequency.

[0187] Test Example 1 and Comparative Example 1

[0188] Thermal stability of coating

[0189] Figure 3 The thermal stability of plasma polymerized phenyl silicone and diphenyl silicone coatings is shown by plotting the coating thickness versus processing in flowing nitrogen for 10 minutes at the indicated temperatures. Figure 3 It can be seen from the Figures that the thermal stability of plasma polymerized phenyl silicone and diphenyl silicone during deposition is not very high when the processing temperature is above 300° C. Specifically, both materials show significant film thickness loss when heated in flowing nitrogen at temperatures above 300° C., especially at 400° C. and above for 10 minutes.

[0190] Coating quality

[0191] Thermal instability leads to Figure 4 The significant amount of exhaust shown, Figure 4 is a graph comparing the surface energy of the coated carrier and cover wafers processed for 10 minutes at the indicated temperatures and in flowing nitrogen as described in Test #1. Specifically, according to Test #1, the exhaust gas surface energy changes by more than 10 mJ / m 2 Display, and less than 5mJ / m 2 The surface energy change of is consistent with the case without degassing. Although not shown in the figure, the surface energy of the phenyl silicone cover and the diphenyl silicone cover is about 75mJ / m at room temperature (about 16°C). 2 , that is, the surface energy of blank glass. Figure 4 As seen in Figure 2, the phenyl silicone coating (open circle data points) experienced greater than 10 mJ / m when the processing temperature was changed from room temperature (about 16°C) to 300°C and to 600°C. 2 The surface energy of the phenyl silicone coating changes from about 75mJ / m at room temperature to 2 When it drops to 300℃, it is about 50mJ / m 2 The increase in surface energy of the phenyl silicone overlay from 300°C to 600°C is consistent with material previously deposited on the overlay (which was previously detached from the support) burning out at those higher temperatures. Similarly, the diphenyl silicone overlay (open square data points) also shows a surface energy change of greater than 10 mJ / m when the processing temperature changes from 300°C to 600°C. 2 However, the surface energy of the diphenylsilicone coating (open square data points) remains roughly the same from room temperature to 300°C—75 mJ / m 2 Thus, at temperatures at least up to 300°C and below 400°C, diphenylsilicone can be used for deposition with little outgassing.

[0192] Surface activation

[0193] The surfaces of plasma polymerized phenyl silicone and diphenyl silicone are easily modified by plasma exposure to nitrogen or to a mixture of nitrogen and oxygen as shown in Table 1. The plasma activation increases the surface energy of the phenyl silicone coating from 40 mJ / m to 100 mJ / m by the N2-O2 mixture. 2Raised to the surface energy close to blank glass. This surface modification is carried out in Oxford (Oxford) PlasmaLab 100, but can be completed by low pressure or atmospheric discharge. Plasma treatment can be carried out by two consecutive steps. Specifically, with hydrogen plasma treatment [30 seconds (s), C2H4 flow is 10sccm, H2 flow is 50sccm, chamber pressure is 5mT, 1500W coil, and there is 50W RF bias at 13.56MHz frequency], then immediately carry out N2 plasma treatment (5mT chamber pressure, N2 flow is 40sccm, 1500W coil, frequency is 50W bias at 13.56MHz, continue 5 seconds) or N2-O2 plasma treatment (5 seconds, N2 flow is 35sccm, O2 flow is 5sccm, the chamber pressure of 15mT, 800W coil, frequency is 50W RF bias at 13.56MHz) without extinguishing plasma. By raising the surface energy close to that of blank glass, the thin glass flakes are bonded to the carrier at room temperature using rapid self-propagating bonding.

[0194] Table 1 shows the contact angles ("W" for water, "HD" for hexadecane and "DIM" for diiodomethane) and the surface energy ("D" for the dispersion component, "P" for the polar component and "T" for the total surface energy, measured by the Wu model (described above)) of the phenyl silicone layer and the diphenyl silicone layer. Specifically, Table 1 shows the contact angles and surface energies of a blank support, a coated but untreated support, and a coating treated with nitrogen or with nitrogen and oxygen. Thus, for example, the first row of Table 1 shows that the blank support has a W contact angle of 8.37, a HD contact angle of 19.67, a DIM contact angle of 24.67, and a total surface energy of 75.92 mJ / m 2 , of which the dispersion component accounts for 34.56mJ / m 2 , and the polar component accounts for 41.36mJ / m 2 Similarly, the second row of Table 1 shows that the untreated support coated with phenyl silicone has a W contact angle of 81.63, a HD contact angle of 2.83, a DIM contact angle of 53.2, and a total surface energy of 40.09 mJ / m 2 , of which the dispersion component accounts for 30.36mJ / m 2 , and the polar component accounts for 9.73mJ / m 2 .

[0195] Table 1

[0196]

[0197] Combined with quality

[0198] After the surface energy of the coating was raised to a level close to that of blank glass by, for example, treating the coated support with N2-O2, it was bonded to a 100 μm thin glass sheet (purchased from Corning Incorporated, Corning, NY). The bonding quality between the coating and the thin glass flakes was demonstrated by the changes in bonding energy and bubble area of ​​the thin glass flakes of plasma polymerized phenyl silicone and diphenyl silicone coatings bonded to the support after processing using an MPT-RTP600s rapid thermal processing system in flowing nitrogen for 10 minutes at the indicated temperatures, as shown in Figure 5 As shown. As can be seen, as the binding energy decreases, the bubble area increases, indicating that the percentage of the surface of the thin glass flake that is bonded to the coating decreases. More specifically, for phenyl silicone, when the sample is heated at a temperature above 300°C, such as when heated at 400°C or when heated at 500°C, the percentage change in bubble area (according to Test #2 above, and shown by the hollow diamond data points) increases by well over 5% (when heated at 400°C, the bubble area changes by almost 20%, and when heated at 500°C, the bubble area changes by more than 15%). Therefore, this material is useful for temperatures up to about 300°C. Similarly, for diphenyl silicone, when the sample is heated at a temperature above 400°C, such as when heated at 500°C or when heated at 600°C, the percentage change in bubble area (according to Test #2 above, and shown by the hollow square data points) increases by well over 5% (when heated at 500°C, the bubble area changes by more than 10%, and when heated at 600°C, the bubble area changes by about 25%). Therefore, the material is useful for temperatures up to about 400°C.

[0199] annealing

[0200] To reduce outgassing, the coated supports were annealed at 400°C in flowing nitrogen for 10 minutes prior to any surface activation of the surface modification layer and prior to any measurements and bonding to the wafer. Figure 6 A comparison of the exhaust (according to Test #1) of a diphenylsilicone ("DPSO") coating with and without an initial annealing step is shown. More specifically, Figure 6 The surface energies of the coated carrier and the surface energies of the covered wafers after heating in flowing nitrogen for 10 minutes at the indicated temperatures are shown. Measurements made with an initial annealing step are labeled "400C Exhaust" or "Exhaust 400C", while measurements made without an initial annealing step are labeled "As Deposited" or "As Deposited" to represent the as-deposited condition. Figure 6 As shown in Figure 2, when the support is heated at a temperature of 300°C to about 600°C, the surface energy of the DPSO deposited on the support is maintained approximately constant at 50 mJ / m 2= 25 mJ / m2, see solid diamond data points; the surface energy of the deposited cover wafer on the carrier with freshly deposited DPSO (according to test #1) increases from about 75 mJ / m2 after heating at 300°C. 2 After heating to 400℃ and above, it is about 50mJ / m 2 , see the open diamond data points; the surface energy of DPSO deposited on a support and then subjected to an initial annealing step of heating at 400°C for 10 minutes has a surface energy of about 55 mJ / m after heating at 300°C. 2 The surface energy of the surface is about 50 mJ / m after heating at 400°C to about 500°C. 2 The surface energy is about 60 mJ / m after heating at 600 °C. 2 , see the solid square data points; and the surface energy of the cover wafer (according to test #1) disposed on a carrier having DPSO deposited and then annealed at 400°C for 10 minutes increased from about 65 mJ / m after heating at 300°C. 2 After heating to 600℃, it changes to about 60mJ / m 2 , see the open square data points. Therefore, as shown by the open square data points, the surface energy of the capped wafer on the annealed DPSO varies by less than 5 mJ / m over the range of 300°C to 600°C. 2 , which is consistent with the no venting obtained from Test #1.

[0201] Bonding quality after annealing

[0202] Figure 7 The binding energy and percent change in bubble area (according to test #2) are shown for samples that were subjected to an initial annealing step at 400°C for 10 minutes in flowing nitrogen prior to the test shown. That is, 0.7 mm EAGLE The carrier was then heated at 400°C for 10 minutes in flowing nitrogen, followed by surface activation of the coated carrier using N2-O2 plasma to raise the surface energy to close to that of blank glass, and then bonded to a thin glass sheet - 100 μm The glasses were bonded to form the test articles. The test articles were then processed in a MPT-RTP600s Rapid Thermal Processing System at the indicated temperatures for 10 minutes in flowing nitrogen. Figure 7 The measurements show that the binding energy of the test article combined with phenyl silicone decreases rapidly, that is, from about 700 mJ / m when heated at 300°C to about 1.5 mJ / m 2 When heated to 600℃, it drops to about 0mJ / m 2, see the solid diamond data points; when the article is heated at 300°C, the bubble area percentage change of the test article incorporating phenyl silicone remains below 5%, but when the article is heated at 400°C and above, it quickly increases by more than 10% (indicating outgassing), see the open diamond data points; when the article is heated at temperatures from about 300°C to about 600°C, the binding energy of the test article incorporating diphenyl silicone remains at about 750 mJ / m 2 About 550mJ / m 2 The thin glass sheets remained debondable from the carrier within a range of , and the solid square data points; the bubble area percentage change for the test articles incorporating diphenyl silicone remained below 10% when the articles were heated at temperatures between 300°C and 600°C, see the hollow square data points. Although there was some outgassing of the test articles incorporating diphenyl silicone, especially at around 500°C, the samples remained intact throughout the test and could be debonded even after heating at 600°C, indicating that the diphenyl silicone prepared for these test articles would be useful over a wide temperature range, including those up to at least 600°C, i.e., the range used for LTPS processing. On the other hand, Figure 7 The phenyl silicone prepared for the test article may be useful for processing devices requiring temperatures as high as 300°C, such as color filters or touch sensors.

[0203] Example 2

[0204] In two separate experiments, plasma polymerized hexamethyldisiloxane (HMDSO) coatings were deposited on 0.7 mm EAGLE 100 mm thick films in a dielectric barrier discharge (DBD) type linear atmospheric plasma at room temperature or 100 °C. The coated substrate was deposited on a substrate (using a power of about 100 to 200 watts, a frequency of 13.56 MHz, using He as a carrier gas to deliver HMDSO at a flow rate of about 30 or about 50 sccm, an O2 flow rate of 0-10 sccm, additional He as the main gas, room temperature or 100°C deposition, and a plasma head-substrate distance of about 2 mm). Table 3 shows the flow rates of HMDSO and O2 during deposition for two separate experiments, as well as the surface energy and roughness measured by atomic force microscopy (AFM). The coated substrate was then exposed to a clean 100 μm thin glass sheet (made by The thin glass was bonded to the treated substrate and subjected to 600°C treatment for 10 minutes in a N2 environment. Table 3 also shows the deposition conditions, surface energy, bonding energy, and bubble area changes. After processing at 600°C, the thin glass can be easily debonded from the treated substrate. Note that the bonding energy is only 364 mJ / m 2The 8-9% change in bubble area percentage after heating at 600°C is consistent with the presence of some but minimal outgassing. It is worth noting that Example 2 was not performed in a clean room and, therefore, the carrier, thin glass flake, and coating were contaminated with particles during processing. It is believed that if this example was performed in a clean room, the bubble area change would be even smaller due to reduced contamination of the carrier, thin glass flake, and / or coating, as the better bonding quality between the thin glass flake and the carrier increases the nucleation barrier.

[0205] Table 2

[0206]

[0207] It will be apparent to those skilled in the art that various modifications and variations may be made to the embodiments disclosed herein without departing from the spirit and scope of the claimed subject matter. Various variations and modifications may be made to the above embodiments without substantially departing from the spirit and various principles. All such variations and modifications are intended to be included within the scope of protection of this specification and the appended claims. For example, some non-limiting embodiments include the following.

[0208] Embodiment 1: A product comprising:

[0209] a first sheet material comprising a first sheet material bonding surface;

[0210] a second sheet material comprising a second sheet material bonding surface; and

[0211] a coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising a plasma polymerized organosiloxane compound;

[0212] The first coating bonding surface is bonded to the first sheet bonding surface, and the second coating bonding surface is bonded to the second sheet bonding surface.

[0213] Embodiment 2: The article of embodiment 1, wherein the plasma-polymerized organosiloxane compound is formed by depositing a monomer on at least one of the first sheet bonding surface and the second sheet bonding surface.

[0214] Embodiment 3: The article as described in embodiment 2, wherein the monomer comprises formula (R 1 ) m Si(X 1 ) n A compound wherein each R 1 are independently aryl, alkyl, alkenyl, alkynyl or a combination thereof; m is 1, 2 or 3; each X 1 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl, or a combination thereof; and n is 1, 2 or 3.

[0215] Embodiment 4: The product according to embodiment 3, R 1 is aryl, and / or X 1 It is an alkoxy group.

[0216] Embodiment 5: The article as described in embodiment 3, wherein the monomer is at least one monomer selected from the following group: phenyltrimethoxysilane, phenyltriethoxysilane, phenyltribromosilane, phenyltrichlorosilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dibromodiphenylsilane, dichlorodiphenylsilane, bis(dimethylamino)diphenylsilane, bis(diethylamino)diphenylsilane, phenylsilane and diphenylsilane.

[0217] Embodiment 6: The article of embodiment 2, wherein the monomer comprises a disiloxane compound having the following structure, wherein R 2 -R 7 Each is independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl or a combination thereof.

[0218]

[0219] Embodiment 7: The article of embodiment 6, wherein the monomer is hexamethyldisiloxane.

[0220] Embodiment 8: The article of embodiment 1, wherein the coating comprises poly(diphenylsiloxane).

[0221] Embodiment 9: The article as described in any one of embodiments 1-8, wherein the surface energy of the first coating bonding surface is 40 mJ / m 2 Up to 75mJ / m 2 between.

[0222] Embodiment 10: The article of any one of embodiments 1-9, wherein the coating has a thickness of less than 100 nm.

[0223] Embodiment 11: The article as described in any one of embodiments 1-10, wherein the coating comprises a bottom coating and a top coating, the bottom coating is between the top coating and the second sheet, the bottom coating has a thickness between 10nm and 80nm, and the top coating has a thickness between 10nm and 50nm.

[0224] Embodiment 12: The article of any one of embodiments 1-11, wherein after the article is subjected to a temperature of 600° C. in a nitrogen atmosphere for 10 minutes, the first coating bonding surface bonds to the first sheet bonding surface, and the bonding energy is less than 700 mJ / m 2 .

[0225] Embodiment 13: The article of any one of Embodiments 1-12, wherein the percent change in bubble area is less than 10% when the article is subjected to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere.

[0226] Embodiment 14: A method of manufacturing an article, the method comprising:

[0227] forming a coating comprising a plasma-polymerized organosiloxane compound on the bonding surface of the second sheet by depositing a monomer on the bonding surface of the second sheet using plasma CVD, the coating comprising a coating bonding surface; and bonding the coating bonding surface to the bonding surface of the first sheet.

[0228] Embodiment 15: The method of embodiment 14 further comprises: exposing the bonding surface to oxygen, nitrogen or a combination thereof to increase the surface energy of the coating bonding surface before the bonding surface of the first sheet is bonded to the coating bonding surface, wherein the surface energy of the coating bonding surface is increased to 40 mJ / m 2 Up to 75mJ / m 2 between.

[0229] Embodiment 16: The method according to embodiment 14, wherein the monomer comprises a formula (R 1 ) m Si(X 1 ) n A compound wherein each R 1 are independently aryl, alkyl, alkenyl, alkynyl or a combination thereof; m is 1, 2 or 3; each X 1 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl, or a combination thereof; and n is 1, 2 or 3.

[0230] Embodiment 17: The method as described in Embodiment 16, R 1 is aryl, and / or X 1 It is an alkoxy group.

[0231] Embodiment 18: A method as described in embodiment 16, wherein the monomer comprises at least one monomer selected from the following group: phenyltrimethoxysilane, phenyltriethoxysilane, phenyltribromosilane, phenyltrichlorosilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dibromodiphenylsilane, dichlorodiphenylsilane, bis(dimethylamino)diphenylsilane, bis(diethylamino)diphenylsilane, phenylsilane and diphenylsilane.

[0232] Embodiment 19: The method of embodiment 14, wherein the monomer comprises a disiloxane compound having the following structure, wherein R 2 -R 7Each is independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl or a combination thereof.

[0233]

[0234] Embodiment 20: The method of embodiment 19, wherein the monomer is hexamethyldisiloxane.

[0235] Embodiment 21. The method of Embodiment 14, wherein the coating comprises poly(diphenylsiloxane).

[0236] Embodiment 22: The method as described in any one of Embodiments 14-20, wherein the thickness of the coating is less than 100 nm.

[0237] Embodiment 23: A method as described in any one of embodiments 14-21, wherein the coating comprises a bottom coating and a top coating, the bottom coating is between the top coating and the second sheet, the bottom coating has a thickness between 10nm and 80nm, and the top coating has a thickness between 10nm and 50nm.

[0238] Embodiment 24: The method of any one of Embodiments 14-22, further comprising subjecting the coating to a thermal anneal at a temperature of at least 300° C. in a nitrogen atmosphere before bonding the first sheet to the coating.

[0239] Embodiment 25: The method of Embodiment 24, comprising subjecting the coating to a thermal anneal at a temperature of at least 400°C.

[0240] Embodiment 26: An article comprising:

[0241] a first sheet material comprising a first sheet material bonding surface;

[0242] a second sheet material comprising a second sheet material bonding surface; and

[0243] a coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising poly(diphenylsiloxane);

[0244] The first coating bonding surface is bonded to the first sheet bonding surface, and the second coating bonding surface is bonded to the second sheet bonding surface.

[0245] Embodiment 27: The article of embodiment 26, wherein the poly(diphenylsiloxane) coating is formed by depositing a monomer on at least one of the first sheet bonding surface and the second sheet bonding surface, wherein the monomer is deposited on at least one of the first sheet bonding surface and the second sheet bonding surface, and the monomer comprises a diphenylsilane compound having the following structure, wherein X 2 and X3 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl, or a combination thereof.

[0246]

[0247] Embodiment 28: The article of embodiment 26, wherein the surface energy of the first coating bonding surface is 40 mJ / m 2 Up to 75mJ / m 2 between.

[0248] Embodiment 29: The article of any one of Embodiments 26-28, wherein the coating has a thickness of less than 100 nm.

[0249] Embodiment 30: An article as described in any one of embodiments 26-29, wherein the coating comprises a bottom coating and a top coating, and the bottom coating is disposed between the top coating and the second sheet, the thickness of the bottom coating is between 10nm and 80nm, and the thickness of the top coating is between 10nm and 50nm.

[0250] Embodiment 31: The article of any one of Embodiments 26-30, wherein after subjecting the article to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere, the first coating bonding surface bonds to the first sheet bonding surface with a bonding energy of less than 700 mJ / m 2 .

[0251] Embodiment 32: The article of any one of Embodiments 26-31, wherein the percent change in bubble area is less than 10% when the article is subjected to a temperature of 600° C. for 10 minutes in a nitrogen atmosphere.

[0252] Embodiment 33: A method of manufacturing an article, the method comprising:

[0253] Forming a coating comprising poly(diphenylsiloxane) on the bonding surface of the second sheet by depositing a monomer on the bonding surface of the second sheet, the coating comprising a coating bonding surface; and bonding the coating bonding surface to the bonding surface of the first sheet.

[0254] Embodiment 34: The method of embodiment 33, wherein the monomer comprises a diphenylsilane compound having the following structure, wherein X 2 and X 3 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl, or a combination thereof.

[0255]

[0256] Embodiment 35: The method of embodiment 33 or embodiment 34, wherein the thickness of the coating is less than 100 nm.

[0257] Embodiment 36: A method as described in any one of embodiments 33-35, wherein the coating comprises a bottom coating and a top coating, the bottom coating is between the top coating and the second sheet, the thickness of the bottom coating is between 10nm and 80nm, and the thickness of the top coating is between 10nm and 50nm.

[0258] Embodiment 37: The method of any one of Embodiments 33-36, further comprising subjecting the coating to thermal annealing at a temperature of at least 300° C. in a nitrogen atmosphere before bonding the first sheet to the coating.

[0259] Embodiment 38: The method of Embodiment 37, comprising subjecting the coating to a thermal anneal at a temperature of at least 400°C.

Claims

1. A product comprising: a first sheet material comprising a first sheet material bonding surface; a second sheet material comprising a second sheet material bonding surface; and a coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising plasma polymerized poly(diphenylsiloxane); The first coating bonding surface is bonded to the first sheet bonding surface, and the second coating bonding surface is bonded to the second sheet bonding surface, The thickness of the coating is greater than or equal to 10 nm and less than 100 nm; After subjecting the article to a temperature of 600°C for 10 minutes in a nitrogen atmosphere, the first coating bonding surface is bonded to the first sheet bonding surface with a bonding energy of less than 700 mJ / m 2 ,and When the article was subjected to a temperature of 600°C for 10 minutes in a nitrogen atmosphere, the percentage change in bubble area was less than 10%.

2. The article of claim 1, wherein the poly(diphenylsiloxane) coating is formed by depositing a monomer on at least one of the first sheet bonding surface and the second sheet bonding surface, wherein: The monomer is deposited on at least one of the first sheet material bonding surface and the second sheet material bonding surface, and the monomer includes a diphenylsilane compound having the following structure, wherein X 2 and X 3 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl or a combination thereof 3. The article of claim 1, wherein the surface energy of the first coating bonding surface is 40 mJ / m 2 Up to 75mJ / m 2 between.

4. The article of claim 1, wherein: The coating layer comprises a bottom coating layer and a top coating layer, and the bottom coating layer is disposed between the top coating layer and the second sheet, the bottom coating layer has a thickness between 10 nm and 80 nm, and the top coating layer has a thickness between 10 nm and 50 nm.

5. The article of claim 2, wherein: The monomer is at least one monomer selected from the group consisting of dimethoxydiphenylsilane, diethoxydiphenylsilane, dibromodiphenylsilane, dichlorodiphenylsilane, bis(dimethylamino)diphenylsilane, bis(diethylamino)diphenylsilane, phenylsilane and diphenylsilane.

6. A method of manufacturing an article, the method comprising: forming a coating comprising poly(diphenylsiloxane) on the bonding surface of the second sheet by depositing a monomer on the bonding surface of the second sheet using plasma chemical vapor deposition, the coating comprising a coating bonding surface; as well as bonding the coating bonding surface to the bonding surface of the first sheet, The method further comprises subjecting the coating to a thermal annealing at a temperature of at least 300° C. in a nitrogen atmosphere before bonding the first sheet to the coating, comprising subjecting the coating to a thermal annealing, in: The thickness of the coating is greater than or equal to 10 nm and less than 100 nm; After subjecting the article to a temperature of 600°C for 10 minutes in a nitrogen atmosphere, the first coating bonding surface is bonded to the first sheet bonding surface with a bonding energy of less than 700 mJ / m 2 ,and When the article was subjected to a temperature of 600°C for 10 minutes in a nitrogen atmosphere, the percentage change in bubble area was less than 10%.

7. The method according to claim 6, wherein the monomer comprises a diphenylsilane compound having the following structure, wherein: X 2 and X 3 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl or a combination thereof 8. The method of claim 6, wherein: The coating layer comprises a bottom coating layer and a top coating layer, the bottom coating layer is between the top coating layer and the second sheet, the bottom coating layer has a thickness between 10 nm and 80 nm, and the top coating layer has a thickness between 10 nm and 50 nm.

9. The method of claim 8, further comprising: Exposing the bonding surface to oxygen, nitrogen or a combination thereof to increase the surface energy of the coating bonding surface prior to bonding the bonding surface of the first sheet to the coating bonding surface, the surface energy of the coating bonding surface being increased to 40 mJ / m 2 Up to 75mJ / m 2 between.

10. The method of claim 6, comprising subjecting the coating to a thermal anneal at a temperature of at least 400°C.

11. The method of claim 7, wherein: The monomer is at least one monomer selected from the group consisting of dimethoxydiphenylsilane, diethoxydiphenylsilane, dibromodiphenylsilane, dichlorodiphenylsilane, bis(dimethylamino)diphenylsilane, bis(diethylamino)diphenylsilane, phenylsilane and diphenylsilane.

12. An article manufactured by the method of any one of claims 6 to 11, comprising: a first sheet material comprising a first sheet material bonding surface; a second sheet material comprising a second sheet material bonding surface; and a coating comprising a first coating bonding surface and a second coating bonding surface, the coating comprising plasma polymerized poly(diphenylsiloxane); The first coating bonding surface is bonded to the first sheet bonding surface, and the second coating bonding surface is bonded to the second sheet bonding surface, The thickness of the coating is greater than or equal to 10 nm and less than 100 nm; After subjecting the article to a temperature of 600°C for 10 minutes in a nitrogen atmosphere, the first coating bonding surface is bonded to the first sheet bonding surface with a bonding energy of less than 700 mJ / m 2 ,and When the article was subjected to a temperature of 600°C for 10 minutes in a nitrogen atmosphere, the percentage change in bubble area was less than 10%.

13. The article of claim 12, wherein the poly(diphenylsiloxane) coating is formed by depositing a monomer on at least one of the first sheet bonding surface and the second sheet bonding surface, wherein: The monomer is deposited on at least one of the first sheet material bonding surface and the second sheet material bonding surface, and the monomer includes a diphenylsilane compound having the following structure, wherein X 2 and X 3 are independently hydrogen, halogen, hydroxy, alkoxy, amino, aryl, alkyl, alkenyl, alkynyl or a combination thereof 14. The article of claim 12, wherein the surface energy of the first coating bonding surface is 40 mJ / m 2 Up to 75mJ / m 2 between.

15. The article of claim 12, wherein: The coating layer comprises a bottom coating layer and a top coating layer, and the bottom coating layer is disposed between the top coating layer and the second sheet, the bottom coating layer has a thickness between 10 nm and 80 nm, and the top coating layer has a thickness between 10 nm and 50 nm.

16. The article of claim 13, wherein: The monomer is at least one monomer selected from the group consisting of dimethoxydiphenylsilane, diethoxydiphenylsilane, dibromodiphenylsilane, dichlorodiphenylsilane, bis(dimethylamino)diphenylsilane, bis(diethylamino)diphenylsilane, phenylsilane and diphenylsilane.

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