TWI654088B - Object and method for controlled engagement of a polymer surface with a carrier - Google Patents

Abstract

A substrate having a polymer bonding surface having a first surface energy; a carrier having a glass bonding surface having a second surface energy; and a plasma polymerization surface modification layer which The polymer bonding surface is releasably bonded to the glass bonding surface. The plasma polymerization layer may be formed to reduce the surface energy of the glass bonding surface before bonding. Moreover, after being subjected to vacuum annealing for one hour in an environment having a temperature of 120 ° C., the substrate can be non-destructively disengaged from the carrier.

Description

Articles and methods for controlled joining of polymer surfaces to carriers

This application claims the priority right of US Provisional Application Serial No. 61/931924 filed on January 27, 2014, the content of which is the basis of this document and is incorporated herein by reference in its entirety.

The present invention relates to an object and method for processing a flexible sheet on a carrier, and more particularly, to an object and method for processing a flexible glass sheet on a glass carrier.

Flexible substrates offer the prospect of cheaper devices using roll-to-roll processing, as well as the possibility of making thinner, lighter, more flexible and durable displays. However, the technology, equipment and processes required for roll-to-roll processing of high-quality displays have not been fully developed. Because panel makers have invested heavily in toolsets for processing large glass sheets, laminating flexible substrates to carriers and making display devices from sheet-to-sheet processing provides: A shorter term solution to the value proposition of thinner, lighter and more flexible displays. Demonstrations have been demonstrated on polymer sheets such as polyethylene naphthalate (PEN), where device fabrication uses Sheet to sheet manufacturing of PEN laminated to a glass carrier. The upper temperature limit of PEN limits the quality of the device and the process that can be used. In addition, the high permeability of the polymer substrate causes the environmental degradation of the OLED device, and in this case, a near air-tight packaging is required. Thin-film packaging offers the prospect of overcoming this limitation, but it has not been proven to provide acceptable yields in large volumes.

In a similar manner, a display device can be manufactured using a glass carrier laminated to one or more thin glass substrates. It is expected that the low permeability of thin glass and improved temperature and chemical resistance will allow flexible displays with higher performance and longer life.

However, thermal, vacuum, solvent, and acidic and flat panel display (FPD) processes require robust bonding for thin glass to be bonded to a carrier. The FPD process typically involves vacuum deposition (sputtered metals, transparent conductive oxides and oxide semiconductors, chemical vapor deposition (CVD) deposition of amorphous silicon, silicon nitride, and silicon dioxide, and metal and insulators Dry etching), thermal processes (including about 300-400 ° C CVD deposition, up to 600 ° C p-Si crystals, 350-450 ° C oxide semiconductor annealing, up to 650 ° C dopant annealing, and about 200-350 ° C contact annealing ), Acidic etching (metal etching, oxide semiconductor etching), solvent exposure (peeling off photoresist, deposition of polymer packages), and ultrasonic exposure (in solvent stripping and aqueous cleaning of photoresist, typically In alkaline solution).

Adhesive wafer bonding has been widely used in micromechanical systems (MEMS) and semiconductor processing for back-end steps. In these back-end steps, the manufacturing process is less demanding. Brewer Science and Henkel's commercial adhesives are typically thick polymer adhesive layers that are 5-200 microns thick. The large thickness of these layers creates the possibility of a large amount of volatile components, captured solvents, and adsorbed substances contaminating the FPD process. These materials thermally decompose and outgas above about 250 ° C. These materials can also cause contamination in downstream steps by acting as sinks for gases, solvents, and acids, which can be released in subsequent processes.

U.S. Provisional Application Serial No. 61 / 596,727 (hereinafter US'727), filed on February 8, 2012, entitled Processing Flexible Glass with a Carrier , discloses concepts that involve the following: For example, a sheet of a flexible glass sheet is bonded to a carrier, and then the bonding strength in some areas is increased, while maintaining the processing of the sheet / carrier to form a device thereon (e.g., an electronic or display device, an electronic or display device). The ability to remove many parts of the sheet after a component, an organic light emitting device (OLED) material, a photovoltaic (PV) structure or a thin film transistor). At least a portion of the thin glass is bonded to the carrier so that the device process fluid is prevented from entering between the sheet and the carrier, thereby reducing the chance of contaminating downstream processes, that is, the joint sealed portion between the sheet and the carrier is airtight And, in some preferred embodiments, the seal surrounds the exterior of the article, thereby preventing liquid or gas from invading in or outside any area of the sealed article.

US'727 continues to reveal that in the manufacturing process of low temperature polysilicon (LTPS) (compared to the low temperature of solid-phase crystallization, which can be up to about 750 ° C), a device close to 600 ° C or greater can be used. Temperature, vacuum and wet etching environment. These conditions limit the materials that can be used and place high demands on the carrier / sheet. Therefore, there is a need for a vehicle method that leverages the manufacturer's existing capital infrastructure and allows for thin glass (i.e. 0.3mm thick glass) without pollution or loss of bonding strength between the thin glass and the carrier, and the thin glass is easily de-bond from the carrier at the end of the process.

A commercial advantage of the method disclosed in US'727 is that, as noted in US'727, manufacturers will be able to leverage their existing capital investment in processing equipment while obtaining thin glass sheets for use in, for example, PV, OLED, LCD And the advantages of patterned thin film transistor (TFT) electronic equipment. In addition, this method allows process flexibility, including: process flexibility for cleaning and surface preparation of thin glass sheets and carriers to facilitate bonding; process flexibility for strengthening the bonding between the sheet and the carrier at the bonding area ; Process flexibility for maintaining the releasability of the sheet from the carrier at the non-joined (or reduced strength joint / low-strength joint) area; and process flexibility for cutting the sheet to facilitate extraction from the carrier.

In the glass-to-glass bonding process, the glass surface is cleaned to remove all metal, organic, and particulate residues, leaving a nearly silanol-terminated surface. The glass surfaces are first brought into intimate contact, where Van der Waals and / or hydrogen bonding forces pull the surfaces together. Utilizing heat and pressure as required, the surface silanol groups condense to form strong covalent Si-O-Si bonds across the interface, thereby permanently melting the glass blocks. Metal, organic, and particulate residues will prevent bonding by masking the surface, thus preventing the tight contact required for bonding. A high surface concentration of silanol is also required to form strong bonds, because the number of bonds per unit area will be determined by the probability that two silanol substances on the opposite surface will react to condense into water. Zhuravlel has reported an average number of hydroxyl groups per nm ² of 4.6 to 4.9 for fully hydrated silicon dioxide. Zhuravlel, LT, The Surface Chemistry of Amorphous Silika, Zhuravlev Model, Colloids and Surfaces A: Physiochemical Engineering Aspects 173 (2000) 1-38. In US'727, a non-joined area is formed within the joint perimeter, and the main way to describe this non-joined area is to increase the surface roughness. An average surface roughness greater than 2 nm Ra prevents glass-to-glass bonding from forming during the high temperature of the bonding process. In US Provisional Patent Application Serial No. 61 / 736,880 (hereinafter US'880), entitled Facilitated Processing for Controlling Bonding Between Sheet and Carrier , filed by the same inventor on December 13, 2012, controlled The bonding region is formed by controlling Van der Waals bonding and / or hydrogen bonding between the carrier and the thin glass sheet, but covalent bonding regions are still used. Therefore, although the objects and methods used to handle flakes and carriers in US'727 and US'880 can withstand the harsh environment of FPD processing, it is undesirable for some applications because thin glass and glass carriers are used in Strong covalent bonding in the bonding region prevents re-use of the carrier. The bonding region is, for example, covalently bonded by Si-O-Si, with an adhesive force of about 1000-2000 mJ / m ² (approximately the glass Breaking strength). Prying or peeling cannot be used to separate the covalently bonded portions of thin glass from the carrier, and therefore, the entire sheet cannot be removed from the carrier. Instead, the non-joined area with the device thereon is scored and extracted, leaving the joined perimeter of the thin glass sheet on the carrier.

In view of the above, there is a need for a sheet-carrier object that can withstand the harsh conditions of FPD processing including high temperature processing (there is no outgassing that is incompatible with the semiconductor or display manufacturing process in which the sheet-carrier object is used), However, the entire area of the sheet is allowed to be removed from the carrier (one-time removal, or partial removal) to This allows the carrier to be reused for processing another sheet. This specification describes a way to control the adhesion between the carrier and the sheet to create a temporary bond that is strong enough to be preserved in FPD processing (including LTPS processing), but weak enough to allow the sheet even after high temperature processing. Disengage from the vehicle. Such controlled bonding can be utilized to produce objects with reusable carriers, or alternatively to produce objects with a patterned area of controlled bonding and covalent bonding between the carrier and the sheet. More precisely, the present disclosure provides a surface modification layer (including various materials and associated surface heat treatments) that can be provided on the sheet, on the carrier, or both, in order to control the room temperature between the sheet and the carrier. Dewar force bonding and / or hydrogen bonding and high temperature covalent bonding. Even more precisely, the room temperature bonding can be controlled enough to hold the sheet and carrier together during vacuum processing, wet processing, and / or ultrasonic cleaning processing. And at the same time, high temperature covalent bonding can be controlled to prevent permanent bonding between the sheet and the carrier during high temperature processing, and to maintain sufficient bonding to prevent delamination during high temperature processing. In alternative embodiments, the surface modification layer can be used to create a variety of controlled bonding areas (where the carrier and sheet are still fully bonded through various processes including vacuum processing, wet processing, and / or ultrasonic cleaning Treatment) along with covalently bonded areas to provide other processing options, such as maintaining the airtightness between the carrier and the sheet even after dicing the object into small pieces for additional device processing. In addition, some surface modification layers provide control of the bond between the carrier and the sheet while reducing outgassing during harsh conditions in FPD (e.g., LTPS) processing environments, such as high temperatures And / or vacuum. In addition, in alternative embodiments, some surface modification layers may be used on a carrier having a glass bonding surface to controllably bond a sheet having a polymer bonding surface. The polymer bonding surface may be a portion of a polymer sheet having electronic or other structures formed thereon, or alternatively, the polymer bonding surface may be a portion of a composite sheet including a glass layer on which electronic or Other structures.

Other features and advantages will be described in the following detailed description, and to a certain extent, those skilled in the art will easily understand these features and advantages based on the description, or by practicing this written description and accompanying drawings Illustrate various aspects to recognize these characteristics and advantages. It should be understood that the foregoing general description and the following detailed description are merely exemplary of various aspects and are intended to provide an overview and framework for understanding the nature and characteristics of the claimed invention.

The accompanying drawings are included to provide a further understanding of the principles of the invention, and the accompanying drawings are incorporated into and constitute a part of this specification. The drawings illustrate one or more embodiments, and together with the description serve to explain the principles and operations of the present invention through examples. It should be understood that the various features disclosed in this specification and in the drawings may be used in any and all combinations. By way of non-limiting example, various features may be combined with each other, as set forth in the scope of the accompanying patent application.

2‧‧‧ objects

5‧‧‧line

8‧‧‧Thickness / Thickness

10‧‧‧ carrier / glass carrier

12‧‧‧first surface

14‧‧‧ joining surface

16‧‧‧ around

18‧‧‧ thickness

20‧‧‧ thin sheet / thin glass sheet / sheet

22‧‧‧first surface

24‧‧‧Joint surface

Around 26‧‧‧

28‧‧‧ thickness

30‧‧‧ surface modified layer

38‧‧‧ thickness

40‧‧‧joint area / controlled joint area

50‧‧‧Controlled junction area / area / array

Around 52‧‧‧

56‧‧‧ Required part / intermediate layer

57‧‧‧periphery

402‧‧‧line

404‧‧‧line

406‧‧‧line

502‧‧‧total surface energy

504‧‧‧polar component

506‧‧‧Scattered

760‧‧‧ stacked

770‧‧‧glass / sheet

771‧‧‧ glass sheet / sheet

772‧‧‧Glass sheet / sheet

776‧‧‧first major surface / primary surface / first surface

778‧‧‧Second major surface / primary surface / second surface

780‧‧‧ Cover sheet / cover material

781‧‧‧cover sheet / cover material

790‧‧‧ surface modified layer

791‧‧‧ interface

792‧‧‧ interface

793‧‧‧ interface

794‧‧‧ interface

900‧‧‧ the first substrate / carrier

902‧‧‧ surface

910‧‧‧Second substrate / cover material / carrier

912‧‧‧Surface / Bare Surface / Cover Material Surface / Cover Material

920‧‧‧ septa

930‧‧‧heating room

940‧‧‧arrow

1001‧‧‧line

1002‧‧‧line

1003‧‧‧line

1004‧‧‧line

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1302‧‧‧line

1303‧‧‧line

1304‧‧‧line

1312‧‧‧Total surface energy

1314‧‧‧Polar component

1316‧‧‧Scattered

1401‧‧‧line

1402‧‧‧line

1403‧‧‧line

1404‧‧‧line

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Figure 1 is a schematic side view of an article having a carrier bonded to a sheet with a surface modifying layer between the carrier and the sheet.

Figure 2 is an expanded and partially sectional view of the object in Figure 1.

Figure 3 is a graph of surface hydroxyl concentration on silicon dioxide as a function of temperature.

Figure 4 is a graph of the surface energy of the SC1-clean glass sheet as a function of annealing temperature.

Figure 5 is a graph of the surface energy of a thin fluoropolymer film deposited on a glass sheet as a percentage of one of the constituent materials from which the film was made.

FIG. 6 is a schematic plan view of a sheet bonded to a carrier through a bonding area.

Figure 7 is a schematic side view of a glass sheet stack.

FIG. 8 is an expanded view of one embodiment of the stack in FIG. 7.

Figure 9 is a schematic diagram of the test device.

Figure 10 is a series of graphs for the surface energy of various materials under different conditions (surface energy of different parts of the test device in Figure 9) versus time.

Figure 11 is a graph of% bubble area change versus temperature for various materials.

Figure 12 is another graph of% bubble area change relative temperature for various materials.

Figure 13 is a graph of the surface energy of a fluoropolymer film deposited on a glass sheet as a percentage of one of the gases used during the deposition.

Figure 13A is a graph of the surface energy of a fluoropolymer film deposited on a glass sheet as a percentage of one of the gases used during the deposition.

FIG. 14 is a graph of the surface energy versus deposition time for the surface modification layer.

FIG. 15 is a graph of the thickness on the double logarithmic scale versus the deposition time for the surface modified layer.

Figure 16 is a graph of surface energy versus processing temperature for different surface modified layers.

Figure 17 is a graph of the surface coverage of the surface modification layer.

Figure 18 is a summary of the performance of the organic transistor fabricated on a 200 micron PEN film bonded to a glass carrier.

In the following detailed description, for purposes of explanation and without limitation, example embodiments that disclose specific details are set forth in order to provide a thorough understanding of the various principles of the invention. However, those of ordinary skill who have benefited from this disclosure should understand that the present invention may be practiced in other embodiments that depart from the specific details disclosed herein. In addition, descriptions of well-known devices, methods, and materials may be omitted so as not to obscure the description of various principles of the present invention. Finally, wherever applicable, the same element reference refers to the same element.

Ranges may be expressed herein as from "about" one particular value, and / or to "about" another particular value. When expressing this range, another embodiment includes from one specific value and / or to another specific value. Similarly, when values are expressed as approximate values by using the antecedent "about", it should be understood that specific values form another embodiment. It should be further understood that the endpoints of each of the ranges are significant relative to the other endpoint and independently of the other endpoint.

The directional terms as used herein-for example, up, down, left, right, front, back, top, bottom-are for reference only to the drawings drawn and are not intended to imply absolute orientation.

As used herein, the singular forms "a" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes aspects having two or more such "components" unless the context clearly indicates otherwise.

In both US'727 and US'880, solutions are provided that allow thin glass sheets to be processed on a carrier, whereby at least a portion of the thin glass sheets remain "non-joined" so that devices processed on thin glass sheets can Removed from the vehicle. However, the periphery of the thin glass is permanently (or covalently, or hermetically) bonded to the carrier glass via the formation of covalent Si-O-Si bonds. The periphery of this covalent bond prevents the reuse of the carrier, as the thin glass in this permanent junction cannot be removed without damaging the thin glass and the carrier.

To maintain favorable surface shape characteristics, the carrier is typically a display-grade glass substrate. Therefore, in some cases, it is wasteful and costly to dispose of the vehicle after only one use. Therefore, in order to reduce the cost of manufacturing a display, it is desirable to be able to reuse a carrier to process more than one sheet substrate. This disclosure describes articles and methods for allowing flakes to pass harsh environmental treatments including high temperature processing in FPD processing lines-where high temperature processing is Processed at a temperature of 400 ° C, and may vary depending on the type of device being made, for example, at most about in the case of amorphous silicon or amorphous indium gallium zinc oxide (IGZO) backplane processing A temperature of 450 ° C is at most about 500-550 ° C in a crystalline IGZO process, or at most about 600-650 ° C, as is typical in an LTPS process--and still allows the flakes to be easily removed from the carrier without any problems. Destruction of a sheet or a vehicle (eg, where one of the carrier and the sheet is broken or cracked into two or more pieces), whereby the carrier can be reused.

As shown in FIGS. 1 and 2, the object 2 has a thickness of 8 and includes a carrier 10 having a thickness of 18 and a sheet 20 having a thickness of 28 (that is, having A sheet having a thickness of 300 microns, including but not limited to, for example, the following thicknesses: 10-50 microns, 50-100 microns, 100-150 microns, 150-300 microns, 300, 250, 200, 190, 180, 170, 160 , 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, or 10 microns), and a surface modification layer 30 having a thickness of 38. The article 2 is designed to allow designing for thicker sheets (i.e., approximately .4mm, for example, .4mm, .5mm, .6mm, .7mm, .8mm, .9mm, or 1.0mm of other sheet materials), although the sheet 20 itself 300 microns. That is, the thickness 8 which is the sum of the thicknesses 18, 28, and 38 is designed to be equal to the thickness of the thicker sheet, and one piece of equipment--for example, equipment designed to place electronic device components on a substrate sheet-- It is designed to handle this thicker sheet. For example, if the processing equipment is designed for a 700 micron sheet and the sheet has a thickness 28 of 300 microns, then assuming a negligible thickness of 38, the thickness 18 will be chosen to be 400 microns. That is, the surface modification layer 30 is not shown to scale; instead, the surface modification layer is greatly exaggerated for illustration purposes only. In addition, the surface modification layer is shown in a cross section. In fact, when a reusable carrier is provided, the surface modification layer will be evenly disposed on the bonding surface 14. Typically, the thickness 38 will be about a few nanometers, such as 0.1 to 2.0 nm or up to 10 nm, and in some cases, up to 100 nm. The thickness 38 can be measured by elliptically polarized light. In addition, the presence of the surface modification layer can be detected by surface chemical analysis, such as by ToF Sims mass spectrometry. Therefore, the contribution of thickness 38 to the thickness 8 of the object is negligible and can be omitted from the calculation for determining the appropriate thickness 18 of the carrier 10 for processing a given sheet 20 having a thickness of 28. However, to the extent that the surface modification layer 30 has any significant thickness 38, this thickness may be considered for determining the thickness 18 of the carrier 10 for a given thickness 28 of the sheet 20 and a given thickness targeted by the design processing equipment.

The carrier 10 has a first surface 12, a bonding surface 14, a periphery 16, and a thickness 18. In addition, the carrier 10 may have any suitable material, including, for example, glass. The carrier need not be glass, but may instead be ceramic, glass-ceramic, or metal (because surface energy and / or bonding can be controlled in a manner similar to that described below in connection with glass carriers). If the carrier 10 is made of glass, the carrier may have any suitable composition, including aluminosilicate, borosilicate, aluminoborosilicate, soda-lime silicate, and may be an alkali metal-containing or Alkali-free, depending on its end use. The thickness 18 may be about 0.2 to 3 mm or more, such as 0.2, 0.3, 0.4, 0.5, 0.6, 0.65, 0.7, 1.0, 2.0, or 3 mm or more, and will depend on thickness 28 and thickness 38 (as noted above, This is true when this thickness is not negligible). In addition, the carrier 10 may be made of one layer as shown, or made of multiple layers (including multiple sheets of the same or different materials) joined together. In addition, the vehicle may have a Gen 1 size or larger, for example, Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or larger (for example, 100 mm x 100 mm to 3 meters x 3 meters or larger Sheet size).

The sheet 20 has a first surface 22, a bonding surface 24, a periphery 26, and a thickness 28. The perimeters 16 and 26 may have any suitable shape, may be the same as each other, or may be different from each other. In addition, the sheet 20 may have any suitable material, including, for example, glass, ceramic, or glass-ceramic. In some cases, the sheet 20 may be a polymer or a composite sheet having a polymer and / or glass bonding surface. When the sheet 20 is made of glass, the sheet may have any suitable composition including aluminosilicate, borosilicate, aluminoborosilicate, soda-lime silicate, and may be alkali metal-containing or Alkali, it depends on its end use. The thermal expansion coefficient of the sheet can be relatively closely matched to the thermal expansion coefficient of the carrier in order to prevent objects from Warpage during processing at warm temperatures. When the object 2 is processed at a lower temperature, that is, the case where CTE matching is not such a concern, the polymer sheet can be used with a glass carrier. Of course, there may be other situations where a polymer sheet can be used with a glass carrier. As indicated above, the thickness 28 of the sheet 20 is 300 microns or less. In addition, the sheet may have a Gen 1 size or larger, for example, Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or larger (for example, a sheet of 100 mm x 100 mm to 3 meters x 3 meters or larger Size).

Not only does the item 2 need to have the correct thickness for processing in existing equipment, but sometimes it will also need to be preserved in the harsh environment in which it can be processed. For example, flat panel display (FPD) processing may include wet processing, ultrasonic processing, vacuum processing, and in some cases high temperatures (e.g., 400 ° C). For some processes, as noted above, the temperature can be 500 ℃, or 600 ° C and up to 650 ° C.

In order to preserve in the harsh environment in which the article 2 is to be treated, such as during FPD manufacturing, the bonding surface 14 should be bonded to the bonding surface 24 with sufficient strength without the sheet 20 being separated from the carrier 10. Moreover, this strength should be maintained during processing so that the sheet 20 does not separate from the carrier 10 during processing. In addition, in order to allow the sheet 20 to be removed from the carrier 10 (so that the carrier 10 can be reused), the bonding surface 14 should not be generated by the initial design bonding force and / or by modification of the initial design bonding force. Bonding force (e.g., may Occurs during processing at a temperature of 400 ° C.) The bonding to the bonding surface 24 is too strong. The surface modification layer 30 can be used to control the bonding strength between the bonding surface 14 and the bonding surface 24 in order to achieve these two goals. The controlled bonding force is achieved by controlling the contribution of van der Waals (and / or hydrogen bonding) and covalent attraction energy to the total adhesion energy, which is adjusted by adjusting the thickness of the sheet 20 and the carrier 10 Polar and non-polar surface energy components to control. This controlled bond is strong enough for FPD processing (including wet processes, ultrasonic processes, vacuum processes, and thermal processes, including 400 ° C, and in some cases, 500 ℃ or 600 ° C and up to 650 ° C processing temperature), and maintained to be able to be disengaged by applying a sufficient separation force and also by not causing a destructive force on the sheet 20 and / or the carrier 10. This disengagement allows removal of the sheet 20 and the devices made thereon, and also allows reuse of the carrier 10.

Although the surface modification layer 30 is shown as a solid layer between the sheet 20 and the carrier 10, this need not be the case. For example, the layer 30 may be about 0.1 to 2 nm thick and may not completely cover each bit of the bonding surface 14. For example, coverage can be 100%, 1% to 100%, 10% to 100%, 20% to 90%, or 50% to 90%. In other embodiments, the layer 30 may be up to 10 nm thick, or in other embodiments, even up to 100 nm thick. The surface modification layer 30 may be regarded as being disposed between the carrier 10 and the sheet 20, although it may not contact any of the carrier 10 and the sheet 20. In any case, an important aspect of the surface modification layer 30 lies in its ability to modify the bonding surface 14 and the bonding surface 24 to control the strength of the bonding between the carrier 10 and the sheet 20. The material and thickness of the surface modification layer 30 and the treatment of the bonding surfaces 14 and 24 before bonding can be used to control the strength of the bonding (energy of adhesion) between the carrier 10 and the sheet 20.

In general, the energy of adhesion between two surfaces is given by ("A theory for the estimation of surface and interfacial energies. I.derivation and application to interfacial tension", LA Girifalco and RJGood, J. Phys.Chem (, V 61, p904): W = Y ₁ + Y ₂ - Y ₁₂ (1) where Y ₁ , Y ₂ and Y ₁₂ are the surface energy of surface 1, surface 2 and the interface energy of surface 1 and surface 2, respectively. Individual surface energy is usually a combination of two terms; that is, the dispersion component γ ^d and the polar component γ ^p Y = Y ^d + Y ^p (2)

When adhesion is mainly due to the London dispersion force (γ ^d ) and the polar force (γ ^p ) such as hydrogen bonding, the interfacial energy can be given by (Girifalco and RJGood, as mentioned above):

After substituting (3) into (1), the energy of adhesion can be roughly calculated as: In equation (4) above, only the Van der Waals (and / or hydrogen bonding) components of the adhesive energy are considered. These components include polar-polar interaction (Keesom), polar-nonpolar interaction (Debye), and non-polar-nonpolar interaction (London). However, other attractive energies may also exist, such as covalent bonding and electrostatic bonding. Therefore, in a more general form, write the above equation as: Wherein w _c and w _e is a covalent and electrostatic adhesion energy. Covalent adhesion energy is quite common, as is common in silicon wafer bonding, where an initially hydrogen-bonded pair of wafers is heated to a higher temperature to convert most or all of the silanol-silanol hydrogen bonds to Si- O-Si covalent bond. Although the initial, room temperature hydrogen bonding produces an adhesive energy of about 100-200 mJ / m ² that allows separation of the bonding surfaces, a fully covalently bonded crystalline circle pair as achieved during high temperature processing (about 400 to 800 ° C) It has an adhesion energy of about 1000-3000 mJ / m ² , which does not allow separation of the bonding surfaces; instead, the two wafers act as a monolith. On the other hand, if both surfaces are completely coated with a low surface energy material such as a fluoropolymer (thick enough to shield the effect of the underlying substrate), the adhesion energy will be the adhesion energy of the coating material, and will be Very low, resulting in low or no adhesion between the bonding surfaces 14, 24, whereby the sheet 20 cannot be handled on the carrier 10. Consider two extreme conditions: (a) two standard clean 1 (SC1, as known in this technology) clean glass surfaces, whose silanol groups are saturated and joined together at room temperature via hydrogen bonding (by approx. 100-200 mJ / m ² ), and then heated to a high temperature (the adhesion energy becomes 1000-3000 mJ / m ² ) to convert the silanol group into a covalent Si-O-Si bond. The latter adhesion energy is too high for the pair of glass surfaces to be detached; and (b) the two glass surfaces completely coated with a fluoropolymer having a low surface adhesion energy (approximately 12 mJ / m ² per surface), It is joined at room temperature and heated to a high temperature. In the latter case (b), not only do the surfaces not bond (because the total adhesive energy of about 24 mJ / m ² is too low when the surfaces are placed together), but the surfaces do not bond at high temperatures because they do not exist (Or very few) polar reactive groups are present. Between these two extreme cases, there is a range of adhesion energy, for example, between 50-1000 mJ / m ² , which can produce the desired degree of controlled bonding. Therefore, the inventors have discovered various ways to provide an adjustable surface modification layer 30 that generates an adhesive energy between these two extreme cases and makes it possible to produce a controlled joint, the controlled Bonding is sufficient to maintain a pair of glass substrates (e.g., glass carrier 10 and thin glass sheet 20) bonding to each other during the severe conditions of FPD processing, and the degree of this controlled bonding (even in, for example After the high-temperature treatment at 400 ° C.), the sheet 20 is allowed to be released from the carrier 10 after the treatment is completed. In addition, the detachment of the sheet 20 from the carrier 10 may be performed by mechanical force, and in a manner such that there is no destructive damage to at least the sheet 20, and preferably also such that there is no destructive damage to the carrier 10 .

Equation (5) describes that the adhesion energy is a function of the four surface energy parameters plus covalent and electrostatic energy (if any).

Appropriate adhesion energy can be achieved by a wise choice of the surface modifier, that is, the surface modifier layer 30, and / or heat treatment of the surface prior to bonding. Appropriate adhesion energy can be obtained through the selection of one or both of the chemical modifiers of the bonding surface 14 and the bonding surface 24, which in turn control van der Waals (and / or hydrogen bonding, Because these terms are used interchangeably throughout this specification) adhesion energy and high temperature processing (for example, approximately 400 ° C) possible covalent bond adhesion energy. For example, using SC1 to clean the bonding surfaces of glass (its original silanol groups are saturated and have a high polarity component of surface energy) and coating them with low-energy fluoropolymers, this provides the surface with polar and nonpolar groups Control of score coverage. This not only provides control over the initial Van der Waals bonding (and / or hydrogen bonding) at room temperature, but also provides control over the range / degree of covalent bonding at higher temperatures. Performs control of the initial van der Waals bonding (and / or hydrogen bonding) at room temperature to provide bonding of one surface to another, allowing vacuum processing and or spin-rinsing-drying -dry; SRD) type treatment, and in some cases also provides an easy-to-form bond between one surface and the other-where the easy-to-form bond can be applied externally to the entire area of the sheet 20 at room temperature In the case of force (such as when pressing the sheet 20 into the carrier 10), it is performed using a brush or using a reduced pressure environment. That is, the initial van der Waals joint provides at least a minimum degree of joint that holds the sheet and the carrier together so that they do not separate while one is held and the other is subjected to gravity. In most cases, the initial van der Waals bonding (and / or hydrogen bonding) will have a range that allows the object to also undergo vacuum processing, SRD processing, and ultrasonic processing without delaminating the sheet from the carrier. Via the surface modification layer 30 (including the material from which the surface modification layer is made and / or the surface treatment of the surface to which the surface modification layer is applied) and / or by bonding the surfaces together, This precise control of the Van der Waals (and / or hydrogen bonding) and covalent interactions at an appropriate level by the heat treatment achieves the desired adhesion energy, which allows the sheet 20 to be bonded to the carrier 10 throughout the FPD-type process, At the same time, the sheet 20 is allowed to separate from the carrier 10 after the FPD type processing (by an appropriate force to avoid damage to the sheet 20 and / or the carrier). In addition, where appropriate, an electrostatic charge can be applied to one or both glass surfaces to provide another level of control over adhesion energy.

For example, FPD processing for p-Si and oxide TFTs typically involves thermal processes at temperatures above 400 ° C, above 500 ° C, and in some cases at 600 ° C, or at temperatures above 600 ° C up to 650 ° C. The isothermal temperature causes the thin glass sheet 20 and the glass-to-glass bonding of the glass carrier 10 in the absence of the surface modification layer 30. Therefore, controlling the formation of Si-O-Si bonds results in reusable carriers. One method to control the formation of Si-O-Si bonds at high temperatures is to reduce the concentration of surface hydroxyl groups on the surfaces to be joined.

As shown in Figure 3, this figure is an Iler's plot of the surface hydroxyl concentration on silicon dioxide as a function of temperature (RKIller: The Chemistry of Silica (Wiley-Interscience, New York, 1979)). The number of OH groups decreases as the surface temperature increases. Therefore, heating the silicon dioxide surface (and glass surfaces by similar methods, such as the bonding surface 14 and / or the bonding surface 24) reduces the concentration of surface hydroxyl groups, thereby Reduce the probability of hydroxyl interaction on the two glass surfaces. This reduction in surface hydroxyl concentration reduces the Si-O-Si bonds formed per unit area, thereby reducing adhesion. However, eliminating surface hydroxyls requires high temperatures ( Above 750 ° C to completely eliminate surface hydroxyl groups) Long annealing time. This long annealing time and high annealing temperature lead to expensive processes and impractical processes because it may be higher than the strain point of typical display glass.

From the above analysis, the inventors have found that objects including flakes and carriers suitable for FPD processing (including LTPS processing) can be made by balancing the following three concepts: (1) by controlling the initial room temperature bonding to the load And / or sheet bonding surface modification, which can be performed by controlling Van der Waals bonding (and / or hydrogen bonding) to generate moderate adhesive energy (for example, before surface bonding, having each surface> 40mJ / m ² surface energy) to promote initial room temperature bonding and sufficient to preserve in non-high temperature FPD processes such as vacuum processing, SRD processing, and / or ultrasonic processing; (2) loading in one way And / or sheet surface modification, this method is thermally stable to preserve during the FPD process without outgassing, which can cause delamination and / or unacceptable contamination during device fabrication, for example, where Unacceptable contamination of semiconductor and / or display manufacturing processes using objects; and (3) controlled bonding at high temperatures, which can be controlled by controlling the surface hydroxyl concentration of the carrier and being capable of high temperature (e.g., 400 ° C) to control the concentration of other substances that form strong covalent bonds, so that the bonding energy between the bonding surface of the carrier and the bonding surface of the sheet can be controlled, so that even at high temperatures (especially at 500-650 During the thermal process in the range of ℃, such as after FPD process, the adhesive force between the carrier and the sheet is maintained within a range that allows the use of the sheet without destroying at least the sheet (and preferably not the sheet or the carrier). Either) the separation force disengages the wafer from the carrier and is still sufficient to maintain the engagement between the carrier and the wafer so that the carrier and the wafer do not delaminate during the manufacturing process.

In addition, the inventors have discovered that the use of the surface modification layer 30 (as appropriate along with the preparation of the bonding surface) can balance the above concepts in order to easily achieve a controlled bonding area, that is, to provide sufficient space between the sheet 20 and the carrier 10 The bonding area for room temperature bonding to allow the object 2 to be processed in FPD type processes (including vacuum processes and wet processes), and to control the gap between the sheet 20 and the carrier 10 (even between At a high temperature of 400 ° C) of the covalently bonded junction area to allow the sheet 20 to be removed from the carrier 10 after the object 2 has been subjected to a high temperature process (e.g., FPD type process or LTPS process) without Damage, and preferably no damage to the vehicle). A series of tests were used to evaluate the potential bonding surface preparation and surface modification layer of reusable carriers suitable for FPD processing. Different FPD applications have different requirements, but at this time the LTPS and oxide TFT processes seem to be the most stringent, and therefore the tests representing the steps in these processes are selected because these tests are the intended application of Object 2. Vacuum processes, wet cleaning (including SRD processes and ultrasound-type processes), and wet etching are common for many FPD applications. Typical Si TFT fabrication requires processing up to 320 ° C. Annealing at 400 ° C is used for the oxide TFT process, and crystallization and dopant activation steps above 600 ° C are used for LTPS processing. Therefore, the following five tests were used to evaluate the following possibilities: The specific bonding surface preparation and surface modification layer 30 allows the sheet 20 to remain bonded to the carrier 10 throughout the FPD process, while in this process (including in After processing at a temperature of 400 ° C.), the sheet 20 is allowed to be removed from the carrier 10 (without damaging the sheet 20 and / or the carrier 10). The tests are performed sequentially and samples are advanced from one test to the next unless there is a type of failure that does not allow subsequent testing.

(1) Vacuum test. Vacuum compatibility test performed in STS multiplexed PECVD loadlock chamber (available from SPTS, Newport, UK)-the loadlock chamber is powered by an Ebara A10S dry pump with soft pump valve (available from Ebara Technologies Inc., Sacramento, CA). The sample was placed in a load lock chamber, and the load lock chamber was subsequently pumped from atmospheric pressure to 70 mTorr within 45 sec. The failure indicated by the notation "F" in the "vacuum" column of the table below is deemed to have occurred in the following cases: (a) loss of adhesion between the carrier and the sheet (based on visual inspection with the naked eye, where Failure is deemed to have occurred if the sheet has been dropped from the carrier or has been partially disengaged from the carrier; (b) Foaming between the carrier and the sheet (e.g., determined by visual inspection with the naked eye) -Take photos of the samples before and after processing, and then compare them to determine that the failure has occurred if the size of the defect increases by the size visible to the naked eye; or (c) the movement of the sheet relative to the carrier (such as by borrowing Judged by visual inspection with the naked eye--photographs were taken of the sample before and after the test, where failure was deemed to have occurred if there were movements such as joint defects such as air bubbles, or edge disengagement, or on a carrier The movement of the sheet). In the table below, the notation "P" in the "vacuum" column indicates that the sample has not expired according to previous criteria.

(2) Wet process test. Semitool SRD-470S (available from Applied Materials, Santa Clara, CA) for wet process compatibility testing test. The test consisted of washing at 500 rpm for 60 seconds, Q-washing to 15 MOhm-cm at 500 rpm, rinsing at 500 rpm for 10 seconds, drying at 1800 rpm under warm flow nitrogen for 90 seconds, and drying at 2400 rpm for 180 seconds. The failure indicated by the notation "F" in the "SRD" column of the table below is deemed to have occurred in the following cases: (a) loss of adhesion between the carrier and the sheet (based on visual inspection with the naked eye, where Failure is deemed to have occurred if the sheet has been dropped from the carrier or has been partially disengaged from the carrier; (b) Foaming between the carrier and the sheet (e.g., determined by visual inspection with the naked eye -Take photos of the samples before and after processing, and then compare them to determine that the failure has occurred if the size of the defect increases by the size visible to the naked eye; or (c) the movement of the sheet relative to the carrier (such as by borrowing Judged by visual inspection with the naked eye--photographs were taken of the sample before and after the test, where failure was deemed to have occurred if there were movements such as joint defects such as air bubbles, or edge disengagement, or on a carrier The movement of the flakes); or (d) the penetration of water under the flakes (as determined by visual inspection with a light microscope at 50x, where the liquid or residue is observable, the failure has been determined to have occurred) . In the table below, the notation "P" in the "SRD" column indicates that the sample has not expired according to previous criteria.

(3) Temperature test up to 400 ℃. Alwin21 Accuthermo610 RTP (commercially available from Alwin21, Santa Clara CA) was used to perform the 400 ° C process compatibility test. The carrier having the sheet bonded to it was cyclically heated in a chamber from room temperature to 400 ° C at 6.2 ° C / min, held at 400 ° C for 600 seconds, and cooled to 300 ° C at 1 ° C / min. The carrier and sheet are then cooled to room temperature. The failure indicated by the notation "F" in the "400 ° C" column of the table below is deemed to have occurred in the following cases: (a) loss of adhesion between the carrier and the sheet (based on visual inspection with the naked eye, Where the sheet has been dropped from the carrier or partially disengaged from the carrier, it is deemed to have failed; (b) blistering between the carrier and the sheet (such as by visual inspection with the naked eye) Judgment--Take a photo of the sample before and after processing, and then compare it, and determine that the failure has occurred when the size of the defect increases by the size visible to the naked eye); or (c) the increase between the carrier and the wafer Adhesion, by which increased adhesion prevents the wafer from disengaging from the carrier (by inserting a blade between the wafer and the carrier, and / or by inserting a piece 1 "wide x 6" long (of which 2-3 " Kapton ^TM tape (K102 series from Saint Gobain Performance Plastic, Hoosik NY) attached to a 100mm square thin glass is adhered to the sheet and the tape is pulled without damaging the sheet or carrier, while trying to separate the sheet from the carrier In the case of damage to the sheet or the carrier, If the wafer and the carrier cannot be disengaged by the execution of any of the disengagement methods, the failure is deemed to have occurred. In addition, after the wafer is attached to the carrier and before the thermal cycle, the representative sample is disengaged. Bonding test to determine that the particular material, including any associated surface treatment, allows the flakes to disengage from the carrier before the temperature cycle. In the table below, the notation "P" in the "400 ° C" column indicates: according to previous criteria, samples Not expired.

(4) Temperature test up to 600 ℃. Alwin21 Accuthermo610 RTP was used to perform the 600 ° C process compatibility test. The carrier with the sheet was cyclically heated from room temperature to 600 ° C at 9.5 ° C / min in the chamber, held at 600 ° C for 600 seconds, and then cooled to 300 ° C at 1 ° C / min. The carrier and sheet are then cooled to room temperature. The failure indicated by the notation "F" in the "600 ° C" column of the table below is deemed to have occurred if: (a) the loss of adhesion between the carrier and the sheet (based on visual inspection with the naked eye, Where the sheet has been dropped from the carrier or partially disengaged from the carrier, it is deemed to have failed; (b) blistering between the carrier and the sheet (such as by visual inspection with the naked eye) Judgment--Take a photo of the sample before and after processing, and then compare it, and determine that the failure has occurred when the size of the defect increases by the size visible to the naked eye); or (c) the increase between the carrier and the wafer Adhesion, by which increased adhesion prevents the wafer from disengaging from the carrier (by inserting a blade between the wafer and the carrier, and / or by adhering a piece of Kapton ^™ tape as described above to the wafer, and pulling Tape) without damaging the sheet or carrier, where there is damage to the sheet or carrier when trying to separate the sheet from the carrier, or where the sheet and carrier cannot be performed by any of the disengagement methods In the case of disengagement, the failure is deemed to have occurred . In addition, after the wafer is bonded to the carrier and before thermal cycling, a disengagement test is performed on a representative sample to determine that the particular material and any associated surface treatments allow the wafer to disengage from the carrier before temperature cycling. In the table below, the notation "P" in the column "600 ° C" indicates that the sample has not expired according to previous criteria.

(5) Ultrasonic test. The ultrasonic compatibility test was performed by cleaning the objects in a four-slot pipeline, where the objects were processed in each slot sequentially from slot # 1 to slot # 4. For each of the four tanks, the tank size is 18.4 "L x 10" W x 15 "D. Two cleaning tanks (# 1 and # 2) contain 1% Semiclean in D1 water at 50 ° C KG, which is available from Yokohama Oils and Fats Industry Co Ltd., Yokohama Japan. The cleaning tank # 1 is agitated with a NEY prosonik 2 104kHz ultrasonic generator (available from Blackstone-NEY Ultrasonics, Jamestown, NY), and NEY prosonik is used 2 104kHz ultrasonic generator agitates cleaning tank # 2. Two cleaning tanks (tank # 3 and tank # 4) contain DI at 50 ° C water. Washing tank # 3 was stirred by a NEY sweepsonik 2D 72kHz ultrasonic generator, and washing tank # 4 was stirred by a NEY sweepsonik 2D 104kHz ultrasonic generator. A process was performed in each of the tanks # 1-4 for 10 min, followed by spin-drying (SRD) after removing the sample from the tank # 4. The failure indicated by the notation "F" in the "ultrasonic" column of the table below is deemed to have occurred in the following cases: (a) loss of adhesion between the carrier and the sheet (based on visual inspection with the naked eye, Where the sheet has been dropped from the carrier or partially disengaged from the carrier, it is deemed to have failed; (b) blistering between the carrier and the sheet (such as by visual inspection with the naked eye) Judgment--Take photos of the samples before and after processing, and then compare them to determine that the failure has occurred when the size of the defect has increased by the size visible to the naked eye); or (c) the formation of other gross defects ( As judged by visual inspection using a light microscope at 50x, where it is judged that a failure has occurred in the presence of particles trapped between the thin glass and the carrier that were not previously observed; or (d) water under the sheet Permeation (as determined by visual inspection using a light microscope at 50x, where the liquid or residue is observable, it has been determined that the failure has occurred. In the table below, the notation in the "ultrasonic" column " P "instructions: according to Former criterion, the sample did not fail. In the following tables, blank samples indicative of "ultrasound" column of this test is not the way.

Joint energy test

The bonding energy is the energy consumed to separate the sheet from the carrier. The bonding energy can be measured in various ways. However, as used herein, the bonding energy is measured as follows.

The double cantilever method (also known as the wedge method) was used to measure the joint energy. In this method, a wedge having a known thickness is placed at the edge between the bonding sheet and the carrier glass. The wedge produces a characteristic delamination distance L. This delamination distance is measured and used to calculate the bonding energy γ _BE with Equation 6.

The Young's modulus E of the EXG composition to both the carrier (1) and the sheet (2) was 73.6 GPa. The typical thickness t _s1 of the carrier is 0.7 mm, and the thickness t _s2 of the sheet is 0.13 mm. Martor 37010.20 blade is used for wedges with a thickness t _w of 95 μm. Samples with very high bonding energies, pre-cracked with independent wedges. This allows easier insertion of the wedge and generation of a characteristic delamination length. For the reported bonding energy data, a value of 2500 indicates a test-limit condition, and for that particular sample, the sheet cannot be disengaged from the carrier.

Preparation of bonding surfaces reduced by heating via hydroxyl groups

The surface modification layer 30 is used to modify one or more of the bonding surfaces 14, 24 so that the object 2 can successfully undergo FPD processing (i.e., where the sheet 20 remains bonded to the carrier 10 during processing, but includes high temperature processing The benefit of being able to be separated from the carrier 10 after the treatment) is demonstrated by treating the object 2 with the glass carrier 10 and the thin glass sheet 20 without the surface modification layer 30 therebetween. Specifically, the preparation of joining surfaces 14, 24 was first attempted to reduce hydroxyl groups by heating, but without surface modification layer 30. The carrier 10 and the sheet 20 are cleaned, the bonding surfaces 14 and 24 are bonded to each other, and the object 2 is then tested. The typical cleaning process used to prepare the glass for bonding is the SCI cleaning process, in which dilute hydrogen peroxide and alkali (usually ammonium hydroxide, but also tetramethylammonium hydroxide solutions, such as JT Baker JTB-100 or JTB -111) Zhongqing Clean glass. Cleaning removes particles from the bonding surface and obtains known surface energy, that is, it provides a baseline of surface energy. The cleaning method does not need to be SC1, and other types of cleaning can be used. For example, the type of cleaning may only have a very small effect on the silanol groups on the surface. The results of various tests are shown in Table 1 below.

Strong but separable initial room temperature joints or Van der Waals joints and / or hydrogen bonds are produced by simply cleaning a thin glass sheet of 100mm square x 100 micron thickness, and a glass carrier, ie, 150mm diameter , 0.50 or 0.63mm thick single mean flat (SMF) wafer, the thin glass sheet and the glass carrier each include Eagle XG® display glass (excluding alkali metal, aluminoborosilicate glass, with An average surface roughness Ra of about 0.2 nm, which is commercially available from Corning Incorporated, Corning, NY). In this example, the glass was cleaned in a 65 ° C bath of 40: 1: 2 DI water: JTB-111: hydrogen peroxide for 10 min. The thin glass or glass carrier may or may not have been annealed at 400 ° C for 10 min in nitrogen to remove residual water-the notation in the "Carrier" column or "Thin glass" column in Table 1 below "400 "° C" indicates that the sample is annealed in nitrogen at 400 ° C for 10 minutes. FPD process compatibility test proves that this SC1-SC1 initial, room temperature joint is mechanically strong enough to successfully complete vacuum test, SRD test and ultrasonic test. However, heating at 400 ° C and above creates a permanent bond between the thin glass and the carrier, that is, the thin glass sheet cannot be damaged without damaging either or both of the thin glass sheet and the carrier. Vehicle removed. Moreover, this was the case even for Example 1c, where each of the carrier and the thin glass was subjected to an annealing step to reduce the concentration of surface hydroxyl groups. Therefore, the bonding of the bonding surfaces 14, 24 through the above-mentioned preparation of separate heating and subsequent bonding of the vehicle 10 and the sheet 12 without the surface modification layer 30 is not used for the FPD process (where the temperature will be 400 ° C) suitable for controlled bonding.

Preparation of bonding surface by hydroxyl reduction and surface modification layer

The hydroxyl reduction and surface modification layer 30, such as achieved by, for example, heat treatment, can be used together to control the interaction of the bonding surfaces 14, 24. For example, the bonding energies of the bonding surfaces 14, 24 (Vandvar bonding and / or hydrogen bonding at room temperature due to polar / dispersed energy components, and covalent bonding at high temperatures due to covalent energy components) may be Controlled so as to provide varying joint strength between cases where room temperature bonding is difficult, to cases where easy room temperature bonding of the bonding surface is allowed and the bonding surface is separated after high temperature processing, to-at high temperature processing After-a condition that prevents surface separation without damage. In some applications, it may be desirable to have no or very weak joints (such as when the surface is in a "non-joined" area, which is described in the sheet / vehicle concept of US'727 And as described below). In other applications, such as for FPD and similar processes (where 500 ℃, or 600 ° C and up to 650 ° C process temperature) for reusable carriers, it is desirable to have sufficient Van der Waals bonding and / or hydrogen bonding at room temperature to initially place the sheet and carrier Together, and still prevent or limit high temperature covalent bonding. For other applications, it may be desirable to have sufficient room temperature bonding to initially place the sheet and the carrier together, and to produce strong covalent bonds at high temperatures (e.g. when the surface is in a "bonding area") As such, the "joint area" is described in the sheet / carrier concept of US'727 and as discussed below). Although not wishing to be bound by theory, in some cases, the surface modification layer can be used to control the bonding of the sheet and the carrier initially at room temperature by placing them together, while reducing the hydroxyl groups on the surface (such as by heating the surface Or, for example, by reacting a hydroxyl group with a surface modifying layer) can be used to control covalent bonding, especially covalent bonding at high temperatures.

The material for the surface modification layer 30 of the engagement surface 14, 24 may be provided with an energy (e.g., as measured on a surface, <40mJ / m ² of energy, and include polar and dispersion components), the thereby generated surface only Weak engagement. In one example, hexamethyldisilazane (HMDS) can be used to create this low-energy surface by reacting with surface hydroxyl groups to leave a trimethylsilyl (TMS) capped surface. HMDS as a surface modification layer can be used together with surface heating to reduce the concentration of hydroxyl groups, thereby controlling room temperature bonding and high temperature bonding. By selecting a suitable joint surface preparation for each joint surface 14, 24, an object having a range of capabilities can be achieved. More specifically, with the focus on providing reusable carriers for LTPS processing, a suitable joint can be achieved between the thin glass sheet 20 and the glass carrier 10 for the vacuum processing test, SRD processing test, 400 Each of the ° C (parts a and c) treatment test and the 600 ° C (parts a and c) treatment test are preserved (or each is successfully completed).

In one example, the HMDS treatment of both thin glass and carrier after SC1 cleaning produces a weak bonding surface, thereby challenging bonding using Van der Waals (and / or hydrogen bonding) forces at room temperature. A mechanical force is applied to join the thin glass to the carrier. As shown in Example 2a of Table 2, this joint is very weak, so that the deflection of the carrier is observed in the vacuum test and the SRD treatment, and foaming is observed in the 400 ° C and 600 ° C thermal processes (possibly due to outgassing), and Particle defects were observed after ultrasonic treatment.

In another example, the HMDS treatment of only one surface (the carrier in the cited example) produces strong room temperature adhesion, which is preserved during vacuum treatment and SRD treatment. However, thermal processes at 400 ° C and above bond thin glass to the carrier permanently. This is not surprising, as the relative hydroxyl concentration of 4.6-4.9 / nm ² of the fully hydroxylated silicon dioxide has been calculated by Sindorf and Maciel in J. Phys. Chem. 1982, 86, 5208-5219. The maximum surface coverage of trimethylsilyl on silicon oxide was 2.8 / nm ² , and was 2.7 / nm ² as measured by Suratwala et al. In Journal of Non-Crystalline Solids 316 (2003) 349-363. That is, although the trimethylsilyl group is bonded to some surface hydroxyl groups, some unbound hydroxyl groups will remain. Therefore, given sufficient time and temperature, the expected surface silanol groups are condensed to permanently join the thin glass and the carrier.

The altered surface energy can be generated by heating the glass surface to reduce the surface hydroxyl concentration before HMDS exposure, thereby generating an increased polar component of the surface energy. This reduces the driving force for forming covalent Si-O-Si bonds at high temperatures and results in stronger room temperature bonding, such as Van der Waals bonding (and / or hydrogen bonding). Figure 4 shows the surface energy of the Eagle XG® display glass carrier after annealing and after HMDS treatment. The increased annealing temperature before the HMDS exposure increases the total (polar and dispersed) surface energy after the HMDS exposure by increasing the polarity distribution (line 404) (line 402). It can also be seen that the dispersed contribution to the total surface energy (line 406) is kept largely unchanged by heat treatment. Although not wishing to be bound by theory, increase the polar component of the energy in the surface after HMDS treatment and The further increase in total energy seems to be due to the existence of some exposed glass surface areas even after HMDS treatment due to sub-monolayer TMS coverage with HMDS.

In Example 2b, a thin glass sheet was heated in a vacuum at a temperature of 150 ° C. for one hour before bonding to a non-heat-treated carrier with a coating of HMDS. This heat treatment of thin glass sheets is not sufficient to prevent The thin glass sheet is permanently bonded to the carrier at a temperature of 400 ° C.

As shown in Examples 2c-2e of Table 2, changing the annealing temperature of the glass surface before HMDS exposure can change the bonding energy of the glass surface in order to control the bonding between the glass carrier and the thin glass sheet.

In Example 2c, the carrier was annealed in a vacuum at a temperature of 190 ° C. for 1 hour, and then exposed to HMDS to provide a surface modification layer 30. In addition, the thin glass sheet was annealed in a vacuum at 450 ° C. for 1 hour, and then bonded to a carrier. The obtained article was preserved in the vacuum test, the SRD test, and 400 ° C (parts a and c, but part b was not successfully completed because of the increased foaming), but failed in the 600 ° C test. Therefore, although there is increased resistance to high temperature bonding as compared to Example 2b, this is not sufficient to generate An object processed at a temperature of 600 ° C (for example, LTPS processing), in which the carrier is reusable.

In Example 2d, the carrier was annealed in a vacuum at a temperature of 340 ° C. for 1 hour, followed by HMDS exposure to provide a surface modification layer 30. Again, the thin glass sheet was annealed in a vacuum at 450 ° C for 1 hour, and then bonded to the carrier. The results are similar to those of Example 2c, where the article was preserved in the vacuum test, SRD test, and 400 ° C (parts a and c, but part b was not successfully completed because of the increased foaming), but in the 600 ° C test Failure.

As shown in Example 2e, both the thin glass and the carrier were annealed in a vacuum at 450 ° C for 1 hr, then the HMDS of the carrier was exposed and the bonding of the carrier and the thin glass sheet was subsequently improved. This improved temperature resistance to permanent bonding . The two surfaces were annealed to 450 ° C to prevent permanent bonding after RTP annealing at 600 ° C for 10 minutes, that is, this sample successfully completed the 600 ° C treatment test (parts a and c, but failed to pass part b successfully because of increased Foam; similar results were found for the test at 400 ° C).

In Examples 2a to 2e above, each of the carrier and the sheet is Eagle XG® glass, where the carrier is a 630 micron thick 150 mm diameter SMF wafer, and the sheet is 100 mm square and 100 micron thick. HMDS is applied by pulse vapor deposition in a YES-5 HMDS oven (commercially available from Yield Engineering Systems, San Jose CA), and it is one atomic layer thick (i.e., about 0.2 to 1 nm), despite surface coverage It may be less than a single layer, that is, some of the surface hydroxyl groups are not covered by HMDS, as indicated by Maciel and as discussed above. Due to the small thickness of the surface modification layer, there is almost no risk of outgassing, which can cause contamination of the device fabrication. In addition, as indicated by the "SC1" notation in Table 2, each of the carrier and wafer was cleaned using the SC1 process prior to heat treatment or any subsequent HMDS processing.

The comparison between Example 2a and Example 2b shows that the bonding energy between the sheet and the carrier can be controlled by changing the number of surfaces including the surface modification layer. Moreover, controlling the joining energy can be used to control the joining force between two joining surfaces. In addition, the comparison of Examples 2b-2e shows that the bonding energy of the surface can be controlled by changing the parameters of the heat treatment, and the bonding surface is subjected to the heat treatment before the surface modification material is applied. Again, heat treatment can be used to reduce the number of surface hydroxyl groups and thus control the degree of covalent bonding, especially the degree of covalent bonding at high temperatures.

Other materials that can act in different ways to control the surface energy on the bonding surface can be used in the surface modification layer 30 in order to control the room temperature bonding force and the high temperature bonding force between the two surfaces. For example, if one or two bonding surfaces are modified with a surface modifying layer to generate a moderate bonding force, a reusable carrier can also be created that covers or spatially obstructs substances such as hydroxyl groups to prevent Strong permanent covalent bonds are formed between the carrier and the sheet at high temperatures. One way to generate adjustable surface energy and cover the surface hydroxyl groups to prevent the formation of covalent bonds is the deposition of a plasma polymer film such as a fluoropolymer film. Plasma polymerization is self-sourced under atmospheric pressure or reduced pressure and plasma excitation (DC or RF parallel plate, Inductively Coupled Plasma (ICP) Electron Cyclotron Resonance (ECR) downstream microwave or RF plasma) Gas deposition of thin polymer films, such source gases as fluorocarbon sources (including CF4, CHF3, C2F6, C3F6, C2F2, CH3F, C4F8, CFCs or hydrofluorocarbons), such as alkanes (including Methane, ethane, propane, butane), olefins (including ethylene, propylene), alkynes (including acetylene), and aromatic compounds (including benzene, toluene), hydrogen, and other gas sources, such as SF6. Plasma polymerization produces a layer of highly crosslinked material. Control of reaction conditions and source gases can be used to control film thickness, density, and chemical properties to tailor-made functional groups for the application.

Figure 5 shows the total surface energy (line 502) (including 502) of a plasma polymerized fluoropolymer (PPFP) film deposited from a CF4-C4F8 mixture using an Oxford ICP380 etching tool (available from Oxford Instruments, Oxfordshire UK). Polar component (line 504) and dispersion component (line 506)). The film is deposited on an Eagle XG® glass sheet, and the spectral ellipsometry display film is 1-10 nm thick. As can be seen from Figure 5, glass carriers treated with a plasma polymerized fluoropolymer film containing less than 40% C4F8 exhibit a surface energy of> 40 mJ / m ² and are bonded by van der Waals or hydrogen at room temperature. Bonding creates a controlled bond between the thin glass and the carrier. When the carrier and the thin glass were initially bonded at room temperature, promoted bonding was observed. That is, when the sheet is placed on the carrier and pressed together at one point, the wavefront travels across the carrier, but is viewed on a SC1 treated surface that does not have a surface modifying layer on it To lower speeds. Controlled bonding is sufficient to withstand all standard FPD processes, including vacuum processes, wet processes, ultrasonic processes, and thermal processes up to 600 ° C, that is, this controlled bonding successfully completes the 600 ° C processing test without thin glass self-loading Move or delaminate. Disengagement is accompanied by peeling using a blade and / or Kapton ^™ tape as described above. The process compatibility of two different PPFP films (deposited as described above) is shown in Table 3. PPFP 1 of Example 3a was formed using C4F8 / (C4F8 + CF4) = 0, that is, formed using CF4 / H2 and not using C4F8, and PPFP 2 of Example 3b was deposited using C4F8 / (C4F8 + CF4) = 0.38 . The two types of PPFP films are preserved in vacuum treatment test, SRD treatment test, 400 ° C treatment test and 600 ° C treatment test. However, after 20 minutes of ultrasonic cleaning of PPFP 2, delamination was observed, indicating an insufficient adhesion to withstand this treatment. Nevertheless, the surface modification layer of PPFP2 may be suitable for applications such as where ultrasonic processing is not necessary.

In Examples 3a and 3b above, each of the carrier and the sheet is Eagle XG® glass, where the carrier is a 630 micron thick 150 mm diameter SMF wafer, and the sheet is 100 mm square and 100 micron thick. Due to the small thickness of the surface modification layer, there is almost no risk of outgassing, which can cause contamination of the device fabrication. In addition, because the surface modification layer does not show degradation, there is even less risk of outgassing. In addition, as indicated in Table 3, each of the flakes was cleaned using a SC1 process before a heat treatment at 150 ° C in a vacuum for one hour.

Other materials that can act in different ways to control surface energy can be used as surface modification layers to control the room temperature bonding force and high temperature bonding force between the sheet and the carrier. For example, a bonding surface that can produce a controlled bond can be produced by a silane-treated glass carrier and / or glass flakes. Silane is selected so as to produce suitable surface energy, and so as to have sufficient thermal stability for the application. The carrier or thin glass to be processed can be cleaned by processes such as: O2 plasma or UV-ozone, and SC1 or standard clean two (SC2, known in this technology), In order to remove organics and other impurities (e.g., metals) that would interfere with the silane reaction with the surface silanol groups. Detergents based on other chemical methods can also be used, for example, HF or H2SO4 washing chemical methods. The carrier or thin glass may be heated to control the surface hydroxyl concentration before the silane is applied (as discussed above, in conjunction with the surface modification layer of HMDS), and / or may be heated after the silane application to complete the silane with the surface hydroxyl condensation. The concentration of unreacted hydroxyl groups after silylation can be made low enough before bonding to prevent A permanent bond between the thin glass and the carrier at a temperature of 400 ° C, that is, to form a controlled bond. This method is described below.

Example 4a

The bonding surface was treated with O2 plasma and SC1 glass carrier and then treated with 1% dodecyltriethoxysilane (DDTS) in toluene, and annealed at 150 ° C for 1hr in vacuum to complete the condensation. . The DDTS treated surface exhibits a surface energy of 45 mJ / m ² . As shown in Table 4, the glass flakes (which had been cleaned by SC1 and heated in a vacuum at 400 ° C. for one hour) were bonded to a carrier bonding surface having a DDTS surface modification layer on the carrier bonding surface. This object was preserved in the wet process test and vacuum process test, but without the formation of bubbles under the carrier due to the thermal decomposition of the silane, it was not preserved in the thermal process above 400 ° C. This thermal decomposition is expected for all linear alkoxy and chloroalkylsilanes R1 _x Si (OR2) _y (Cl) _z (where x = 1 to 3 and y + z = 4-x), resulting in good thermal stability Except for methyl, dimethyl and trimethylsilane (x = 1 to 3, R1 = CH ₃ ).

Example 4b

The bonding surface was treated with O2 plasma and SC1 glass carrier and then treated with 1% 3,3,3, trifluoropropyltritheoxysilane (TFTS) in toluene, and under vacuum at 150 ° C Anneal for 1hr to complete the condensation. The TFTS treated surface exhibited a surface energy of 47 mJ / m ² . As shown in Table 4, the glass flakes (which had been cleaned by SC1 and subsequently heated in a vacuum at 400 ° C. for one hour) were bonded to a carrier bonding surface having a TFTP surface modification layer on the carrier bonding surface. This object is preserved in the vacuum process test, the SRD process test and the 400 ° C process test without the permanent bonding of the glass flakes and the glass carrier. However, the 600 ° C test caused bubbles formed under the carrier due to the thermal decomposition of the silane. This is not surprising due to the limited thermal stability of propyl. Although this sample failed due to blistering at the 600 ° C test, the material and heat treatment of this example can be used for some applications where it can tolerate bubbles and its adverse effects, such as a reduction in surface flatness, or an increase Waviness.

Example 4c

Its bonding surface was treated with O2 plasma and SC1 glass carrier and then treated with 1% phenyltriethoxysilane (PTS) in toluene, and annealed in vacuum at 200 ° C for 1hr to complete the condensation. The PTS-treated surface exhibited a surface energy of 54 mJ / m ² . As shown in Table 4, the glass flakes (which had been cleaned by SC1 and subsequently heated in a vacuum at 400 ° C. for one hour) were bonded to a carrier bonding surface having a PTS surface modification layer. This object is preserved in a vacuum process, an SRD process, and a thermal process up to 600 ° C without the permanent bonding of glass flakes and glass carriers.

Example 4d

The bonding surface was treated with O2 plasma and SC1 glass carrier, and then treated with 1% diphenyldiethoxysilane (DPDS) in toluene, and annealed in vacuum at 200 ° C for 1 hr to complete the condensation. The DPDS treated surface exhibited a surface energy of 47 mJ / m ² . As shown in Table 4, the glass flakes (which had been cleaned by SC1 and subsequently heated in a vacuum at 400 ° C. for one hour) were bonded to a carrier bonding surface having a DPDS surface modification layer. This object is preserved in vacuum test and SRD test and thermal process up to 600 ℃ without permanent bonding of glass flakes and glass carriers.

Example 4e.

The bonding surface was treated with O2 plasma and SC1 glass carrier and then treated with 1% 4-pentafluorophenyltriethoxysilane (PFPTS) in toluene, and annealed in vacuum at 200 ° C for 1hr to Complete the condensation. The PFPTS treated surface exhibited a surface energy of 57 mJ / m ² . As shown in Table 4, the glass flakes (which had been cleaned by SC1 and subsequently heated in a vacuum at 400 ° C. for one hour) were bonded to a carrier bonding surface having a PFPTS surface modification layer. This object is preserved in vacuum test and SRD test and thermal process up to 600 ℃ without permanent bonding of glass flakes and glass carriers.

In Examples 4a to 4e above, each of the carrier and the sheet is Eagle XG® glass, wherein the carrier is a 630 micron thick 150 mm diameter SMF wafer, and the sheet is 100 mm square and 100 micron thick. The silane layer is a self-assembled monolayer (SAM) and is therefore less than about 2 nm thick. In the above examples, the SAM was generated using an organosilane having an aryl or alkyl non-polar tail and a mono, di, or triolate head group. These silanes react with the silanol surface on the glass to directly connect organic functional groups. Weak interactions between non-polar head groups organize the organic layer. Due to the small thickness of the surface modification layer, there is almost no risk of outgassing, which can cause contamination of the device fabrication. In addition, because the surface modification layer did not show degradation in Examples 4c, 4d, and 4e, there was an even smaller outgassing risk. In addition, as indicated in Table 4, each of the glass flakes was cleaned using a SC1 process before a heat treatment in a vacuum at 400 ° C for one hour.

As can be seen from the comparison of Examples 4a-4e, controlling the surface energy of the bonding surface to above 40mJ / m ^{2 in} order to promote the initial room temperature bonding is not the only consideration to produce a controlled bonding, which is resistant to FPD treatment and still allows The sheet was removed from the carrier without damage. Specifically, as seen from Examples 4a-4e, each carrier has a surface energy of 40 mJ / m ² or more, thereby promoting initial room temperature bonding so that the object is preserved during vacuum processing and SRD processing. However, Examples 4a and 4b did not successfully complete the 600 ° C treatment test. As noted above, for some applications it is also important for bonding: at most high temperatures (e.g., 400 ℃, 500 ℃ or 600 ° C, up to 650 ° C, if the article is designed to be used in a process in which it is appropriate), and the joint is not degraded to a point where it is insufficient to hold the sheet and the carrier together, The covalent bonding that occurs at these high temperatures is also controlled so that there is no permanent bond between the sheet and the carrier. As shown by the examples in Table 4, aromatic silanes, especially phenylsilanes, are suitable for providing controlled bonding that will promote initial room temperature bonding and will withstand FPD processing and still allow the sheet to self-load Remove without damage.

Surface modification layer of fluorocarbon compound and its treatment

Another example of using plasma polymer film to adjust the surface energy of the bonding surface and generate alternative polar bonding sites on the bonding surface is: surface modification layer The thin film is deposited from a mixture of fluorocarbon gas sources, and then a polar group based on nitrogen is formed on the surface modification layer by using various methods.

The surface modification layer can be formed by plasma polymerization of various mixtures of fluorocarbon gas sources to provide various surface energies, including surface energies greater than about 50 mJ / m ² , such as by fitting by S. Wu (1971) Developed a theoretical model for the contact angle (CA) of three different test liquids (in this case, deionized water (water), hexadecane (HD), and di-iodomethane (DIM) Calculation. (References: S. Wu, J. Polym. Sci. C, 34, 19, 1971, hereinafter referred to as the "Wu model"). Surface energy on the joint surface of the vehicle greater than about 50 mJ / m ² Bonding of the glass to the thin glass sheet is beneficial because it facilitates the initial room temperature bonding of the carrier and the thin glass sheet and allows FPD processing of the carrier / thin glass sheet without disengagement during the manufacturing process. In some cases, Depending on the composition of the surface modification layer and the deposition conditions, a surface modification layer having this surface energy can allow disengagement by peeling, even treating the carrier at a temperature of up to about 600 ° C and in some cases, even higher temperatures And thin glass sheets. Generally speaking, the source gas includes etching gas and polymer As discussed above in connection with FIG. 5, the etching gas may be CF4, and the polymer forming gas may be C4F8. Alternatively, as shown in FIG. 13, the etching gas may be CF4 and the polymer forming gas It can be CHF3. As shown in both Figure 5 and Figure 13, generally speaking, the lower the percentage of polymer-forming gas, the higher the total surface energy 502 and 1312 of the resulting bonding surface, where the total surface energy is the polar component Combination of 504, 1314 (triangular data points) and dispersed components 506, 1316 (square data points). The percentage of polymer-forming gas (such as CHF3) during plasma polymerization can be similarly achieved by using an inert gas (such as Ar). Control to control the resulting surface energy, as shown in Figure 13A, which shows the total surface energy in mJ / m2. Although not wishing to be bound by theory, an inert gas can act as an etchant, diluent, or both In any case, it is obvious that the surface energy of the carrier glass can be modified by the separate CHF3 without any CF4 in the air stream. The deposition of the surface modification layer can occur at atmospheric pressure or reduced pressure, and utilize Plasma excitation is performed, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream microwave or RF plasma. Plasma polymerization surface modification layer can be placed on the carrier , Sheet, or both. As indicated in the example above in conjunction with Table 3, plasma polymerization produces a layer of highly crosslinked material. Control of reaction conditions and source gases can be used to control the thickness, density, and chemical properties of the surface-modified layer film The functional group is specially made for the application. Moreover, by controlling the properties of the film, the surface energy of the bonding surface of the carrier can be adjusted. However, the surface energy is one of the considerations in controlling the degree of bonding.

The degree of controlled or moderate bonding can additionally be adjusted by controlling the polar bonding to achieve the desired surface energy. One way to control polar bonding is to expose the surface modifying layer (formed as above) to another process to incorporate polar groups, such as by a nitrogen-containing plasma treatment. This treatment increases adhesion by forming polar functionalities based on nitrogen on a thin surface modification layer. The nitrogen-based polar groups formed during subsequent processing do not condense with the silanol group to cause permanent covalent bonding, and thus can control the sheet and the carrier during subsequent processing performed to place the film or structure on the sheet. Degree of engagement between. Methods for forming polar groups based on nitrogen include, for example, nitrogen plasma treatment (Example 5b-d, k, l), ammonia plasma treatment (Example 5e, f, hj), and nitrogen / hydrogen plasma treatment (Example 5m). .

It was observed that the thin glass sheet and the glass carrier bonded with the surface modified layer treated with the nitrogen-containing plasma were not permanently adhered after annealing at 600 ° C, that is, part (c) where they successfully completed the 600 ° C temperature test. In addition, this modest joint is strong enough to be maintained during FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above), and remains releasable by the application of a sufficient peel force Join. Disengagement allows removal of devices made on thin glass and reuse of carriers. Nitrogen plasma treatment of the surface modification layer can obtain one or more of the following advantages: high surface energy and low water contact angle, which results in strong adhesion between the sheet and the carrier after initial bonding, and minimal bubble defects ( (See examples 5b-f and il); the reduction in defect formation during heat treatment is due to the improved thermal stability of the surface modification layer (examples 5c, 5d, 5k, 5l, i.e., samples treated with N2 exhibit reduced Formation of bubbles, as visually observed); and / or easier process windows, because the separation of the surface modification layer, its formation and treatment allow optimization of the carrier / surface modification layer and surface modification by different processes Layer / thin glass interface (examples 5b-f and hm). That is, the base material of the surface modification layer and its own deposition process can be configured to optimize the interaction between the surface modification layer and the bonding surface of the carrier. Subsequently, independently, after the surface modification layer is deposited on the carrier, the properties of the surface modification layer can be modified by processing to optimize the surface modification layer and the thin sheet to be placed thereon. interaction.

In the example of Table 5 below, various conditions were used to deposit a plasma polymerized film on a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY). Before the surface modification layer is deposited, the vehicle is cleaned using SC1 and / or SC2 chemistry and standard cleaning techniques. The film was deposited in the Oxford Plasmalab 380 Inductively Coupled Plasma (ICP) system, which has a 13.56MHz RF source on both the coil and the platform, and the platform temperature is fixed at 30C. Nitrogen and ammonia plasma treatments for surface modified layers of samples 5a-5j were performed in an STS multiplexed PECVD equipment with triode electrode configuration mode (available from SPTS, Newport, UK), where the carrier was placed It is placed on a platform heated to 200C, and 380kHz RF energy of a specified wattage is applied to the platform. A shower head is arranged above the platform, and 13.5MHz RF energy of the specified wattage is applied to the showerhead. For the energy applied to both Oxford ICP and STS PECVD, the value is shown as # / # W, where the value before the slash is the watt applied to the top electrode (coil on ICP or sprinkler on PECVD) The value after the slash is the wattage applied to the platform. Where only one value is shown, this value is for the top electrode. The flow rate of gas into the chamber is shown in Table 5 (the flow rate is calculated as standard cubic centimeters per minute-sccm). Therefore, for example, in the "surface treatment" column of Table 5, the notation of Example 5g is interpreted as follows: In an Oxford ICP device, 30 sccm of CF4, 10 sccm of C4F8, and 20 sccm of H2 are flowed together into a chamber having a pressure of 5 mTorr; 1000W of 13.5MHz RF energy was applied to the coil, and 50W of 13.56MHz RF energy was applied to the 30C platform on which the carrier was placed; and the deposition time was 60 seconds. The notation of the remaining examples in the surface treatment column can be interpreted in a similar manner. As another example, in the "plasma treatment" column, the notation of the treatment in Example 5h is interpreted as follows: After the surface modification layer is formed according to the parameters in the surface treatment column of Example 5h, 100 sccm of NH3 is immediately supplied to A STS PECVD chamber with a pressure of 1 Torr and a temperature of 200 ° C; 100 W of 13.56 MHz was applied to the showerhead; and the process was performed for 30 seconds. The notation of the remaining examples in the "plasma treatment" column can be interpreted in a similar way. The surface energy, that is, the polar component and the dispersed component, are adapted by fitting the contact angles of three different test liquids (in this case, deionized water (water), cetane (HD), and diiodomethane (DIM)) CA) Wu model is calculated in mJ / m ² (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D) are displayed, as well as the total energy (T).

In Examples 5b-5f and 5h-5l of Table 5, nitrogen-based polar groups are formed on the surface modification layer, wherein these polar groups are in the carrier and the sheet (for example, the glass carrier and the glass sheet). Moderate adhesions occur between them to create a temporary bond that is strong enough to preserve during FPD processing, but weak enough to allow disengagement. After the treatment, the concentration of the polar groups on the surface of the surface modification layer is greater than the concentration of the other polar groups in the body of the surface modification layer.

Examples of treatment by NH3 plasma (5e, f and h-j).

In an ICP plasma system, a moderate surface energy SML is deposited from 30sccm CF4, 10sccm C4F8, and 20sccm H2 using a 1500W coil and 50W platform RF power at 5mT (Comparative Example 5a), and a 1000W coil and 50W platform RF power at 5mT Another moderate surface energy SML was deposited from 30sccm CF4, 10sccm C4F8, 20sccm H2 (Comparative Example 5g). The surface energy of the untreated fluoropolymer film is shown in Table 5. The samples were transferred to a STS PECVD system and exposed to an ammonia plasma using the conditions listed in Table 5 (Examples 5e, 5f, 5h-j). The surface tension, as measured by the Wu equation using DI water and hexadecane, increased from about 40 mJ / m2 to about 65-80 mJ / m2 depending on the ammonia plasma conditions. A thin glass sheet was bonded to each of these NH3 plasma modified samples. After the temperature test at 600 ° C, it was visually observed that there was almost no change in the bubble area (no formal outgassing test was performed), and the thin glass pieces in all these samples were easy to disengage by hand.

Examples of processing by N2 plasma (5c, d, k, l).

In an ICP plasma system, a moderate surface energy SML is deposited from 30sccm CF4, 10sccm C4F8, and 20sccm H2 using a 1500W coil and 50W platform RF power at 5mT (Comparative Example 5a), and a 1000W coil and 50W platform RF power at 5mT Another moderate surface energy SML was deposited from 30sccm CF4, 10sccm C4F8, 20sccm H2 (Comparative Example 5g). The surface energy of the untreated fluoropolymer film is shown in Table 5. Samples 5c, d, k, and l were subjected to N2 plasma in the ICP system using the conditions listed in Table 5. Handle in place. Surface energy increased from about 40 mJ / m2 to more than 70 mJ / m2 depending on the plasma conditions. A thin glass sheet was bonded to each of these samples. The thin glass pieces of all samples were easily debonded by hand after a temperature test at 600 ° C.

Example (5m) of treatment by simultaneous N2 and H2 plasma.

In an ICP plasma system, moderate surface energy SML was deposited from 30sccm CF4, 10sccm C4F8, and 20sccm H2 using a 1000W coil and a 50W platform RF power at 5mT (Comparative Example 5g). The surface tension of the untreated fluoropolymer film is shown in Table 5. In the ICP system, the conditions listed in Table 5 were used to subject samples 5m to simultaneous N2 + H2 plasma in situ processing. No surface energy is shown that is different from the untreated fluoropolymer film.

Example (5b) of treatment by sequential N2 and H2 plasma.

In an ICP plasma system, moderate surface energy SML was deposited from 30sccm CF4, 10sccm C4F8, 20sccm H2 using a 1500W coil and a 50W platform RF power at 5mT (Comparative Example 5a). The surface energy of the untreated fluoropolymer film is shown in Table 5. This sample was then subjected to sequential N2 and H2 plasma in situ processing in the ICP system using the conditions listed in Table 5. Surface energy rises to over 70mJ / m2. This value is similar to that obtained with an ammonia plasma or a nitrogen plasma. A thin glass piece was bonded to this sample and subjected to a temperature test at 600 ° C. Thereafter, the thin glass piece could be disengaged from the carrier, that is, the sample successfully completed part (c) of the 600 ° C processing test.

The XPS data reveals the effects of ammonia plasma treatment and nitrogen plasma treatment on the surface modification layer. Specifically, the ammonia plasma treatment roughly halved the carbon content of the surface modification, reduced the fluorine concentration by about a quarter, and increased the nitrogen content by about 0.4 at%. It can also be seen that silicon, oxygen, and other glass components increase, which is the same as the removal of fluoropolymer by ammonia plasma. When a small amount of nitrogen is added to the surface consistent. Nitrogen plasma treatment increases the nitrogen content to 2 at%, and similar to ammonia reduces the carbon and fluorine content. Silicon, oxygen, and other glass components also increase, which is consistent with a decrease in film thickness. Therefore, it was confirmed that the ammonia plasma treatment and the nitrogen plasma treatment add polar groups to the surface modification layer and reduce the thickness of the surface layer. The resulting thickness of the surface modified layer is usually less than 20 nm. Therefore, the effective surface modification layer usually balances the thickness of the surface modification layer with the subsequent surface treatment time to achieve a controlled joint.

The thin glass sheet bonded to the carrier according to the examples in Table 5 above is a substrate made of Corning® Willow® glass, which is an aluminoborosilicate alkali-free glass (commercially available from Corning Incorporated, Corning NY ) And has a thickness of 100, 130 and 150 microns. Prior to bonding, Willow® glass is cleaned using an oxygen plasma followed by SC1 and / or SC2 chemistry and standard cleaning techniques.

In the example of Table 5, although the bonding surface on which the surface modification layer is disposed is glass, this need not be the case. Instead, the bonding surface may be another suitable material having surface energy and properties similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

It is demonstrated in the examples in Tables 3 and 5 that the use of the plasma modified fluoropolymer surface modification layer less than 20 nm thick controls the bonding energy of the glass bonding surface. The initial bonding of a glass sheet to such a glass carrier with a surface modifying layer thereon is similar to bonding glass to glass: the front end of the bond moves quickly due to the strong mutual attraction between the sheet and the coated glass carrier. This physical attraction is due to the polar groups (almost silanol groups) on the thin glass sheet and the polarities on the surface modification layer of the carrier with or without hydrogen-bonded molecular water. Keesom interaction between sexual groups. However, the fluoropolymer surface modification treatment prevents permanent bonding of the sheet to the carrier at temperatures up to 600 ° C related to the device fabrication. To provide a mandatory cost advantage for the low yield acid thinning of thicker glass, the carrier must be reusable. This is a concern when using a fluorinated surface modification layer because the fluoropolymer deposition process etches the surface of the carrier. Although their surface modification layers have been used to demonstrate repeated use of the carrier, the surface roughness has increased from 0.3 nm to about 1.2 nm Ra. This increase in roughness can affect vehicle reusability by restricting the bonding area and thereby reducing the bonding energy (the bonding energy on a carrier that has been reused after the surface modification layer has been deposited, removed, and re-deposited). In addition, the increase in surface roughness may limit the reuse of carriers in other applications, such as applications that use the carrier itself as a display substrate, due to non-compliance with specifications for the roughness introduced into glass. It has also been observed that after annealing a pair of bonded thin glass sheets and a carrier at a temperature of> 300 ° C, roughness has been induced on the bonded surface side of the thin glass sheet. The increased roughness on the sheet bonding surface may be due to the etching of the thin glass bonding surface by desorption of fluorine-containing gas from the bonding surface of the carrier treated by the surface modification layer. In some cases, this increase in the roughness of the joint surface is not continuous. In other cases, although the increase in roughness is small, such an increase may be unacceptable because it may limit, for example, reuse of the vehicle. In addition, there may be reasons for which the use of fluorinated gases in certain manufacturing operations is undesirable, such as health and safety.

Thus, there may be cases where the use of alternate polarity is desirable to produce sufficient engagement surface energy (e.g., as described above in conjunction with Table 5 in the example discussed,> 50mJ / m ^2), for producing a controlled engagement, That is, the bond is strong enough to preserve during FPD processing, but allows the sheet to be separated from the carrier without damage (even after high temperature processing, such as after 400 ° C or above or 600 ° C or above). Therefore, the inventors have explored alternative ways to form suitable polar joints that can be used for controlled joints of wafers and carriers.

The inventors have explored that the use of a hydrocarbon polymer or more typically a carbonaceous layer would be available to etch glass, which would leave little or no fluorine. However, several key challenges must be overcome. For the bonding of the carbonaceous layer to the glass, the surface energy of the carbonaceous layer should be greater than about 50 mJ / m ² . To provide a bond that is strong enough to preserve in wet processing without liquid infiltration between the sheet and the carrier, in some cases, the carbonaceous surface modification layer should have a surface energy of 65 mJ / m2 or higher. At 65 mJ / m2, the surface energy of the carrier (for bonding to a thin glass sheet) is sufficient to prevent the penetration of liquid (such as water) between the carrier and the sheet during subsequent processing. With a surface energy of about 50 mJ / m2, bonding to a thin glass sheet may be adequate for most FPD processing, but heat treatment may be required to prevent liquid infiltration. Specifically, the polar component of the hydrocarbon layer must be increased in order to achieve strong dipole-dipole bonding directly to the silanol-based thin glass sheet or mediated by hydrogen-bonded molecular water. The carbonaceous layer should also exhibit thermal, chemical, and vacuum compatibility so that it will be suitable for carrier-sheet objects that will undergo at least amorphous silicon (aSi) TFT, color filter (CF), or Capacitive touch device manufacturing process. This seems possible because aliphatic hydrocarbons such as polyethylene exhibit large thermal stability in an inert atmosphere. Unlike fluoropolymers, which can be depolymerized in some cases, HDPE is only carbonized. Although HDPE can be carbonized, if the thickness of the polymer is low enough, it can still be viewed through it. The last concern is that mechanical stability and wet process compatibility seem to require higher adhesion than can be achieved with van der Waals alone. It should be understood that a bonding energy of about 250 mJ / m2 to about 275 mJ / m2 is beneficial for preservation in a wet ultrasonic process using glass flakes. This large bonding energy can be attributed to particles and edge defects, rather than the basic requirements of the bonding process. Under optimal bonding, two clean glass surfaces can produce a bonding energy of about 150 mJ / m2. Some covalent bonding is needed to achieve a bond strength of 250-275 mJ / m2.

The surface modification layers explored in the examples in Tables 6-12 are organic surface modification layers based on fluorine-free source materials. As will be described in more detail below, an amorphous hydrocarbon layer (or just a carbonaceous layer) can be produced on a glass carrier (Table 6), but the surface energy does not generate a clean glass surface for preservation in the FPD process. Adhesive enough. This is not surprising because organic surface modification layers based on methane and hydrogen do not contain strong polar groups. To increase the number of polar groups available for bonding to thin glass sheets, additional gas was added during the plasma polymerization and sufficient surface energy was achieved (Table 7). However, although sufficient surface energy can be achieved in some situations, this single step process involves a certain amount of complexity in obtaining a suitable mixture of source materials. Therefore, a two-step process was developed, in which: in the first step, a surface modification layer is formed (for example, similar to the way in which this step is performed in the example of Table 6 is formed from two gases); then, in the second step The surface modification layer is treated in various ways to increase the surface energy and polar groups available for bonding to thin glass sheets. Despite more steps, this process is less complicated for management to achieve desirable results. The treatment increases the polar groups at the surface of the surface modification layer that will be bonded to the sheet. Therefore, polar groups can be used to join the carbonaceous layer to the sheet, although the body of the surface modification layer may not contain polar groups in some cases. Various ways to deal with the initial surface modification layer are explored in the examples in Table 8-12. Middle: In the example of Table 8, the surface modification layer is treated with NH3; in the example of Table 9, the surface modification layer is treated with N2; in the example of Table 10, the surface modification layer is sequentially treated with N2 followed by H2 ; The examples in Table 11, sequentially treating the surface modification layer with N2-O2 and then N2; in the example in Table 12, treating the surface modification layer with N2-O2; and in the alternative examples after Table 12, separately The surface modification layer was treated with O2. These examples show the use of nitrogen and oxygen polar groups, but other polar groups may be possible.

Carbonaceous surface modification layer using hydrocarbons (e.g. methane CH4) and optionally hydrogen (e.g. H2)

Another example of using a plasma polymerization film to adjust the surface energy of the bonding surface and cover the surface hydroxyl groups on the bonding surface is the deposition of a surface modification layer film from a carbon-containing gas (for example, a hydrocarbon gas such as methane) and polymerizing in the plasma It is used together with another gas (for example, hydrogen H2) if necessary. However, in most cases, hydrogen flow is preferred because in other cases, the deposited material tends to be graphite, dark, and has a low energy band gap. This point is the same in all carbonaceous surface modified layer examples of Tables 6-12 and 16. The surface modification layer may be formed at atmospheric pressure or reduced pressure, and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream microwave or RF plasma. The plasma polymerized surface modification layer can be placed on a carrier, a sheet, or both. As noted above in connection with the examples in Table 3, plasma polymerization results in layers of highly crosslinked material. Control of reaction conditions and source gases can be used to control the thickness, density, and chemical properties of the surface-modified layer film, to specifically design the functional group for the application, and by controlling the film properties, the surface energy of the bonding surface can be adjusted. Surface energy can be adjusted to control the degree of bonding, that is, In order to prevent permanent covalent bonding between the sheet and the carrier during subsequent processing performed to place the film or structure on the sheet.

In the example of Table 6 below, various conditions were used to deposit a plasma polymerized film on a glass carrier. The deposition parameters explored in the example in Table 6 are: gas ratio (methane: hydrogen); pressure, ICP coil and RF bias power. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY). Prior to film deposition, the vehicle is cleaned using SC1 and / or SC2 chemistry and standard cleaning techniques. The film is deposited in an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) inductively coupled plasma (ICP) tool, where the carrier is placed on a platform with a specified wattage (indicated in the "RF Offset" column) ) Of 13.56MHz RF energy is applied to the platform, a coil is placed above the platform, and a specified wattage (indicated in the "coil" column) of 13.5MHz RF energy is applied to the coil. The flow rates of the methane source (CH4) and hydrogen source (H2) into the chamber are shown in the columns of CH4 and H2 respectively (the flow rate is calculated as standard cubic centimeters per minute-sccm). Let CH4 and H2 gas flow together. The ratio of H2: CH4 source gas is also displayed in the "H2 / CH4" column, and the pressure of the chamber (in mTorr) is displayed in the "pressure" column. Therefore, for example, the notation of Example 6a in Table 6 is interpreted as follows: In an Oxford ICP device, CH4 of 6.7sccm and H2 of 33.3sccm are flowed together into a chamber with a pressure of 20mTorr; 13.5MHz RF energy of 1500W is applied To the coil and apply 300W of 13.56MHz RF energy to the platform on which the carrier is placed. For all deposits, the platform temperature is 30C. The notation for the remaining examples can be interpreted in a similar way. Surface energy is obtained by using three different test liquids (in this case, deionized water (shown in column "W"), cetane (shown in column "H"), and diiodomethane (column "DIM" The contact angle (CA) and Wu model are shown in mJ / m ² (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D) are displayed, as well as the total energy (T).

The surface energy of Examples 6a-6j changed from about 40 mJ / m ² to about 50 mJ / m ² . Basically, however, the surface energy of these examples is less than about 50 mJ / m ² (considered suitable for controllably bonding glass carriers to glass flakes). The thickness of the surface modification layer was about 6 nm. These examples did not produce sufficient adhesion between the carrier and the thin glass sheet that was maintained during the FPD process, that is, the carrier and the thin glass sheet were observed to blister during the vacuum test, and during the wet process test Hot water infiltration was observed.

Although these surface-modifying layers are not suitable for bonding to thin glass sheets per se, they can be used for other applications, such as applying polymer flakes to glass carriers for electronic or other structural processes to thin polymer sheets Material, as discussed below. Alternatively, the sheet may be a composite sheet having a polymer surface that may be bonded to a glass carrier. In this case, the composite sheet A glass layer may be included, on which electronic or other structures may be placed, and the polymer portion forms a bonding surface for controlled bonding with the glass carrier.

In the example of Table 6, although the bonding surface on which the surface modification layer is disposed is glass, this need not be the case. Instead, the bonding surface may be another suitable material having surface energy and properties similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

Single-step formation of surface modified layer using a mixture of non-fluorinated sources

Another example of using a plasma polymerization film to adjust the surface energy of the bonding surface and cover the surface hydroxyl groups on the bonding surface is the deposition of a surface modification layer film from a mixture of non-fluorinated gas sources, including carbon-containing gases, such as hydrocarbons. Deposition of the surface modification layer can occur at atmospheric pressure or reduced pressure, and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modification layer can be placed on a carrier, a sheet, or both. As noted above in connection with the examples in Table 3, plasma polymerization results in layers of highly crosslinked material. Control of reaction conditions and source gases can be used to control the thickness, density, and chemical properties of the surface-modified layer film, to specifically design the functional group for the application, and by controlling the film properties, the surface energy of the bonding surface can be adjusted. The surface energy can be adjusted to control the degree of bonding, that is, to prevent permanent covalent bonding between the sheet and the carrier during subsequent processing performed to place the film or structure on the sheet.

In the example of Table 7 below, various conditions were used to deposit a plasma polymerized film on a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY). Prior to film deposition, the vehicle is cleaned using SC1 and / or SC2 chemistry and standard cleaning techniques. The film was deposited in the Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) inductively coupled plasma (ICP) configuration mode, where the carrier was placed on the platform and the specified wattage (in the "RF Offset" column 13.56MHz RF energy is applied to the platform, a coil is placed above the platform, and 13.5MHz RF energy of the specified wattage (indicated in the "coil" column) is applied to the coil. The flow rates of methane (CH4), nitrogen (N2), and hydrogen (H2) source gases into the chamber are shown in the columns of CH4, N2, and H2, respectively (the flow rate is calculated as standard cubic centimeters per minute-sccm) . The CH4, N2, and H2 gases are caused to flow together. The ratio of N2: CH4 source gas is also displayed in the "N2 / CH4" column, and the pressure of the chamber (in mTorr) is displayed in the "pressure" column. Therefore, for example, the notation of Example 7g in Table 7 is interpreted as follows: In an Oxford 380 ICP device, 15.4sccm of CH4, 3.8sccm of N2, and 30.8sccm of H2 are flowed together into a chamber having a pressure of 5mTorr; 1500W 13.5MHz RF energy is applied to the showerhead; and 50W 13.56MHz RF energy is applied to the platform on which the carrier is placed. For all samples in Table 7, the platform temperature was 30C. The notation for the remaining examples can be interpreted in a similar way. Surface energy is obtained by using three different test liquids (in this case, deionized water (shown in column "W"), cetane (shown in column "H"), and diiodomethane (column "DIM" The contact angle (CA) and Wu model are shown in mJ / m ² (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D) are displayed, as well as the total energy (T). In addition, the "thickness" column shows the thickness value (in Angstroms) of the surface modification layer deposited according to the conditions indicated for that particular example.

Example 7a shows a surface modified layer made from solitary methane. Under these deposition conditions, the surface modified layer formed by methane achieves a surface energy of only about 44 mJ / m ² on the carrier. Although it is not at the desired level for glass-to-glass controlled bonding, it is suitable for bonding polymer bonding surfaces to glass carriers.

Examples 7b to 7e show surface modified layers made from plasma polymerization of methane and nitrogen at various ratios of N2: CH4. Under these deposition conditions, the surface modified layer formed by methane-nitrogen reached a surface energy of about 61 mJ / m ² (Example 7e) to about 64 mJ / m ² (Example 7d) on the carrier. This surface energy is sufficient to controllably bond a thin glass sheet to a glass carrier.

Example 7f shows a surface modified layer made from plasma polymerization of methane and hydrogen (H2). Under these deposition conditions, the surface reforming layer formed by methane-hydrogen achieves a surface energy of about 60 mJ / m ² on the carrier, which is sufficient to controllably bond the thin glass sheet to the glass carrier.

Examples 7g to 7j show surface modified layers made from plasma polymerization of methane, nitrogen and hydrogen. Under these deposition conditions, the surface modified layer formed by methane-nitrogen-hydrogen reaches a surface energy of about 58 mJ / m ² (Example 7g) to about 67 mJ / m ² (Example 7j) on the carrier, which is sufficient A thin glass sheet is controllably bonded to the glass carrier.

It was observed that joining of the thin glass sheet and the carrier with the surface modified layer formed according to Examples 7b to 7j did not permanently adhere after annealing at 450 ° C, that is, part (c) which successfully completed the 400 ° C temperature test. Disengagement allows removal of devices made on thin glass and reuse of carriers.

The thin glass sheet bonded to each of the carriers according to the examples in Table 7 (7b to 7j) is a substrate made of Corning® Willow® glass, which is an aluminum borosilicate alkali-free glass (commercially available) From Corning Incorporated, Corning NY) and has thicknesses of 100, 130, and 150 microns. Prior to bonding, Willow® glass is cleaned using an oxygen plasma followed by SC1 and / or SC2 chemistry and standard cleaning techniques.

In the example of Table 7, although the bonding surface on which the surface modification layer is disposed is glass, this need not be the case. Instead, the bonding surface may be another suitable material having surface energy and properties similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

The surface modification layer of the example of Table 7 is formed in a single step process. That is, appropriate surface energy and polar groups are achieved by depositing a surface modifying layer from a selected mixture of gases under appropriate conditions. Despite reaching the right gas and Conditions, but the process involves a certain amount of complexity in achieving the proper gas mixture. Therefore, a simpler process is sought. It is assumed that proper surface energy and appropriate polar groups can be achieved in a two-step process, each of which will be simple and stable. Specifically, it is assumed that in the first step, a carbonaceous surface modification layer will be deposited, and in the second step, the surface modification layer will be processed to increase the surface energy and generate appropriate polar groups for controlled bonding In which, the polar group can be more concentrated on the surface of the surface modification layer that will be bonded to the sheet without the polar group in the bulk material. According to the example in Table 6, it is known that pressure and coil power have the greatest impact on surface energy. In addition, it is known that the thickness of the film appears to increase with increasing bias and decreasing pressure. Therefore, based on these results, for further exploration of treatments to increase surface energy and incorporate polar groups, the starting point was chosen: 20sccm CH4 40sccm H2 5mT 1500 / 50W 60s amorphous hydrocarbon polymer A surface modification layer deposition process that produces a carbonaceous surface modification layer with a thickness of about 6.5 nm. For the base surface modification layer, various processes are performed in the second step, as listed in the examples in Table 8-11, in order to modify the polar groups at the surface of the surface modification layer to be joined to the sheet and the concentration. Although specific examples of the starting material and the processing material for the surface modification layer are discussed below, in general, the carbonaceous layer is formed of a carbon-containing source, and a polar group is subsequently added by subsequent processing. Similarly, although specific polar groups are shown by way of example, other polar groups may be possible.

Polar groups are introduced into the carbonaceous surface modified layer by NH3 treatment

Another example of using a plasma polymerized membrane to adjust the surface energy of a bonding surface and generate alternative polar bonding sites on the bonding surface is a thin surface modified layer film from a carbon source (e.g., methane (carbon-containing gas source)) From the deposition of hydrogen H2, then Nitrogen treatment of the newly formed surface modified layer. The nitrogen treatment can be performed using, for example, an ammonia plasma treatment. Deposition of the surface modification layer can occur at atmospheric pressure or reduced pressure, and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modification layer can be placed on a carrier, a sheet, or both. As noted above in connection with the examples in Table 3, plasma polymerization results in layers of highly crosslinked material. Control of reaction conditions and source gas can be used to control film thickness, density, and chemical properties, to specifically use functional groups for the application, and by controlling film properties, the surface energy of the bonding surface can be adjusted. Nitrogen-based polar groups formed during subsequent ammonia plasma processing do not condense with the silanol group to cause permanent covalent bonding, and therefore can control the sheet during subsequent processing performed to place the film or structure on the sheet Degree of engagement with the vehicle.

In the examples in Table 8 below, various conditions were used to deposit a plasma polymerized surface modification layer film on a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY). Prior to film deposition, the vehicle is cleaned using SC1 and / or SC2 chemistry and standard cleaning techniques. Surface treatment is deposited in an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) in an inductively coupled plasma (ICP) configuration mode, in which the carrier is placed on a platform and 13.56 MHz RF energy of a specified wattage is applied On the platform, a coil is arranged above the platform, and 13.5MHz RF energy of a specified wattage is applied to the coil. For the applied energy, more commonly, the value is shown as # / # W, where the value before the diagonal line is the wattage applied to the coil (sprinkler), and the value after the diagonal line is the wattage applied to the platform. Where only one value is shown, this value is for the coil. The flow rate of gas into the chamber is shown in Table 8 (the flow rate is calculated as standard cubic centimeters per minute-sccm). During the plasma treatment of the surface modification layer (SML), the temperature of the chamber was 30 ° C. Therefore, for example, the notation of Example 8a in the "Surface Treatment" column of Table 8 is interpreted as follows: In an Oxford ICP device, 40 sccm of CH4 is flowed into a chamber having a pressure of 5 mTorr; 1500 W of 13.5 MHz RF energy is applied to Shower head; applying 50W of 13.56MHz RF energy to the platform on which the carrier is placed; the chamber is at a temperature of 30 ° C; and the deposition time is 60 seconds. The notation of the remaining examples in the surface treatment column can be interpreted in a similar manner, with the exception that the surface treatment is performed in STS multiplexed PECVD (available from SPTS, Newport, UK). The carrier is placed on the ground electrode maintained at 200C, and the gas is introduced through the 13.56MHz RF drive sprinkler. For another example, in the "plasma treatment" column, the notation of the treatment in Example 8a is interpreted as follows: After the surface modification layer is formed according to the parameters in the surface treatment column of Example 8a, 100 sccm of NH3 is supplied to Chamber with a pressure of 1 Torr and a temperature of 200 ° C; 300W of 13.56MHz RF was applied to the showerhead and processed for 60 seconds. The notation of the remaining examples in the "plasma treatment" column can be interpreted in a similar way. The surface energy is determined by using the contact angle of three different test liquids (in this case, deionized water, hexadecane (H) and diiodomethane (DIM)) and the Wu model in mJ / m ² (mJ / m ² Square meters). For surface energy, the polar component (P) and the dispersed component (D) are displayed, as well as the total energy (T).

Examples 8a and 8b show a plasma-polymerized hydrocarbon surface modification layer, which was subsequently treated with a nitrogen-containing gas (ammonia). In the case of Example 8a, ammonia itself used 300 W of power, while in Example 8b, ammonia was diluted with helium and polymerization was performed at a lower power of 50 W. However, in each case, sufficient surface energy was obtained on the carrier bonding surface to allow it to be controllably bonded to a thin glass sheet. Examples 8c and 8d show a plasma-modified hydrocarbon surface modified layer formed by a hydrocarbon-containing gas (methane) and a hydrogen-containing gas (H2), and then subsequently treated with a nitrogen-containing gas (ammonia). In the case of Example 8c, ammonia itself used 300 W of power, while in Example 8d, ammonia was diluted with helium and polymerization was performed at a lower power of 50 W. It was observed that joining the thin glass sheet and the carrier with the surface modified layer formed according to Examples 8a-8d did not permanently adhere after annealing at 450 ° C, that is, it was able to be preserved in part (c) tested at a temperature of 400 ° C . No outgassing test was performed on these samples. In addition, these examples are strong enough to be preserved in FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above) and remain removable by the application of a sufficient peeling force Join. Disengagement allows removal of devices made on thin glass and reuse of carriers.

The thin glass sheet bonded to each of the carriers according to the examples in Table 8 is a substrate made of Corning® Willow® glass, which is an aluminum borosilicate alkali-free glass (commercially available from Corning Incorporated, Corning NY) and has thicknesses of 100, 130 and 150 microns. Before joining, use an oxygen plasma SC1 and / or SC2 chemistry and standard cleaning techniques are then used to clean Willow® glass.

In the example of Table 8, although the bonding surface on which the surface modification layer is disposed is glass, this need not be the case. Instead, the bonding surface may be another suitable material having surface energy and properties similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

Polar groups are introduced into the carbonaceous surface modified layer by N2 treatment

Another example of using a plasma polymer film to adjust the surface energy of a bonding surface and generate alternative polar bonding sites on the bonding surface is a surface modification layer film from a carbon source (e.g., a carbon-containing gas such as methane) and self-hydrogen The deposition of H2 was followed by the nitrogen treatment of the newly formed surface modified layer. The nitrogen treatment for forming a nitrogen-based polar group on the surface modification layer may be performed by a plasma treatment using N2 gas. Deposition of the surface modification layer can occur at atmospheric pressure or reduced pressure, and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modification layer can be placed on a carrier, a sheet, or both. As noted above in connection with the examples in Table 3, plasma polymerization results in layers of highly crosslinked material. Control of reaction conditions and source gases can be used to control the thickness, density, and chemical properties of the surface-modified layer film, to specifically design the functional group for the application, and by controlling the film properties, the surface energy of the bonding surface can be adjusted. The nitrogen-based polar groups formed during subsequent plasma processing do not condense with the silanol group to cause permanent covalent bonding, and therefore it is possible to control the flakes and the during subsequent processing performed to place the film or structure on the sheet. The degree of bonding between vehicles.

In the examples in Table 9 below, various conditions were used for nitrogen treatment of the plasma polymerized film deposited on a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY). Before the surface modification layer is deposited, the vehicle is cleaned using SC1 and / or SC2 chemistry and standard cleaning techniques. The surface modification layer was deposited in an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) in an inductively coupled plasma (ICP) configuration mode, where the carrier was placed on a platform and a 50W 13.56MHz RF energy was applied On the platform, a coil is arranged above the platform, and 1500W of 13.5MHz RF energy is applied to the coil. 20 sccm of methane (CH4) and 40 sccm of hydrogen (H2) were flowed into the chamber under a pressure of 5 mTorr. The surface treatment time was 60 sec, and the platform temperature was 30C for all the samples listed in Table 9. After the previous deposition, the surface modified layer was treated with nitrogen. Specifically, during processing, 13.56 MHz RF energy of the specified wattage (indicated in the "RF Offset" column) is applied to the platform, with a coil placed above the platform, and the specified wattage (in the "Coil" column) is applied. (Note) 13.5 MHz RF energy is applied to the coil. N2 flows into the chamber at a rate of 40 sccm for the time listed in the time table (counted as seconds-s). Therefore, for example, the notation for nitrogen treatment of Example 9a in Table 9 is interpreted as follows: In an Oxford ICP device, 40sccm of N2 is flowed into a chamber with a pressure of 5mTorr; 1500W of 13.5MHz RF energy is applied to the shower head ; And apply 13.56MHz RF energy of 300W to the platform on which the vehicle is placed, and control the temperature of the platform to 30C; and the process is performed for 10 seconds. The notation for the remaining examples can be interpreted in a similar way. Surface energy is obtained by using three different test liquids (in this case, deionized water (shown in column "W"), cetane (shown in column "HD"), and diiodomethane (box "DIM" (Shown in)) and the contact angle (CA) and Wu model are calculated in mJ / m2 (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D) are displayed, as well as the total energy (T).

Examples 9a-9j show that various conditions can be used for the nitrogen treatment of the surface modified layer formed by methane / hydrogen, thereby obtaining various surface energies, that is, from about 53 mJ / m ² (Example 9i) to about 63 mJ / m ² (Example 9b) surface energy, which is suitable for bonding to thin glass sheets. These surface energies obtained after the nitrogen treatment increase from about 42 mJ / m ² (obtained from a base layer formed from methane-hydrogen plasma polymerization). It was observed that joining the thin glass sheet and the carrier with the surface modified layer formed according to Examples 9a-9j did not permanently adhere after annealing at 450 ° C, that is, part (c) where it successfully completed the 400 ° C temperature test. No outgassing test was performed on these samples. In addition, these examples are strong enough to be preserved in FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above) and remain removable by the application of a sufficient peeling force Join. Disengagement allows removal of devices made on thin glass and reuse of carriers.

The thin glass sheet bonded to each of the carriers according to the examples in Table 9 is a substrate made of Corning® Willow® glass, which is an aluminum borosilicate alkali-free glass (commercially available from Corning Incorporated, Corning NY) and has thicknesses of 100, 130 and 150 microns. Prior to bonding, Willow® glass is cleaned using an oxygen plasma followed by SC1 and / or SC2 chemistry and standard cleaning techniques.

In the example of Table 9, although the bonding surface on which the surface modification layer is disposed is glass, this need not be the case. Instead, the bonding surface may be another suitable material having surface energy and properties similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

Polar groups are introduced to the carbonaceous surface modified layer by sequential N2 followed by H2 treatment

Another example of using a plasma polymerized membrane to adjust the surface energy of a bonding surface and generate alternative polar bonding sites on the bonding surface is a surface modification layer film from a carbon source (e.g., methane (carbon-containing gas)) and hydrogen The deposition of H2, followed by the sequential formation of the surface modification layer, followed by hydrogen treatment. Deposition of the surface modification layer can occur at atmospheric pressure or reduced pressure, and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modification layer can be placed on a carrier, a sheet, or both. As noted above in connection with the examples in Table 3, plasma polymerization results in layers of highly crosslinked material. Control of reaction conditions and source gases can be used to control the thickness, density, and chemical properties of the surface-modified layer film, to specifically design the functional group for the application, and by controlling the film properties, the surface energy of the bonding surface can be adjusted. Nitrogen-based polarity formed during subsequent plasma processing The groups do not condense with the silanol group to cause permanent covalent bonding, and thus can control the degree of bonding between the sheet and the carrier during subsequent processing performed to place the film or structure on the sheet.

In the example of Table 10 below, various conditions were used to treat a plasma polymerized film deposited on a glass carrier (using nitrogen and then sequentially using hydrogen). The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY). Prior to film deposition, the vehicle is cleaned using SC1 and / or SC2 chemistry and standard cleaning techniques. The film was deposited in an inductively coupled plasma (ICP) configuration mode in Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK), where the carrier was placed on a platform and 50W 13.56MHz RF energy was applied to the platform A coil is placed above the platform, and 1500W of 13.5MHz RF energy is applied to the coil. 20 sccm of methane (CH4) and 40 sccm of hydrogen (H2) were flowed into the chamber under a pressure of 5 mTorr. The surface treatment time was 60 sec, and the platform temperature was 30C for all the samples listed in Table 9. After the previous deposition, the surface modification layer was sequentially treated with nitrogen and then with hydrogen. To be precise, in each case, for the nitrogen treatment: 40 sccm of N2 was flowed into the chamber, and 13.5 MHz RF energy of 1500 W was applied to the chamber; the chamber was under a pressure of 5 mTorr; and 50 W of 13.56 MHz RF energy was applied to the platform; and processing was performed for 60 seconds. Subsequently, during the hydrogen treatment, 13.56 MHz RF energy of the specified wattage (indicated in the "RF" column of Table 10) is applied to the platform, and a coil is placed above the platform to assign the specified wattage (in the "coil" column) (Note) 13.5 MHz RF energy is applied to the coil. H2 flows into the chamber at a rate of 40 sccm for the time listed in the time table (counted in seconds -s). So, for example, in Table 10, the notation of the hydrogen treatment of Example 10a (after thin film deposition and its N2 treatment as described above) is interpreted as follows: In an Oxford ICP device, 40 sccm of H2 is flowed into a chamber with a pressure of 20 mTorr In the room; 13.5MHz RF energy of 750W was applied to the showerhead; and 13.56MHz RF energy of 50W was applied to the platform on which the carrier was placed; and the process was performed for 15 seconds. The notation for the remaining examples can be interpreted in a similar way. Surface energy is obtained by using three different test liquids (in this case, deionized water (shown in column "W"), cetane (shown in column "H"), and diiodomethane (column "DIM" (Shown in)) and the contact angle (CA) and Wu model are calculated in mJ / m2 (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D) are displayed, as well as the total energy (T).

The sequence of the plasma polymerized surface modification layer formed by methane-hydrogen is N2 and the subsequent H2 plasma treatment can be performed under various conditions to achieve various surface energies. As can be seen from Table 10, the surface energy changed from about 60 mJ / m ² (Example 10d) to about 64 mJ / m ² (Examples 10a, 10n, 10o, and 10p), which are suitable for bonding to thin glass sheets. It was observed that joining the thin glass sheet and the carrier with the surface-modified layer formed according to Examples 10a-10p did not permanently adhere after annealing at 450 ° C, that is, it was able to successfully complete the 400 ° C processing test portion (c). In addition, these examples are strong enough to be preserved in FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above) and remain removable by the application of a sufficient peeling force Join. Disengagement allows removal of devices made on thin glass and reuse of carriers.

The thin glass sheet bonded to each of the carriers according to the example in Table 10 is a substrate made of Corning® Willow® glass, which is an aluminum borosilicate alkali-free glass (commercially available from Corning Incorporated, Corning NY) and has thicknesses of 100, 130 and 150 microns. Prior to bonding, Willow® glass is cleaned using an oxygen plasma followed by SC1 and / or SC2 chemistry and standard cleaning techniques.

In the example of Table 10, although the bonding surface on which the surface modification layer is disposed is glass, this need not be the case. Instead, the bonding surface may be another suitable material having surface energy and properties similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

As a variation of the example in Table 10, sequential nitrogen followed by hydrogen treatment of the surface reforming layer formed by methane is also performed. In this case, when an initial surface modification layer is formed on a glass carrier by plasma polymerization, methane (hydrogen-free) is used alone. Specifically, 40 sccm of methane was allowed to flow at a pressure of 5 mTorr at 1500/50 W for 60 seconds. The surface energy measurement was about 42 mJ / m ² . After sequential treatment with nitrogen (40sccm N2, 1500 / 50W power at 5mTorr pressure, 1500 / 50W power, for 15 seconds) and subsequent hydrogen (40sccm H2, 1500 / 50W power at 5mTorr pressure, 15 seconds), sequentially bonded to the carrier The surface energy achieved on the surface is increased to about 64 mJ / m ² , which is suitable for joining thin glass sheets to a glass carrier.

The sequence of N2 and H2 treatment of the carbonaceous surface modification layer as described above achieves a surface energy of about 64mJ / m2 and forms an initial room temperature bond with a thin glass sheet, wherein the bonding front end speed is slightly less than that using a fluorinated surface modification layer The typical situation. As an example in Table 10, it was observed that these samples did not adhere permanently after annealing at 450 ° C, that is, they were able to successfully complete part (c) of the 400 ° C processing test. In addition, these examples are strong enough to be preserved in FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above) and remain removable by the application of a sufficient peeling force Join. Disengagement allows removal of devices made on thin glass and reuse of carriers.

Polar groups are introduced into the carbonaceous surface modified layer by sequential N2-O2 followed by N2 treatment

Based on the viewpoint of trying to generate more polar sulfonium imine groups on the surface to increase the bonding front-end speed, the sequence of the carbonaceous surface modified layer was investigated by N2-O2 followed by N2 plasma treatment.

An example of using a plasma polymerization membrane to adjust the surface energy of a bonding surface and generate alternative polar bonding sites on the bonding surface is a carbonaceous surface modification layer film from a carbon source (e.g., a carbon-containing gas (e.g., methane)) and From the deposition of hydrogen H2, followed by the N2-O2 and N2 treatment of the surface modification layer just formed. Deposition of the surface modification layer can occur at atmospheric pressure or reduced pressure, and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. Plasma The polymeric surface modification layer may be disposed on a carrier, a sheet, or both. As noted above in connection with the examples in Table 3, plasma polymerization results in layers of highly crosslinked material. Control of reaction conditions and source gases can be used to control the thickness, density, and chemical properties of the surface-modified layer film, to specifically design the functional group for the application, and by controlling the film properties, the surface energy of the bonding surface can be adjusted. The nitrogen-based polar groups formed during subsequent plasma processing do not condense with the silanol group to cause permanent covalent bonding, and therefore it is possible to control the flakes and the during subsequent processing performed to place the film or structure on the sheet. The degree of bonding between vehicles.

In the examples in Table 11 below, various conditions were used to treat the plasma polymerized film deposited on a glass carrier to increase surface energy and incorporate polar groups. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY). Before the surface modification layer is deposited, the vehicle is cleaned using SC1 and / or SC2 chemistry and standard cleaning techniques.

In step 1, a surface modification layer is deposited in an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) in an inductively coupled plasma (ICP) configuration mode, where the carrier is placed on a platform and 50 W of 13.56MHz RF energy is applied to the platform. A coil is placed above the platform, and 13.5MHz RF energy of 1500W is applied to the coil. 20 sccm of methane (CH4) and 40 sccm of hydrogen (H2) were flowed into the chamber under a pressure of 5 mTorr. The surface treatment time was 60 sec, and the platform temperature was 30C for all the samples listed in Table 11.

After the previous deposition in step 1, in step 2, the surface modification layer is treated with nitrogen and oxygen. Specifically, during the processing in step 2, 13.56MHz RF energy is applied to the platform. A coil is placed above the platform, and 800W of 13.5MHz RF energy is applied to the coil. N2 and O2 flow into the chamber at the specified rate (in sccm) for the time listed in the time table (counted as seconds-s). Therefore, for example, the notation of step 2 of Example 11a in Table 11 is interpreted as follows: After the surface modification layer is deposited in step 1, in an Oxford ICP device, 35sccm of N2 and 5sccm of O2 are flowed together with a pressure of 15mTorr In the chamber; apply 13.5MHz RF energy of 800W to the shower head; and apply 13.56MHz RF energy of 50W to the platform on which the temperature of the carrier is controlled to 30 ° C; and the process is performed for 5 seconds. The notation for the remaining examples can be interpreted in a similar way.

After the previous treatment in step 2, in step 3, the surface modification layer is treated with nitrogen. Specifically, during the processing in step 3, a 50 W 13.56 MHz RF energy is applied to the platform, a coil is disposed above the platform, and a 1500 W 13.5 MHz RF energy is applied to the coil. N2 flows into the chamber at the specified rate (in sccm) for the time listed in the duration table (counted as seconds-s). Therefore, for example, the notation of step 3 of Example 11a in Table 11 is interpreted as follows: After the surface modification layer is deposited in step 1, and after the nitrogen-oxygen treatment in step 2, in the Oxford ICP equipment, make 40 sccm N2 flows into the chamber with a pressure of 5mTorr; 1500W of 13.5MHz RF energy is applied to the shower head; and 50W of 13.56MHz RF energy is applied to the platform on which the temperature of the carrier is controlled to 30 ° C ; And the process is performed for 15 seconds. The notation for the remaining examples can be interpreted in a similar way.

Surface energy is measured in mJ / m2 (mJ / m2) by using the contact angle (CA) and Wu model of three different test liquids (in this case, deionized water, cetane and diiodomethane). To calculate. For surface energy, the total surface energy (T, which includes a polar component and a dispersed component) is displayed. The bonding energy is calculated as mJ / m2 as described above. The number of bubbles after initial bonding is indicated in the column named "23C% area", and the number of bubbles after 400 ° C temperature test is indicated in the column named "400C% area". The number of air bubbles is determined by an optical scanner as described below in conjunction with "outgassing". Finally, the change in bubble area from the initial temperature at 23 ° C to the temperature test after 400 ° C is indicated in the column named "Δ% area".

Examples 11a-11e show that various conditions can be used for the sequential nitrogen-oxygen and subsequent nitrogen treatment of the surface modification layer formed by methane / hydrogen to obtain various surface energies, that is, from about 65mJ / m ² (Examples 11a and 11e ) To about 70 mJ / m ² (Examples 11b and 11d), these surface energies are suitable for bonding to thin glass sheets. These surface energies obtained after sequential nitrogen-oxygen and subsequent nitrogen treatments increase from about 40-50 mJ / m ² (obtained by forming a base layer from a methane-hydrogen plasma polymerization). It was observed that joining the thin glass sheet and the carrier with the surface modified layer formed according to Examples 11a-11f did not permanently adhere after annealing at 400 ° C, that is, part (c) which successfully completed the 400 ° C temperature test. As shown in Examples 11a-11e, the change in% bubble area during annealing at 400 ° C is consistent with no outgassing. On the other hand, the change in% bubble area during annealing at 400 ° C. of Example 11f is consistent with some outgassing of the material in the surface modification layer. Therefore, in order to obtain that the surface modified layer deposited according to the conditions in Table 11 has no outgassing, Step 3 is important. However, under other deposition / treatment conditions used in steps 1 and 2, step 3 may not necessarily achieve no outgassing results similar to those obtained in step 3 of Examples 11a-e. In addition, these examples are strong enough to be maintained in FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above) and remain adequate after 400 ° C temperature test. The peeling force is applied to disengage. Disengagement allows removal of devices made on thin glass and reuse of carriers.

The effects of these sequential steps on surface energy, bonding energy, and foaming are shown in Table 11. Increasing the oxygen fraction in the N2-O2 step decreases the surface energy and increases foaming during the outgassing test. The use of a short (about 5 seconds) low oxygen fraction (38/2) N2-O2 step and subsequent short (15 seconds) N2 plasma treatment (Example 11d) to generate a surface energy of 69mJ / m2 during a 400 ° C temperature test And 1.2% bubble area (change from% bubble area at 23 ° C to -0.01, indicating no outgassing). The efficacy of samples 11a-e is equivalent to a fluorinated surface modified layer in applications up to 400 ° C temperature testing.

The thin glass sheet bonded to each of the carriers according to the examples in Table 11 is a substrate made of Corning® Willow® glass, which is aluminum borosilicate The salt is free of alkali metal glass (commercially available from Corning Incorporated, Corning NY) and has thicknesses of 100, 130, and 150 microns. Prior to bonding, Willow® glass is cleaned using an oxygen plasma followed by SC1 and / or SC2 chemistry and standard cleaning techniques.

In the example of Table 11, although the bonding surface on which the surface modification layer is disposed is glass, this need not be the case. Instead, the bonding surface may be another suitable material having surface energy and properties similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

The above example illustrates how an inductively coupled plasma (ICP) system can be used to deposit a thin organic surface modification layer suitable for controllably joining thin glass sheets to a glass carrier for processing by a device. However, the tunability of this solution for display applications where substrates with large areas are advantageous is a concern. ICP tools use planar, cylindrical, or hemispherical coils to induce coupled currents to generate a time-varying magnetic field that causes ion circulation. Typically, the second RF source is connected to a platform on which the substrate is placed. The advantage of ICP plasma is that the ICP source can achieve high-order ionization independently of the substrate bias controlled by the platform RF source. Current parallel plate reactive ion etch (RIE) systems cannot achieve higher-order ionization. In addition, bias and ionization are coupled via RF power and pressure. TEL and others have calibrated ICP etchers to Gen 5, but the larger ones have challenged generating a uniform ICP plasma source. On the other hand, the RIE mode process is suitable for parallel plate tools calibrated to Gen 10. Therefore, the inventors explored ways to achieve similar results in the RIE mode process as those achieved using the ICP tools described above.

The RIE mode surface modification layer is generated from a non-fluorinated source material by using only Oxford's RIE mode (no coil power) and 200W bias power (equivalent to the case of fluorinated surface modification layer deposition). The initial efforts at G.S. resulted in dark, thick layers that could be modified to join thin glass sheets with nitrogen modification. However, this dark material produced many air bubbles after undergoing a 400 ° C processing test, which air bubbles covered about 25% of the joint area. Characterization of dark deposits by spectral ellipsometry confirmed that the film is approximately 100 nm thick and exhibits a narrower optical band gap, which is 0.6 eV relative to 1.7 eV of the ICP-deposited surface modified layer. Based on this result, it was concluded that the material may be graphite and increasing the hydrogen content would be a consideration for reducing foaming.

Experiments were performed to capture optical emission spectroscopy (OES) spectra in order to reflect the RIE process variables H2 / CH4 ratio, RF power, and pressure. However, these ratios cannot be matched within the process window of the Oxford tool used. However, this experiment confirms that the process will benefit from the extremely high hydrogen dilution, high RF power, and low pressure of the polymer-forming gas.

In addition to OES, which guides the process conversion from ICP mode to RIE mode, residual gas analysis (RGA) is used to reflect the changes in hydrogen / methane ratio, RF power, and pressure in RIE mode that exist in Oxford. Gaseous substances. The contour map of m / e = / 16 versus pressure and H2 / CH4 gas ratio confirms once again that a high hydrogen dilution is good for matching an ICP ratio of about 44. Higher alkane is associated with a reduced H2 / CH4 gas ratio and an increased pressure. The contour plot shows that m / e = 28/16 increases with both RF and H2 / CH4 gas ratio. Fitting the RGA response surface suggests that the H2 / CH4 and C2H6 / CH4 ratios can be matched at 40: 1 H2 / CH4 and 25mTorr 275W RF. Carbonaceous RIE mode deposited under this condition The surface modification layer matches the ICP mode carbonaceous surface modification layer with a thickness of about 6 nm and an optical band gap of 1.6 eV. Initial experiments with a nitrogen plasma treatment with a carbonaceous RIE surface modification layer also confirmed low foaming.

The kinetics of RIE mode carbonaceous surface modification layer deposition using the process identified by the RGA experiment is shown in Figures 14 and 15. The surface energy including the total surface energy (T) and the polar component (P) and the dispersed component (D) are shown in FIG. 14. As shown in Figure 14, the surface energy is relatively unchanged, with a slight peak at the 60 sec deposition time, and it can be seen in Figure 15 that the film thickness increases almost linearly on a double logarithmic scale. This is not a self-limiting process because etch-back from hydrogen cannot keep up with polymer deposition.

As discussed above, what is understood from experience is: About 50mJ / m2 or The surface energy of 65mJ / m2 is beneficial to minimize the bubble area during initial room temperature bonding and during thermal cycling. According to Figure 14, it can be seen that the surface energy is exactly on the boundary line. In some cases, this may be suitable for joining the wafer to the carrier, depending on the time-temperature cycle to be experienced, and on other FPD processes that must be experienced. However, on the other hand, it will be beneficial to increase the surface energy of the surface modification layer. Any of the above-mentioned subsequent treatments may be used, for example, ammonia treatment, nitrogen treatment, sequential nitrogen followed by hydrogen treatment, nitrogen-oxygen treatment, sequential nitrogen-oxygen followed by nitrogen treatment. For example, nitrogen-oxygen treatment will be described in conjunction with Table 12.

Polar groups are introduced into the carbonaceous surface modified layer by nitrogen-oxygen treatment

Another example of using a plasma polymerized film to adjust the surface energy of a bonding surface and generate alternative polar bonding sites on the bonding surface is a thin surface modified layer film in a RIE mode from a carbon source (for example, methane, that is, a carbon-containing gas) ) And from hydrogen (H2), followed by nitrogen-oxygen treatment of the newly formed surface modified layer. Available examples Such as nitrogen-oxygen plasma treatment to perform nitrogen-oxygen treatment. Deposition of the surface modification layer can occur at atmospheric pressure or reduced pressure. The plasma polymerized surface modification layer can be placed on a carrier, a sheet, or both. As noted above in connection with the examples in Table 3, plasma polymerization results in layers of highly crosslinked material. Control of reaction conditions and source gas can be used to control film thickness, density, and chemical properties, to specifically use functional groups for the application, and by controlling film properties, the surface energy of the bonding surface can be adjusted. The nitrogen-based polar groups formed during the subsequent nitrogen-oxygen treatment do not condense with the silanol group to cause permanent covalent bonding, and therefore it is possible to control the sheet during subsequent processing performed to place the film or structure on the sheet Degree of engagement with the vehicle.

In the example of Table 12 below, various conditions were used to deposit a plasma polymerized surface modification layer film on a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY). Prior to film deposition, the vehicle is cleaned using SC1 and / or SC2 chemistry and standard cleaning techniques. The surface modification layer was deposited in RIE configuration mode in Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK), where the carrier was placed on a platform, and RF energy of 275W was applied to the platform, which was placed above the platform There is a coil, and no energy is applied to the coil. In step 1, 2 sccm of methane (CH4) and 38 sccm of hydrogen (H2) were flowed into the chamber under a pressure of 25 mTorr. The surface treatment time was 60 sec, and the platform temperature was 30C for all the samples listed in Table 12. After the previous deposition, the surface modification layer is treated with nitrogen and oxygen in step 2. Specifically, during the processing in step 2, 13.56 MHz RF energy of the specified wattage (indicated in the "RF" column) is applied to the platform, and a coil is disposed above the platform, and no energy is applied to the coil. N2 to The rate of sccm listed in the "N2" column flows into the chamber, and O2 flows into the chamber at the rate of sccm listed in the "O2" column, and the time listed in the "time (s)" column of the chronological table (Counted as seconds-s). The chamber is under the pressure (in mTorr) listed in the "Pr" column. Therefore, for example, the notation of nitrogen and oxygen treatment for step 2 of Example 12b in Table 12 is interpreted as follows: In an Oxford ICP device, 25sccm of N2 and 25sccm of O2 are flowed into a chamber with a pressure of 10mTorr; 300W of 13.5MHz RF energy is applied to the platform on which the vehicle is placed, the temperature of the platform is controlled to 30C; and the processing is performed for 10 seconds. The notation for the remaining examples can be interpreted in a similar way.

The surface energy is determined by the contact angle of three different test liquids (in this case, deionized water (W), hexadecane (HD), and diiodomethane (DIM)) and the Wu model. Joules per square meter). For surface energy, the polar component (P) and the dispersed component (D) are displayed, as well as the total energy (T). It also shows the thickness of the surface modification layer ("th" in Angstroms), the average surface roughness of the carrier ("Ra" in Angstroms) after the deposition of the surface modification layer and its N2-O2 treatment, and the bonding Energy ("BE" in mJ / m2), and the bubble area after initial bonding of the thin glass sheet to the carrier via a surface modification layer at room temperature and the bubble area after heating the carrier through a 400 ° C process test % Bubble area change between ("Δ bubble area").

The thin glass sheet bonded to each of the carriers according to the example in Table 12 is a substrate made of Corning® Willow® glass, which is an aluminum borosilicate alkali-free glass (commercially available from Corning Incorporated, Corning NY) and has thicknesses of 100, 130 and 150 microns. Prior to bonding, Willow® glass is cleaned using an oxygen plasma followed by SC1 and / or SC2 chemistry and standard cleaning techniques.

In the example of Table 12, although the bonding surface on which the surface modification layer is disposed is glass, this need not be the case. Instead, the bonding surface may be another suitable material having surface energy and properties similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

According to the treatment in the example in Table 12, it can be seen that after the treatment at 400 ° C: Examples 12a to 12j all have a percentage bubble area change of less than 2 which is consistent with no outgassing at this temperature, see the bubble% column in Table 12; And samples 12a, 12b, 12c, 12g, and 12j each have a bonding energy that allows the sheet to be disengaged from the carrier after this temperature test, see column BE in Table 12; however, examples 12d, 12e, 12f, 12h, and 12i cannot Disengage after the 400 ° C process test, as indicated by the value 2500 in the BE column of Table 12.

According to the example in Table 12, the surface energy, bubble area, bonding energy, and thickness are mapped by% O2, RF, and pressure by ellipsometry. It can be seen that the decrease in thickness is associated with increased RF power (compare Example 12g with Example 12b) and% O2 (compare Example 12a with Example 12b), consistent with the ashing of the hydrocarbon layer. The bonding energy depends only on the pressure: samples treated at 10 mTorr can be unbonded after annealing at 400 ° C (see Examples 12a, 12b, 12c, 12g). Those samples treated above 35mTorr and above 35mTorr cannot be disengaged. See, for example, Example 12d processed at a pressure of 40 mTorr, which has a bonding energy of 2500, and Example 12e, which has a pressure of 70 mTorr and a bonding energy of 2500. The “BE” column indicates the bonding energy of 2500: the thin glass sheet cannot be disengaged from the carrier. The surface energy of all treated membranes is 65-72mJ / m2, It is independent of thickness. See Examples 12a to 12i and 12k. These results suggest that high-pressure N2-O2 plasma treatment produces discontinuous films. In fact, the films are sharpened quickly under high pressure, whereby lower pressures are beneficial. As for blistering, the amount seems to decrease with increasing% O2 * RF. In addition, it can be seen that the H2O partial pressure increases with the increase of% O2 and RF; the thickness of the surface modification layer decreases with the increase in pressure in step 2, and the% bubble area increases with the increase in pressure (hence Low pressure is beneficial); when the processing time is increased, the thickness of the surface modification layer is reduced and the polar groups are reduced, so a shorter processing time is beneficially generated.

Find the right balance of joining energy and foaming. The starting point of the nitrogen-oxygen treatment is 50% O2, 10mTorr 300W and a changed process time. Three groups of samples were prepared using RIE CH4-H2 deposition at 20 seconds, 60 seconds, and 180 seconds, followed by N2-O2 plasma treatment at 0, 5, 15, and 60 seconds. The surface energy and bonding energy peak at the N2-O2 plasma treatment time of 5-15 seconds, which are independent of the CH4-H2 deposition time. The 20-second thin CH4-H2 layer was abraded, and the thin glass sheet was permanently bonded to the carrier. The peak appears before the polymer layer is abraded, which is consistent with the formation of polar groups on the polymer film, not just the abrasion of the exposed glass substrate. The bubble area does increase as the surface modification layer deposition time increases, so it is not beneficial to increase the thickness of the surface modification layer alone to avoid excessive grinding during subsequent N2-O2 surface treatments. Therefore, a good compromise between bonding and bubble area is the balance between the surface modification layer deposition time and the N2-O2 processing time. Based on balanced surface modification layer deposition time (not too long deposition time, which will result in greater thickness, resulting in increased outgassing) and N2-O2 processing time-not too long processing time for grinding or moving Except for the surface modification layer (which results in permanent bonding of the carrier to the sheet), but long enough to incorporate polar groups into the surface modification layer. Good The trade-off is a 60 second RIE deposition of the carbonaceous layer followed by a short N2-O2 processing time of 5-10 seconds. Examples 12a, 12b, 12c, 12g, and 12k are applicable to the RIE mode.

Incorporation of polar groups on the surface modification layer

XPS N1s material formation is used to study the mechanism of N2-O2 plasma treatment to produce highly polar surfaces. In order to study and confirm the material formation of these surface modification layers, the surface chemistry of the relatively thick films of CH4 / H2 deposited on EagleXG® glass wafers was studied so that these thick films achieved complete coverage of the glass, and then N2 / O2 plasma was used for different durations. The advantage of a thick hydrocarbon film is that it allows us to distinguish between those nitrogen substances that are only present on the hydrocarbon film and to separate these nitrogen substances from those that are present on the exposed glass.

The surface composition of the EagleXG® glass wafer was first exposed to a CH4 / H2 plasma for 600 seconds to deposit a thick hydrocarbon film, and then exposed to an N2 / O2 plasma for 5, 15, 60, and 600 seconds. For the 5 and 15 second processing, no elements (such as Al and Ca) present in the glass were detected, which indicates that in those cases, the carbonaceous film layer was thicker than the depth of the XPS probe. The needle depth is about 10 nm.

Exposing the carbonaceous film to the N2 / O2 plasma for 60 seconds and 600 seconds results in a certain degree of thinning of the carbonaceous layer, because under these conditions, XPS can detect the elements present in the glass. This observation was additionally confirmed by considering the surface concentration of carbon. For 60-second and 600-second treatments, the C concentration is less than 10 at%, which strongly implies that, for those conditions, the surface is partially covered by a carbonaceous layer.

NH3 + species were detected only when the real-quality carbonaceous film had been removed by etching. This point strongly suggests that NH3 + substances may only exist on glass, and other substances are involved in the main reaction between nitrogen and the carbonaceous layer. All on the surface The material formation of nitrogen species in terms of atomic percentage (ie, fraction of substance x fraction of nitrogen detected) is presented in Table 13 below.

It can be seen that the main effect of this N2-O2 treatment is the etching of the carbonaceous surface modification layer. In fact, very few carbonaceous materials are present on the surface for 60 and 600 second processing. Other observations are that nitrogen species are present on the surface modification layer even after extremely short N2-O2 treatment times (eg, 5 seconds and 15 seconds). Thereafter, the nitrogen species decreased rapidly, while the ammonia species (indicating the presence of the underlying glass surface) increased rapidly. An XPS evaluation of the formation of carbonaceous surface modified layer of 5-second N2-O2 plasma treated carbon material also revealed that several different materials containing oxygen and nitrogen exist on the surface modified layer. The presence of oxygen-containing species has led to the recognition that a separate O2 plasma may be sufficient to impart polar groups to the surface modifying layer. Indeed, this is the case and it is discussed below.

Based on the assumption that NH3 ⁺ substances exist only on the glass and not on the carbonaceous layer, the surface coverage can be estimated by calculating the ratio of NH3 ⁺ / Σ (all nitrogen compounds). The results of this surface coverage estimation are given in FIG. 17. There is minimal change between 5 and 15 seconds. The largest change occurred between 15 and 60 seconds of N2-O2 plasma treatment time.

The model of N2-O2 plasma treatment of the carbonaceous surface modified layer is as follows. CH4-H2 deposition produces a continuous hydrocarbon layer. In the first second of the N2-O2 plasma treatment, the polar -NH2 group is formed on the polymer surface when the hydrocarbon layer is oxidized and ground. XI Imine or amido groups can also be formed at this time, but XPS is inconclusive. In the case of a longer N2-O2 plasma treatment, the polymer is removed to reach the glass surface, where the polar -NH3 + group is formed by the interaction between the N2-O2 plasma and the glass surface.

O2 alone as the surface treatment of surface modification layer

As an alternative to the N2-O2 treatment of the carbonaceous layer, the use of O2 alone to increase surface energy and generate polar groups on the carbonaceous layer has also been explored. As pointed out above, the formation of the XPS carbon material in the 5-second N2-O2 plasma treatment of the carbonaceous layer confirms that the oxygen-containing material does exist on the surface modification layer. Therefore, an O2 treatment of the carbonaceous layer was attempted. O2 processing is performed in both the ICP mode and the RIE mode.

In 1CP mode, a basic carbonaceous layer is formed according to step 1 in Table 11 above. Subsequently, by performing flow of 40sccm O2, 0sccm N2, using 800 / 50W power and 15mTorr pressure, the surface treatment of step 2 is performed, thereby generating a desired increase in surface energy and generating a desired polar group on the surface of the carbonaceous layer. Thin glass flakes are easily bonded to the surface modification layer at room temperature. In addition, it was observed that this sample did not adhere permanently after annealing at 450 ° C, that is, part (c) of the 400 ° C treatment test could be successfully completed. In addition, this sample is strong enough to be preserved during FPD processing (including the above-mentioned vacuum test (1), wet process test (2), and ultrasonic test (5)), and remains disengageable by the application of a sufficient peeling force . Disengagement allows removal of devices made on thin glass and reuse of carriers.

As an alternative to the N2-O2 treatment of the carbonaceous layer, the use of O2 alone to increase surface energy and generate polar groups on the carbonaceous layer has also been explored. As pointed out above, the formation of the XPS carbon material in the 5-second N2-O2 plasma treatment of the carbonaceous layer confirms that the oxygen-containing material does exist on the surface modification layer. Therefore, try O2 of the carbonaceous layer deal with. O2 processing is performed in both the ICP mode and the RIE mode. In the RIE mode, a base carbonaceous layer is formed according to step 1 in Table 12 above. Subsequently, the surface treatment of step 2 was performed by flowing 50sccm O2, 0sccm N2, and using 200W power under a pressure of 50mTorr. Similar to the ICP mode, these conditions also result in a desired increase in surface energy and a desired polar group on the surface of the carbonaceous layer. Thin glass flakes are easily bonded to the surface modification layer at room temperature. In addition, it was observed that this sample did not adhere permanently after annealing at 450 ° C, that is, part (c) of the 400 ° C treatment test could be successfully completed. In addition, this sample is strong enough to be preserved during FPD processing (including the above-mentioned vacuum test (1), wet process test (2), and ultrasonic test (5)) and remains debondable by the application of a sufficient peeling force . Disengagement allows removal of devices made on thin glass and reuse of carriers.

Therefore, it can be seen that the O2 process operates in a similar manner to the N2-O2 process. Similar considerations apply in terms of the balance between the initial surface modification layer deposition time (which increases thickness) and the O2 treatment time.

Small amount of fluorine

In the XPS analysis of the ICP mode hydrocarbon polymer deposited carbonaceous layer, a few atomic% F was found, that is, about 2.2% F. This is due to the fact that Oxford is used for fluorine and chlorine etching of glass, dielectrics and metals. It has been found that a small amount of fluorine is beneficial to the properties of the surface modification layer of hydrocarbon deposition. A typical reactor cleaning process is SF6-O2 cleaning, followed by O2 cleaning and H2 plasma cleaning. Each step is 30 minutes long and includes pumping / rinsing steps between steps. SF6-O2 is used for initial cleaning because the etch rate of hydrocarbon polymers is considerably higher than that of O2 alone. The H2 plasma cleaning step should remove most of the variable fluorine from the deposits on the reactor wall. If skipped H2 plasma cleaning would then be expected to incorporate higher amounts of fluorine into the hydrocarbon surface modification layer. Fig. 16 The effect of skipping the H2 plasma step in the case of a hydrocarbon surface reforming layer. The bonding energy is reduced, and the permanent bonding is displaced up to 600 ° C without a large increase in blistering. Therefore, a small amount of fluorine in the hydrocarbon surface reforming layer, that is, at least about 3% fluorine is beneficial.

Surface roughness

The variation of the surface roughness of the glass bonding surface due to the deposition of a surface-modified layer formed by the hydrocarbon was investigated. Specifically, a surface reforming layer formed by methane-hydrogen is selected, which is subsequently sequentially treated with nitrogen and then hydrogen. Two carriers were prepared using the surface modification layer formed by methane-hydrogen, followed by in-situ N2 followed by H2 plasma treatment (20CH4 40H2 5mT 1500 / 50W for 60 seconds, followed by 40N2 5mT 1500 / 50W for 15 seconds, followed by 40H2 15mT 1500 / 50W 15 took several seconds). The surface modification layer of the first carrier (Example 14a) was removed by O2 plasma cleaning followed by SC1 cleaning. The surface modification of the second carrier (Example 14b) was kept in place. The third vehicle (Example 14c) was used as a reference and did not have a surface modification layer applied to it. AFM is used to evaluate the surface roughness of: a vehicle to which a surface modification layer is applied and subsequently stripped (Example 14a), a vehicle that still has a surface modification layer on it (Example 14b), and a reference vehicle (Example 14c). The Rq, Ra, and Rz ranges measured by AFM are shown in Table 14 in units of nm (nanometers). The roughness of Examples 14a and 14b cannot be distinguished from the roughness of Example 14c. It should be noted that for Example 14c, the excess z-range of the 5x5 micron scan was due to particles in the scan area. Therefore, it can be seen that the surface-modified layer formed by the hydrocarbon of the present disclosure does not change the surface roughness of the glass bonding surface. In some cases, the unchanged surface roughness of the bonding surface may facilitate, for example, repeated use of the carrier. These The glass carrier in the example is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY).

Overall consideration

The above-mentioned separation of the sheet from the carrier was performed in Example 2-12 at room temperature without adding any additional thermal or chemical energy to modify the bonding interface between the sheet and the carrier. The only energy input is mechanical tensile and / or peeling force.

Because the surface modified layers of Examples 3 and 5-12 are thin organic layers, they are sensitive to oxygen in thermal and plasma treatments. Therefore, these surface modification layers should be protected during device fabrication. The surface modification layer may be protected by using a non-oxygen-containing environment (eg, a N2 environment) during the heat treatment. Alternatively, depositing a protective coating (eg, a thin metal layer) on the edges joining the interface between the thin glass sheet and the carrier is sufficient to protect the surface modification layer from the effects of the oxygen environment at high temperatures.

When both the sheet and the carrier include a glass bonding surface, the surface modifying materials described in Examples 3 to 12 above may be applied to the carrier, to the sheet, or to the surface of the carrier and the sheet to be bonded together Both. Alternatively, when one bonding surface is a polymer bonding surface and the other bonding surface is a glass bonding surface (as further described below), the appropriate surface modification materials (based on the polymer) described in Examples 3 to 12 above are used. (Surface energy of joint surface) Applied to a glass bonding surface. In addition, the entire carrier or sheet need not be made of the same material, but may include different layers and / or materials therein, as long as its joining surface is suitable for receiving the surface modification layer of interest. For example, the bonding surface may be glass, glass-ceramic, ceramic, silicon, or metal, where the remainder of the carrier and / or sheet may be of different materials. For example, the bonding surface of the sheet 20 may be of any suitable material, including, for example, silicon, polycrystalline silicon, single crystal silicon, sapphire, quartz, glass, ceramic, or glass-ceramic. For example, the bonding surface of the carrier 10 may be a glass substrate, or another suitable material having a surface energy similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

As can be seen from the examples discussed herein, the surface modification layer, along with its subsequent processing, provides a way to widely change the surface energy on the glass bonding surface. For example, from all examples, it can be seen that the surface energy of the glass bonding surface can be changed from about 36 mJ / m2 (as in Example 5g) to about 80 mJ / m2 (Example 5f). In the case of using a non-fluorinated source material in a single step process without subsequent surface treatment, it can be seen that the surface energy of the glass bonding surface can be changed from about 37mJ / m2 (Example 16b) to about 67mJ / m2 (Examples 7h and 7j) . In the case of using a carbonaceous surface modification layer and subsequent treatment to increase the polar group, it can be seen that the surface energy of the glass bonding surface can be changed from about 52 mJ / m2 (Example 12j) to about 74 mJ / m2 (Example 8a). In the case of using a non-fluorinated source material in a single-step process or a two-step process, it can be seen that the surface energy of the glass bonding surface can be changed from about 37 mJ / m2 (Example 16b) to about 74 mJ / m2 (Example 8a). In the case of using a fluorine-containing source material or a non-fluorine-containing source material to deposit a surface modification layer and use its subsequent treatment, it can be seen that the surface energy of the glass bonding surface can be changed from about 41 mJ / m2 (example 5m) to about 80 mJ / m2 ( Example 5f).

In addition, as can be seen from the examples discussed herein, the thickness of the surface modification layer can vary greatly. Desirable results are obtained using surface modification layer thicknesses ranging from about 2 nm (as in Example 3) to about 8.8 nm (as in Example 12c).

Use of controlled bonding

Reusable vehicle

One use of controlled bonding through surface modification layers (including materials and associated bonding surface heat treatments) is to provide re-use of a vehicle in an object that has undergone a need A process at a temperature of 600 ° C, as is the case, for example, in the LTPS process. As exemplified by examples 2e, 3a, 3b, 4c, 4d, and 4e and the examples in Table 5 above, surface modification layers (including materials and joint surface heat treatment) can be used to provide repetition of the carrier at these temperature conditions use. Specifically, these surface modification layers can be used to modify the surface energy of the overlapping area between the bonding area of the sheet (having a glass bonding surface) and the bonding area of the carrier (having a glass bonding surface), whereby the entire sheet can be Separate from vehicle after processing. The flakes can be separated all at once, or can be separated in parts, such as when the device created on the part of the flakes is first removed and the remaining part is removed thereafter to clean the carrier for reuse. With the entire sheet removed from the carrier, the carrier can be reused as is by simply placing another sheet on it. Alternatively, the carrier may be cleaned and the sheet may be carried again by reformulating the surface modification layer again. Because the surface modification layer prevents the sheet from permanently joining the carrier, it can be used in 600 ℃ process. Of course, although these surface modification layers can Control the bonding surface energy during processing at a temperature of 600 ° C, but these surface modified layers can also be used to produce flake and carrier combinations that are resistant to processing at lower temperatures and can be used in these lower temperature applications to Control engagement. In addition, in the case where the heat treatment of the object will not exceed 400 ° C, such as by the examples of Examples 2c, 2d, 4b, Table 7-11 (including the examples discussed in the alternatives to the examples of Table 10), Example 12a, 12b, 12c, 12g, 12g and the example of surface treatment using separate O2 are exemplified, the surface modification layer can also be used in the same way.

One advantage of using the surface modification layers described herein is that the carrier can be reused with the same size. Such surface modification layers include, for example, the following surface modification layers: Examples of Table 3, Examples 4b, 4c , 4d, 4e, Examples of Tables 5 and 7-11, Examples 12a, 12b, 12c, 12g, 12j and examples of surface treatment using separate O2. That is, the sheet can be removed from the carrier, the surface modification layer can be removed from the carrier by non-destructive methods (such as O2 or other plasma cleaning), and reused without having to cut the carrier in any way (such as , Cut at the edge of the vehicle).

To provide a controlled joint area

A second use of controlled bonding through a surface modification layer (including material and associated bonding surface heat treatment) is to provide a controlled bonding area between a glass carrier and a glass sheet. More precisely, in the case of using the surface modification layer, a controlled joint area can be formed, in which a sufficient separation force can separate the sheet portion from the carrier without causing the sheet or the carrier to be caused by the joint. Destructed, but still maintaining sufficient bonding force throughout the process to hold the sheet relative to the carrier. Referring to FIG. 6, the glass sheet 20 may be bonded to the glass carrier 10 through the bonding area 40. In the bonding region 40, the carrier 10 and the sheet 20 are covalently bonded to each other so that they serve as a monolith. In addition, there is a controlled joint area 50 with a perimeter 52 in which the carrier 10 and the sheet 20 are connected, but can be separated from each other, even after high temperature processing, such as in This is the case after processing at a temperature of 600 ° C. Although ten controlled joint areas 50 are shown in Figure 6, any suitable number may be provided, including one. As exemplified by examples 2a, 2e, 3a, 3b, 4c, 4d, and 4e, the examples in Table 5 above, the surface modification layer 30 including the heat treatment of the material and the bonding surface can be used on a carrier 10 having a glass bonding surface and A controlled bonding area 50 is provided between the sheets 20 having a glass bonding surface. Specifically, these surface modification layers may be formed in the periphery 52 of the controlled bonding area 50 on the carrier 10 or the sheet 20. Therefore, when the article 2 is processed at a high temperature to form a covalent bond in the bonding region 40 or during the processing of the device, it is possible to provide a receiving area between the carrier 10 and the sheet 20 in an area delimited by the periphery 52. Controlled bonding, whereby the sheet and the carrier can be separated (without devastating damage to the sheet or the carrier) in this area by the separating force, and the sheet and the carrier will not delaminate during a process including ultrasonic processing. The controlled bonding of this application, such as provided by a surface modification layer and any associated heat treatment, can thus improve the vehicle concept in US'727. Specifically, although the vehicle of US'727 proves that the bonded perimeter and non-bonded center area of these vehicles are preserved during FPD processing, the FPD processing includes High temperature processing at about 600 ° C, but ultrasonic processes such as wet cleaning and resist stripping processing are still challenged. Specifically, it is noted that the pressure wave in this solution induces resonances in non-joined regions (such as the non-joined regions described in US'727) in thin glass because the thin glass and the carrier have little or no adhesion in that region Force engagement. Standing waves can be formed in thin glass, where if the ultrasonic agitation has sufficient strength, these waves can cause vibrations, which can cause the thin glass to break at the interface between the bonded and non-bonded areas. This problem can be eliminated by minimizing the gap between the thin glass and the carrier, and by providing sufficient adhesion or controlled bonding in these areas 50 between the carrier 20 and the thin glass 10. As exemplified by Examples 2a, 2e, 3a, 3b, 4c, 4d, 4e, and Table 5, the surface modification layers (including materials and any associated heat treatments) of the bonding surface control the bonding energy in order to provide the Sufficient bonding between the glass bonding surface and the glass surface on the carrier 10 in order to avoid these unwanted vibrations in the controlled bonding area.

Subsequently, during extraction of the desired portion 56 having the periphery 57, the portion of the sheet 20 that is within the periphery 52 may be simply separated from the carrier 10 after processing and after the sheet is separated along the periphery 57. Because the surface modification layer controls the bonding energy to prevent permanent bonding of the sheet to the carrier, it can be used in the temperature 600 ℃ process. Of course, although these surface modification layers can The surface energy of the joints is controlled during processing at a temperature of 600 ° C. These surface modified layers can also be used to produce flake and carrier combinations that are resistant to lower temperature processing and can be used in these lower temperature applications. In addition, in the case where the heat treatment of the object will not exceed 400 ° C, such as by the examples of Examples 2c, 2d, 4b, Table 7-11 (including the examples discussed in the alternative to the examples of Table 10), Example 12a, 12b, 12c, 12g, 12g and the example of surface treatment with separate O2, the surface modification layer can also be used in the same way-in some cases, depending on other process requirements-to control the bonding surface energy .

Used to provide a joint area

The third use of controlled bonding through surface modification layers (including materials and any associated bonding surface heat treatment) is to provide glass carriers and glass flakes. Junction area. Referring to FIG. 6, the glass sheet 20 may be bonded to the glass carrier 10 through the bonding area 40.

In one embodiment of the third use, the bonding area 40, the carrier 10, and the sheet 20 may be covalently bonded to each other so that they serve as a monolith. In addition, there is a controlled bonding area 50 with a perimeter 52 in which the carrier 10 and the sheet 20 are bonded to each other, which is sufficient to withstand processing, and even after high temperature processing, such as in After processing at a temperature of 600 ° C, the sheet is still allowed to separate from the carrier. Therefore, as exemplified by the above examples 1a, 1b, 1c, 2b, 2c, 2d, 4a, 4b, 12d, 12e, 12f, 12h, and 12i, the surface modification layer 30 (including materials and joint surface heat treatment) can be used A bonding area 40 is provided between the carrier 10 and the sheet 20. Specifically, these surface modification layers and heat treatments may be formed outside the periphery 52 of the controlled bonding area 50 on the carrier 10 or the sheet 20. Therefore, when the object 2 is processed at a high temperature, or is processed at a high temperature to form a covalent bond, the carrier and the sheet 20 will be bonded to each other in the bonding region 40 outside the region delimited by the periphery 52. . Subsequently, during the extraction of the desired portion 56 with the perimeter 57, when the sheet 20 and the carrier 10 need to be cut into pieces, the object can be separated along the line 5 because these surface modification layers and heat treatments share the sheet 20 with the carrier 10 The valence bonds, so the sheet 20 and the carrier 10 act as a single piece in this area. Because the surface modification layer provides permanent covalent bonding of the sheet to the carrier, it can be used in 600 ℃ process. In addition, the heat treatment of the object or the initial formation of the bonding area 40 will be In the case of 400 ° C but less than 600 ° C, as exemplified by the materials and heat treatment in Example 4a, the surface modification layer can also be used in the same manner.

In the second embodiment of the third application, in the bonding area 40, the carrier 10 and the sheet 20 can be bonded to each other by controlled bonding through the various surface modification layers described above. In addition, there is a controlled bonding area 50 with a perimeter 52 in which the carrier 10 and the sheet 20 are bonded to each other, which is sufficient to withstand processing, and even after high temperature processing, such as in After processing at a temperature of 600 ° C, the sheet is still allowed to separate from the carrier. Therefore, if the treatment will be performed at a temperature of up to 600 ° C, and it is required to have no permanent or covalent bonding in the region 40, as in the above examples 2e, 3a, 3b, 4c, 4d, 4e and Table 5 As an example, the surface modification layer 30 (including the material and the bonding surface heat treatment) can be used to provide a bonding region 40 between the glass bonding surface of the carrier 10 and the glass bonding surface of the sheet 20. Specifically, these surface modification layers and heat treatments may be formed outside the periphery 52 of the controlled bonding area 50 and may be formed on the carrier 10 or the sheet 20. The controlled bonding region 50 may be formed using a surface modifying layer that is the same as or different from the surface modifying layer formed in the bonding region 40. Alternatively, if the treatment will be performed at a temperature of only up to 400 ° C and it is required to have no permanent or covalent bonding in the region 40, as in the above examples 2c, 2d, 2e, 3a, 3b, 4b, 4c, 4d, 4e, examples in Table 5, examples in Table 7-11 (including examples discussed in the alternatives to the examples in Table 10), examples 12a, 12b, 12c, 12g, 12g, and surfaces using separate O2 The processing example illustrates that the surface modification layer 30 (including the material and the bonding surface heat treatment) can be used to provide a bonding region 40 between the glass bonding surface of the carrier 10 and the glass bonding surface of the sheet 20.

Instead of a controlled engagement in the area 50, there may be non-joined areas in the area 50, where the non-joined areas may be those with increased as described in US'727 The area of surface roughness, or as exemplified by Example 2a, can be provided by a surface modification layer.

For bulk annealing or bulk processing

The fourth use of the controlled bonding described above is for the overall annealing of glass sheet stacks. Annealing is a thermal process used to achieve compaction of glass. Compaction involves reheating the glass body to a temperature below the softening point of the glass, but above the highest temperature reached in subsequent processing steps. This achieves structural rearrangement and slack in the glass before, rather than during, subsequent processing. Annealing prior to subsequent processing is beneficial to maintain precise alignment and / or flatness in the glass body during subsequent processing, as is the case in the manufacture of flat panel display devices, where structures made of many layers need to have very tight tolerances Alignment, even after being subjected to high temperature environments. If the glass is compacted in a high temperature process, the layers of structures deposited on the glass before the high temperature process may not be properly aligned with the layers of structures deposited after the high temperature process.

It is economically attractive to compact stacked glass sheets. However, this makes it necessary to stagger or separate adjacent sheets in order to avoid sticking. At the same time, it is beneficial to maintain the sheet extremely flat and with optical quality, or a Pristine surface finish. In addition, for some stacks of glass sheets, such as sheets with a small surface area, it may be beneficial to "glue" the glass sheets together during the annealing process so that they can be easily moved as a unit without Separated, but easily separated from each other (for example, by peeling off) after the annealing process so that the sheet can be used alone. Alternatively, it may be beneficial to anneal the stack of glass sheets in which the selected glass sheets in the glass sheet are prevented from permanently joining to each other, while at the same time allowing other glass sheets or portions of those other glass sheets (for example, Such as its periphery) are permanently joined to each other. As yet another alternative, it may be beneficial to stack the glass sheets to integrally and selectively permanently join the periphery of a selected pair of adjacent sheets in the stack. The above-mentioned controlled bonding between the glass sheets can be used to achieve the aforementioned overall annealing and / or selective bonding. To control the bonding at any particular interface between adjacent sheets, a surface modifying layer may be used on at least one of the major surfaces facing that interface.

One embodiment suitable for a fully annealed or integrally permanently bonded glass sheet stack in a selected area (eg, around the perimeter) will be described with reference to FIGS. 7 and 8. Among them, FIG. 7 is a schematic side view of the stack 760 of glass sheets 770-772, and FIG. 8 is an expanded view thereof for the purpose of further explanation.

The glass sheet stack 760 may include glass sheets 770-772 and surface modification layers 790, which are used to control the bonding between the glass sheets 770-772. In addition, the stack 760 may include cover sheets 780, 781 disposed on the top and bottom of the stack, and may include a surface modification layer 790 between the cover material and an adjacent glass sheet.

As shown in FIG. 8, each of the glass sheets 770-772 includes a first major surface 776 and a second major surface 778. The glass sheet may be made of any suitable glass material, such as aluminosilicate glass, borosilicate glass, or aluminoborosilicate glass. In addition, the glass may be alkali metal-containing, or may be alkali metal-free. Each of the glass sheets 770-772 may have the same composition, or the sheets may have different compositions. In addition, the glass sheet may be of any suitable type. That is, for example, all of the glass sheets 770-772 may be carriers as described above, may be all sheets as described above, or may be alternately carriers and sheets. Beneficially, when the overall annealing requires different time-temperature cycles for the carrier and for the wafer, a stack of carriers and an independent stack of the wafer are obtained. Alternatively, with the correct surface modification layer material and placement, it may be necessary to obtain a stack with alternating carriers and lamellae, so that when needed, the pairs of carriers and lamellae (i.e., those forming the object) Carriers and wafers) can be covalently bonded to each other as a whole for later processing, while preserving the ability of adjacent objects to be separated from each other. In addition, any suitable number of glass sheets may be present in the stack. That is, although only three glass sheets 770-772 are shown in FIGS. 7 and 8, any suitable number of glass sheets may be included in the stack 760.

In any particular stack 760, any glass sheet may not include a surface modification layer, include one surface modification layer, or include two surface modification layers. For example, as shown in FIG. 8, the sheet 770 does not include a surface modifying layer, the sheet 771 includes a surface modifying layer 790 on its second major surface 778, and the sheet 772 includes two surface modifying layers 790 One of such surface modification layers is on each of its major surfaces 776, 778.

The coverslips 780, 781 can be any material that is suitably resistant (for example, not only in terms of time and temperature, but also other relevant considerations such as outgassing) to a time-temperature cycle of a custom process. Advantageously, the cover sheet may be made of the same material as the glass sheet being processed. When cover sheets 780, 781 are present and have materials that are undesirably bonded to the glass sheet during a given time-temperature cycle after being placed in a stack, the surface modification layer 790 may be included between the glass sheet 771 and the cover as appropriate Between sheet 781, and / or between glass sheet 772 and cover sheet 780. When present between the cover material and the glass sheet, the surface modification layer may be on the cover material (as shown by the cover material 781 and the adjacent sheet 771), and may be on the glass sheet (such as the cover material 780 and the sheet material). 772), or may be on both the cover material and adjacent sheets (not shown) 示). Alternatively, if the cover sheet 780, 781 is present but has a material that will not be joined to the adjacent sheets 772, 772, the surface modification layer 790 need not be present therebetween.

There is an interface between adjacent sheets in the stack. For example, an interface is defined between adjacent glass sheets of the glass sheets 770-772, that is, an interface 791 exists between the sheet 770 and the sheet 771, and an interface 792 exists between the sheet 770 and the sheet 772. In addition, when the cover sheets 780 and 781 exist, there is an interface 793 between the cover material 781 and the sheet 771, and an interface 794 exists between the sheet 772 and the cover material 780.

In order to control the bonding at a given interface 791, 792 between adjacent glass sheets or at a given interface 793, 794 between the glass sheet and the cover sheet, a surface modifying layer 790 may be used. For example, as shown in the figure, at each interface 791, 792, there is a surface modification layer 790 on at least one of the main surfaces facing the interface. For example, for the interface 791, the second major surface 778 of the glass sheet 771 includes a surface modification layer 790 to control the bonding between the sheet 771 and an adjacent sheet 770. Although not shown, the first major surface 776 of the sheet 770 may also include a surface modifying layer 790 thereon to control the engagement with the sheet 771, that is, each of the major surfaces facing any particular interface There is a surface modification layer on it.

A specific surface modification layer 790 (and any associated surface modification treatments) at any given interface 791-794-for example, heat treatment of a specific surface modification layer prior to its application to a specific surface, or Surface heat treatment of the surface contacted by the modified layer) can be selected for the main surfaces 776, 778 facing its specific interface 791-794 to control the bonding between adjacent sheets, and further achieve the The desired result of a fixed time-temperature cycle.

If a stack of glass sheets 770-772 needs to be annealed at a temperature of up to 400 ° C, and each of the glass sheets is separated from each other after the annealing process, bonding at any particular interface such as interface 791 can be used according to the following The materials of any of the examples are controlled together with any associated surface preparation: Examples 2a, 2c, 2d, 2e, 3a, 3b, 4b-4e, Examples of Table 5, Examples of Table 7-11 (including Table 10 The examples discussed above are examples), examples 12a, 12b, 12c, 12g, 12g or examples of surface treatment using separate O2. More specifically, the first surface 776 of the sheet 770 will be treated as "thin glass" in Table 2-4, and the second surface 778 of the sheet 771 will be treated as "Carrier" in Table 2-4 Deal with, or vice versa. A suitable time-temperature cycle with a temperature of up to 400 ° C can then be selected based on the desired degree of compaction, the number of sheets in the stack, and the size and thickness of the sheets in order to achieve the necessary time-temperature throughout the stack.

Similarly, if a stack of glass sheets 770-772 needs to be annealed at a temperature of up to 600 ° C and each of the glass sheets is separated from each other after the annealing process, the bonding at any particular interface such as interface 791 may be Controlled using materials according to any of the following examples along with any associated surface preparation: Examples 2a, 2e, 3a, 3b, 4c, 4d, 4e or the examples of Table 5. More specifically, the first surface 776 of the sheet 770 will be treated as "thin glass" in Table 2-4, and the second surface 778 of the sheet 771 will be treated as "Carrier" in Table 2-4 Deal with, or vice versa. A suitable time-temperature cycle with a temperature of up to 600 ° C can then be selected based on the desired degree of compaction, the number of sheets in the stack, and the size and thickness of the sheets in order to achieve the necessary time-temperature throughout the stack.

In addition, it is possible to perform overall annealing and overall object formation by appropriately configuring a stack of sheets and a surface modification layer between each pair of sheets. If a stack of glass sheets 770-772 is to be annealed at a temperature of up to 400 ° C, and then a pair of adjacent sheets are integrally covalently bonded to each other to form the object 2, suitable materials and associated surface preparations may be Select to control splicing. For example, around the perimeter (or at other areas 40 to be joined), the following can be used to control the joining at the interface between a pair of glass sheets (such as sheets 770 and 771) to be formed as object 2: (i) Around the periphery of the sheets 770, 771 (or other desired bonding area 40), prepared according to any one of the following examples with any associated surfaces: Examples 2c, 2d, 4b, Examples of Tables 7-11 (including The example discussed in the alternative to the example of 10), examples 12a, 12b, 12c, 12g, 12g or examples of surface treatment with separate O2; and (ii) in the inner areas of the sheets 770, 771 (i.e., As in the perimeter area treated in (i), or in the desired controlled joining area 50 where separation of one sheet from another is required), the material according to any of the following examples together with any related Co-surface preparation: Examples 2a, 2e, 3a, 3b, 4c, 4d, 4e or the examples in Table 5. In this case, the device processing in the controlled joint area 50 may be subsequently performed at a temperature of up to 600 ° C.

The material and the heat treatment may be appropriately selected for compatibility with each other. For example, any of the materials 2c, 2d, or 4b may be used for the bonding area 40 together with the material for the controlled bonding area according to Example 2a. Alternatively, the heat treatment for the joining area and the controlled joining area may be appropriately controlled to minimize the effect of the heat treatment in one area that adversely affects the desired degree of joining in the adjacent area.

After the surface modification layer 790 and associated heat treatment for the glass sheets in the stack are appropriately selected, their sheets can be appropriately arranged in the stack, and then heated to 400 ° C. to anneal all the sheets in the stack as a whole. , And the sheets are not permanently joined to each other. Subsequently, the stack can be heated up to 600 ° C to form a covalent bond in the desired bonding region of a pair of adjacent sheets, thereby forming an article 2 having a pattern of bonding regions and controlled bonding regions. The materials of the examples 2a, 2e, 3a, 3b, 4c, 4d, 4e, Table 5 and the associated heat treatments can be used to control the formation of one pair of sheets of the object 2 by covalent bonding through the bonding region 40 and A joint is formed at the interface between separate but adjacent objects 2 of another such sheet so that adjacent objects 2 are not covalently bonded to each other. In the same way that the joints between adjacent objects are controlled, the joints between the objects and the coverslips present in the stack can be controlled.

In addition, similar to the above, it is possible to form the article 2 integrally from the stack 760 without annealing the same stack 760 in advance. Instead, the sheets may have been annealed independently, or annealed in separate stacks and separated from them, and then the sheets are configured for the desired controlled bonding in the stack to produce the object as a whole. According to the global annealing just described above and then forming the object integrally from the same stack, the global annealing is simply omitted.

Although the way of joining at the control interface 791 is explained in detail above, of course, the same control can be performed at the interface 792 or any other interface that may exist in a particular stack-as in a stack with more than three glass sheets Condition, or if there is a cover sheet that will be undesirably bonded to the glass sheet. In addition, the same way of controlling the joint can be used at any interface 791, 792, 793, 794, but different ways of controlling the joint It can also be used at different interfaces to produce the same or different results with respect to the type of bonding desired.

In the process of overall annealing or integrally forming the object 2 and above, when HMDS is used as a material for controlling the bonding at the interface, and HMDS is exposed to the periphery of the stack, it should be covalently bonded in the area where HMDS is desired At this time, heating is performed at about 400 ° C or higher in an oxygen-free atmosphere. That is, if HMDS is exposed to an atmosphere sufficient to oxidize a certain amount of oxygen (at a temperature above about 400 ° C), then the bonding in any such area where HMDS has been oxidized will become Covalent bonding. Other alkyl hydrocarbon silanes can be similarly affected by exposure to oxygen at higher temperatures (eg above about 400 ° C), such alkyl hydrocarbon silanes such as ethyl, propyl, butyl or steryl silane . Similarly, if other materials are used for the surface modification layer, the environment used for the overall annealing should be selected so that the materials will not be degraded during the time-temperature cycle of annealing. As used herein, oxygen-free may mean an oxygen concentration of less than 1000 ppm by volume, and more preferably less than 100 ppm by volume.

Once the stack of sheets has been annealed as a whole, the individual sheets can be separated from the stack. Individual sheets can be processed (e.g., by oxygen plasma, in The surface modification layer 790 is removed by heating in an oxygen environment at a temperature of 400 ° C or by chemical oxidation, SC1 or SC2). Individual sheets can be used, for example, as substrates for electronic devices, such as OLED, FPD, or PV devices when needed).

The above methods of bulk annealing or bulk treatment have the advantage of maintaining the clean sheet surface in an economical manner. Rather, the sheet does not need to be kept in a clean environment from beginning to end, such as in a clean room annealing furnace. Instead, the stack can be formed in a clean environment and subsequently in a standard annealing furnace (i.e., its Medium cleanliness in an annealing kiln), and the surface of the sheet is not soiled by particles because there is no fluid flow between the sheets. Therefore, the surface of the sheet is protected from the environment in which the stack of sheets is annealed. After annealing, the stack of sheets can be easily transported to another processing area (in the same facility or in a different facility), because the sheets maintain a certain degree of adhesion, but they can be separated from each other with sufficient force without damaging the sheets. That is, a glass maker, for example, can assemble and anneal a stack of glass sheets, and then ship the sheets as a stack, where the sheets are held together during shipment (without worrying about their separation during transport), at After reaching their destination, the sheets can be separated from the stack by a consumer, who can use the sheets individually or in smaller groups. Once separation is required, the stack of sheets can be processed again in a clean environment (after washing the stack if necessary).

Examples of bulk annealing

The glass substrate is used in a state of being received from the melt-drawing process. The composition of the melt-drawn glass is (in mole%): SiO2 (67.7), Al2O3 (11.0), B2O3 (9.8), CaO (8.7), MgO (2.3), and SrO (0.5). Seven (7) melt-drawn drawn glass substrates, 0.7 mm thick by 150 mm in diameter, were patterned by the lithography method using a 200 nm deep reference point / cursor using HF. Two (2) nm plasma-deposited fluoropolymers are applied as surface modification layers on all bonding surfaces of all glass substrates, that is, the coated substrate faces each surface of another substrate, and thereafter, each The resulting surface energy of the sheet surface was approximately 35 mJ / m2. Seven coated individual glass substrates are put together to form a single, thick substrate (called a "glass stack"). In a nitrogen flush tube furnace, the glass stack was annealed from a 30 ° C ramp to 590 ° C over a period of 15 minutes, maintained at 590 ° C for 30 minutes, and then ramped down to approximately 230 over a period of 50 minutes. And then the glass stack was removed from the furnace and cooled to room temperature of about 30 ° C in about 10 minutes. After cooling, the substrate is removed from the furnace and easily separated into individual sheets using a razor wedge (ie, the samples are not permanently bonded overall or locally). By comparing the glass datum point to a non-annealed quartz reference, compaction is measured for each individual substrate. Individual substrates were found to be approximately 185 ppm compact. Both of the substrates were subjected as individual samples (not stacked together) to a second annealing cycle (590 ° C / holding for 30 minutes) as described above. The compaction was measured again, and it was found that the substrate was further compacted by less than 10 ppm (actually 0 to 2.5 ppm) due to the second heat treatment (the glass size change after the second heat treatment-compared to the original glass size-minus the first glass size) Glass size changes after heat treatment). Therefore, the inventors have demonstrated that individual glass sheets can be coated, stacked, and heat treated at high temperatures to achieve compaction, cooling, and separation into individual sheets, and have a dimensional change of <10 ppm and even <ppm after the second heat treatment (Compared to its size after the first heat treatment).

Although the furnace in the above annealing example is purged with nitrogen, the annealing furnace can also be purged with other gases including air, argon, oxygen, CO2 or a combination thereof, depending on the annealing temperature and the material of the surface modification layer in a specific environment. Stability at isothermal temperature. Instead of an inert atmosphere, the furnace in the above annealing may be a vacuum environment.

In addition, although not shown, the glass may be annealed in the form of a roll instead of a sheet. That is, a suitable surface modification layer may be formed on one or both sides of the glass ribbon, and then the ribbon is rolled. The entire roll can be subjected to the same treatment as indicated above for the sheet, after which the glass of the entire reel is annealed without bonding one wrap of the glass to an adjacent wrap. After deployment, the surface modification layer can be removed by any suitable process.

Outgassing

Polymer adhesives used in typical wafer bonding applications are typically 10-100 microns thick and lose about 5% of their mass at or near their temperature limit. For these materials that escape from a thick polymer film, it is easy to quantify the amount of mass loss or outgassing by mass spectrometry. On the other hand, it is more challenging to measure outgassing from thin surface treatments that are about 10 nm thick or less. Such thin surface treatments such as the above-mentioned plasma polymer or self-assembled single-layer surface modification layer, And a thin layer of pyrolytic silicone oil. Mass spectrometry is not sensitive enough for these materials. However, there are many other ways to measure outgassing.

The first method for measuring small outgassing is based on surface energy measurement, and will be described with reference to FIG. 9. For this test, the setup shown in Figure 9 can be used. The first substrate or carrier 900 having the surface modification layer to be tested thereon has a surface 902, that is, a surface modification layer corresponding in composition and thickness to the surface modification layer 30 to be tested. The second substrate or cover material 910 is placed so that its surface 912 abuts on the surface 902 of the carrier 900 but is not in contact therewith. Surface 912 is an uncoated surface, that is, the surface of a bare material from which a cover material is made. The spacer 920 is placed at various points between the carrier 900 and the cover material 910 to hold them in a spaced relationship. The spacer 920 should be thick enough to separate the cover material 910 from the carrier 900, allowing the material to move from one to the other, but thin enough to minimize contamination of the surfaces 902 and 912 from the chamber atmosphere during the test The amount. The carrier 900, the spacer 920, and the cover material 910 together form a test object 901.

Prior to the assembly of the test article 901, measure the surface energy of the bare surface 912, such as the surface 902 (i.e., the carrier 900 has a table provided thereon). The surface energy of the surface modification layer). By fitting the Wu model to the contact angles of three test liquids: water, diiodomethane, and hexadecane, the surface energy shown in Fig. 10, that is, both the polar component and the dispersed component was measured.

After assembly, the test object 901 is placed in a heating chamber 930 and heated via a time-temperature cycle. Heating is performed at atmospheric pressure and under flowing N2 gas, which flows in the direction of arrow 940 at a rate of 2 standard liters per minute.

During the heating cycle, changes in the surface 902 (for example, changes in the surface modification layer due to evaporation, pyrolysis, decomposition, polymerization, reaction with the carrier, and de-wetting) are caused by the surface energy of the surface 902 Change to prove. The change in the surface energy of the surface 902 itself does not necessarily mean that the surface modification layer has been outgassed, but indicates the overall instability of the material at that temperature, as its characteristics change due to, for example, the mechanism indicated above. Therefore, the smaller the change in surface energy of the surface 902, the more stable the surface modification layer. On the other hand, due to the closeness of the surface 912 to the surface 902, any material outgassed from the surface 902 will be collected on the surface 912, and the surface energy of the surface 912 will be changed. Therefore, the surface energy change of the surface 912 is a proxy for the outgassing of the surface modification layer existing on the surface 902.

Therefore, one test for outgassing used the surface energy change of the cover material surface 912. Specifically, if the surface energy-the surface energy of the surface 912-changes 10mJ / m2, outgassing is present. This amount of surface energy change is consistent with pollution that can cause loss of film adhesion or degradation of material properties and device performance. The surface energy change of 5mJ / m2 is close to the repeatability of surface energy measurement and the heterogeneity of surface energy. This small change is consistent with minimal outgassing.

During the test that produced the results in Figure 10, carrier 900, cover material 910, and spacer 920 were made of Eagle XG glass, which is an alkali-free metal available from Corning Incorporated, Corning, NY. Aluminoborosilicate display-grade glass, although this need not be the case. The carrier 900 and the cover material 910 are 150 mm in diameter and 0.63 mm thick. Generally, the carrier 910 and the cover material 920 will be made of the same material as the carrier 10 and the sheet 20, respectively, and an outgassing test of the material is required. During this test, the silicon spacer was 0.63 mm thick, 2 mm wide, and 8 cm long, and a gap of 0.63 mm was formed between the surface 902 and the surface 912. During this test, the chamber 930 was incorporated into the MPT-RTP600s rapid heat treatment equipment. The chamber was cycled from room temperature to the test limit temperature at a rate of 9.2 ° C per minute; the chamber was maintained at the test limit temperature for a duration as shown in the chart. The change time shown by "annealing time", and then cooled to 200 ° C at a furnace rate. After the oven has cooled to 200 ° C., the test object is removed, and after the test object has cooled to room temperature, the surface energy of each surface 902 and surface 912 is measured again. Therefore, for example, in the case of using the data of the surface energy change (tested to the limit temperature of 450 ° C.) of the cover material of the material # 1 and the line 1003, the data is collected as follows. The data point at 0 minutes shows a surface energy of 75 mJ / m2 (millijoules per square meter), and it is the surface energy of bare glass, that is, the time-temperature cycle has not been run. The data point at one minute indicates the surface energy measured after a time-temperature cycle performed as follows: Object 901 (with material # 1, which is used as a surface modification layer on carrier 900 to present surface 902) Placed in a heating chamber 930 at room temperature and atmospheric pressure; in the case of N2 airflow at two standard liters per minute, heating the chamber to a test limit temperature of 450 ° C at a rate of 9.2 ° C per minute, and Guaranteed at 450 ° C test limit temperature Hold for 1 minute; then cool the chamber to 300 ° C at a rate of 1 ° C per minute, and then remove the object 901 from the chamber 930; then cool the object to room temperature (no N2 flowing atmosphere); then measure the surface The surface energy of 912 is plotted as a point on line 1003 for 1 minute. The remaining data points (lines 1003, 1004) of material # 1, and material # 2 are then determined in a similar manner at the test limit temperature (450 ° C or 600 ° C as appropriate), using an annealing time of several minutes corresponding to the holding time. (Lines 1203, 1204), material # 3 (lines 1303, 1304), material # 4 (lines 1403, 1404), material # 5 (lines 1503, 1504), material # 6 (lines 1603 and 1604), and material # 7 (Lines 1703, 1704). Lines 1001, 1002, 1201, 1202, 1301, 1302, 1401, 1402, 1501, 1502, 1601, 1602, 1701 and 1702 representing the surface energy of the surface 902 of the corresponding surface modification layer material (Material # 1-7) The data points are determined in a similar manner, with the exception that the surface energy of surface 902 is measured after each time-temperature cycle.

As described below, the above-mentioned assembly process and time-temperature cycle are performed on seven different materials, and the results are plotted in FIG. 10. Of the seven materials, materials # 1-4 and 7 correspond to the surface modification layer materials described above. Materials # 5 and # 6 are comparative examples.

Material # 1 is CHF3-CF4 plasma polymerized fluoropolymer. This material is consistent with the surface modification layer in Example 3b above. As shown in Figure 10, lines 1001 and 1002 show that the surface energy of the vehicle does not change significantly. Therefore, this material is extremely stable at temperatures from 450 ° C to 600 ° C. In addition, as shown by lines 1003 and 1004, the surface energy of the cover material will not change significantly, that is, it changes to 5mJ / m2. Therefore, there is no outgassing associated with this material from 450 ° C to 600 ° C.

Material # 2 is phenylsilane, which is a self-assembled monolayer (SAM) deposited from a 1% toluene solution of phenyltriethoxysilane and cured in a vacuum oven at 190 ° C for 30 minutes. This material is consistent with the surface modification layer in Example 4c above. As shown in Figure 10, lines 1201 and 1202 indicate some changes in surface energy on the carrier. As noted above, this indicates some changes in the surface modification layer and, in comparison, material # 2 is slightly less stable than material # 1. However, as shown by lines 1203 and 1204, the surface energy of the vehicle changes as 5mJ / m2, it is confirmed that there is no outgassing on the surface modification layer.

Material # 3 is pentafluorophenylsilane, which is a SAM deposited from a 1% toluene solution of pentafluorophenyltriethoxysilane and cured in a vacuum oven at 190 ° C for 30 minutes. This material is consistent with the surface modification layer in Example 4e above. As shown in Figure 10, lines 1301 and 1302 indicate some changes in surface energy on the vehicle. As noted above, this indicates some changes in the surface modification layer and, in comparison, material # 3 is slightly less stable than material # 1. However, as shown by lines 1303 and 1304, the surface energy change of the vehicle is 5mJ / m2, it is confirmed that there is no outgassing on the surface modification layer.

Material # 4 is hexamethyldisilazane (HMDS), which was auto-deposited in a YES HMDS oven at 140 ° C. This material is consistent with the surface modification layer in Example 2b of Table 2 above. As shown in Figure 10, lines 1401 and 1402 indicate some changes in surface energy on the vehicle. As noted above, this indicates some changes in the surface modification layer and, in comparison, material # 4 is slightly less stable than material # 1. In addition, the surface energy change of the carrier of material # 4 is greater than that of any of the materials # 2 and # 3, which indicates that material # 4 is slightly less stable than materials # 2 and # 3. However, as shown by lines 1403 and 1404, the surface energy change of the vehicle is 5mJ / m2, it is confirmed that the change of the surface modification layer does not produce outgassing that affects the surface energy of the cover material. However, this is consistent with the way in which HMDS outgassed. That is, HMDS releases ammonia and water, which does not affect the surface energy of the cover material, and may not affect some electronic equipment manufacturing equipment and / or processing. On the other hand, when the outgassed product is captured between the sheet and the carrier, there may be other problems, as pointed out below in connection with the second outgassing test.

Material # 5 is glycidyloxypropylsilane, which is a SAM deposited from a 1% toluene solution of glycidyloxypropyltriethoxysilane and cured in a vacuum oven at 190 ° C for 30 minutes. This is a comparative example material. Although there is a relatively small change in the surface energy of the vehicle, as shown by lines 1501 and 1502, there is a significant change in the surface energy of the cover material, as shown by lines 1503 and 1504. That is, although material # 5 is relatively stable on the surface of the carrier, it does release a significant amount of material on the surface of the cover material, thereby changing the surface energy of the cover material. 10mJ / m2. Although the surface energy at 600 ° C at the end of 10 minutes was within 10 mJ / m2, the change during that time did exceed 10 mJ / m2. See, for example, data points at 1 minute and 5 minutes. Although not wishing to be bound by theory, the slight increase in surface energy from 5 minutes to 10 minutes may be related to some outgassing materials that decompose and fall from the surface of the cover material.

Material # 6 is DC704, which is prepared by dispensing 5ml of Dow Corning 704 diffusion pump oil tetramethyltetraphenyltrisiloxane (commercially available from Dow Corning) on a carrier and placing it in air at 500 Polysiloxane coating prepared on a hot plate at 8 ° C for 8 minutes. It can be seen that the end of smoking indicates the completion of sample preparation. After the sample was prepared in the above manner, the outgassing test described above was performed. This is a comparative example material. As shown in Figure 10, lines 1601 and 1602 indicate some changes in surface energy on the vehicle. As noted above, this indicates some changes in the surface modification layer and, in comparison, material # 6 is slightly less stable than material # 1. In addition, as indicated by lines 1603 and 1604, the surface energy of the vehicle changes 10mJ / M2, confirmed significant outgassing. More specifically, at a test limit temperature of 450 ° C, a 10-minute data point shows a surface energy reduction of about 15 mJ / m2, and an even greater surface energy reduction for the points at 1 minute and 5 minutes small. Similarly, in terms of the change in surface energy of the cover material during a cycle at the test limit temperature of 600 ° C, the surface energy of the cover material is reduced to about 25 mJ / m2 at a data point of 10 minutes, and slightly larger at 5 minutes. , And slightly smaller at 1 minute. All in all, nevertheless, a significant amount of outgassing of this material was confirmed throughout the test.

Material # 7 is a CH4-H2 plasma-deposited polymer, which was sequentially treated with short N2-O2 and N2 plasma. This material is similar to the surface modification layer in the example in Table 11 above. As shown in Figure 10, lines 7001 and 7002 show that the surface energy of the vehicle does not change significantly. Therefore, this material is extremely stable at temperatures from 450 ° C to 600 ° C. In addition, as shown by lines 7003 and 7004, the surface energy of the cover material will not change significantly, that is, it changes to 5mJ / m2. Therefore, there is no outgassing associated with this material from 450 ° C to 600 ° C.

Significantly, for materials # 1-4 and 7, the surface energy indication of the entire time-temperature cycle: the surface energy of the surface of the cover material remains the same as that of the bare glass, that is, no self-carrier surface is collected Outgassing material. In the case of material # 4, as indicated in conjunction with Table 2, the method of preparing the surface of the carrier and the surface of the sheet will have a large effect on whether the object (the sheet is joined to the carrier via the surface modification layer) in the FPD process. The difference. So although Figure 10 The example of material # 4 shown may not be outgassed, but this material may or may not be preserved in a 400 ° C or 600 ° C test, as indicated in conjunction with the discussion in Table 2.

The second way of measuring a small amount of outgassing is based on assembling an article, that is, an article in which a sheet is bonded to a carrier via a surface modification layer, and a percent bubble area change is used to determine outgassing. That is, during the heating of the object, air bubbles formed between the carrier and the sheet indicate the outgassing of the surface modification layer. As pointed out above in conjunction with the first outgassing test, it is difficult to measure outgassing on very thin surface modified layers. In this second test, the outgassing under the sheet can be limited by the strong adhesion between the sheet and the carrier. despite this, 10 nm thick layers (e.g., plasma polymer materials, SAM, and pyrolytic silicone oil surface treatments) can still generate bubbles during heat treatment regardless of their small absolute mass loss. Moreover, the generation of air bubbles between the sheet and the carrier can cause problems with pattern formation, photolithography processing, and / or alignment during device processing on the sheet. In addition, blistering at the boundaries of the joint area between the wafer and the carrier can cause problems with the process fluid from one process contaminating downstream processes. A 5%% bubble area change is significant (indicating outgassing) and is not desirable. on the other hand, The change in% bubble area of 1 is not significant and indicates that there is no outgassing.

The average bubble area of the bonded thin glass by manual bonding in a Class 1000 clean room was 1%. The% bubbles in the bonding carrier vary with the cleanliness of the carrier, the thin glass sheet, and the surface preparation. Because these initial defects serve as nucleation sites for bubble growth after heat treatment, any change in bubble area less than 1% after heat treatment is within the variability of sample preparation. To perform this test, a commercially available desktop scanner (Epson Expression 10000XL Photo) with a transparency unit was used to obtain a first scanned image of the area where the sheet and the carrier were joined immediately after joining. Scan each section using standard Epson software using 508dpi (50 microns / pixel) and 24-bit RGB. The image processing software first prepares the image by: stitching the images of different sections of the sample into a single image as needed, and removing the scanner artifacts (by using the implementation without the sample in the scanner) Calibration reference scan). The joint area is then analyzed using standard image processing techniques such as localization, hole filling, erosion / expansion, and binary blob analysis. You can also use the new Epson Expression 11000XL Photo in a similar way. In transmission mode, bubbles in the joint area are visible in the scanned image, and the value of the bubble area can be determined. Subsequently, the bubble area is compared with the total bonding area (ie, the total overlap area between the sheet and the carrier) to calculate the% area of the bubbles in the bonding area relative to the total bonding area. The samples were then heat treated in an MPT-RTP600s rapid heat treatment system under N2 atmosphere at 300 ° C, 450 ° C, and 600 ° C test limit temperatures for up to 10 minutes. Specifically, the time-temperature cycle performed includes: inserting an object into a heating chamber at room temperature and atmospheric pressure; subsequently heating the chamber to a test limit temperature at a rate of 9 ° C per minute; maintaining the chamber at The test lasted for 10 minutes at the limiting temperature; the chamber was then cooled to 200 ° C at the furnace rate; the object was removed from the chamber and allowed to cool to room temperature; the object was then scanned a second time using an optical scanner. The% bubble area from the second scan is then calculated as above and compared with the% bubble area from the first scan to determine the% bubble area change (Δ% bubble area). As noted above, A 5% change in bubble area is significant and indicates outgassing. Due to the variability of the original% bubble area, the% bubble area change was selected as the measurement criterion. That is, most surface modification layers have a bubble area of about 2% in the first scan due to handling and cleanliness after the sheet and carrier have been prepared and before they are joined. However, variations can occur between materials. The same materials # 1-7 described with respect to the first outgassing test method are used again in this second outgassing test method. Of these materials, materials # 1-4 exhibited about 2% bubble area in the first scan, and materials # 5 and # 6 exhibited significantly larger bubble areas in the first scan, that is, about 4%.

The results of the second outgassing test will be described with reference to FIGS. 11 and 12. The outgassing test results of materials # 1-3 and # 7 are shown in Fig. 11, and the outgassing test results of material # 4-6 are shown in Fig. 12.

The results for material # 1 are shown as square data points in Figure 11. As can be seen from the figure, the% bubble area change is close to zero for the test limit temperatures of 300 ° C, 450 ° C, and 600 ° C. Therefore, material # 1 confirmed no outgassing at these temperatures.

The results for material # 2 are shown as diamond data points in Figure 11. As can be seen from the figure, the% bubble area change is less than 1 for the test limit temperatures of 450 ° C and 600 ° C. Therefore, material # 2 confirmed no outgassing at these temperatures.

The results for material # 3 are shown as triangle data points in Figure 11. As can be seen from the figure, similar to the result of material # 1, the% bubble area change is close to zero for the test limit temperatures of 300 ° C, 450 ° C, and 600 ° C. Therefore, material # 1 confirmed no outgassing at these temperatures.

The results for material # 7 are shown as cross-shaped data points in Figure 11. As can be seen from the figure, the% bubble area change is close to zero for the test limit temperatures of 300 ° C and 450 ° C. Therefore, material # 7 confirmed no outgassing at these temperatures. For the test limit temperature of 600 ° C, material # 7 exhibited a% bubble area change of less than 2%. Therefore, material # 7 demonstrated at least a minimum outgassing at this temperature.

The results for material # 4 are shown as circular data points in Figure 12. As can be seen from the figure, the% bubble area change is close to zero for the test limit temperature of 300 ° C, but for some samples, it is close to 1% at the test limit temperature of 450 ° C and 600 ° C, and for the same material, For other samples, it is about 5% at the test limit temperature of 450 ° C and 600 ° C. The results for material # 4 were extremely inconsistent and depended on the way the surface of the sheet and the carrier were prepared for bonding using the HMDS material. The manner in which the samples are performed, which depends on the manner in which the samples are prepared, is consistent with the examples and associated discussions of this material described in conjunction with Table 2 above. It should be pointed out that, for this material, a sample with a% bubble area change of approximately 1% for 450 ° C and 600 ° C test limit temperatures does not allow the sheet to be separated from the carrier according to the separation test described above. That is, strong adhesion between the sheet and the carrier may have limited generation of air bubbles. On the other hand, a sample with a% bubble area change close to 5% allows the sheet to be separated from the carrier. Therefore, samples that do not have outgassing have undesired results of increased adhesion (preventing the removal of the sheet from the carrier) after the temperature treatment of bonding the carrier and the sheet together, while allowing the removal of the sheet and the carrier. Undesired results with outgassing.

The results for material # 5 are shown as triangle data points in Figure 12. As can be seen from the figure, the% bubble area change is about 15% for the test limit temperature of 300 ° C, and quite high for the higher test limit temperatures of 450 ° C and 600 ° C. Therefore, material # 5 demonstrated significant outgassing at these temperatures.

The results for material # 6 are shown as square data points in Figure 12. As can be seen from this figure, the% bubble area change exceeds 2.5% for the test limit temperature of 300 ° C, and exceeds 5% for the test limit temperature of 450 ° C and 600 ° C. Therefore, Material # 6 demonstrated significant outgassing at the test limit temperatures of 450 ° C and 600 ° C.

Bonding polymer surfaces to glass surfaces

Demonstration displays have been demonstrated on polymer sheets such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and polyimide (PI), where devices Production is made using sheet-to-sheet production of PEN laminated to a glass carrier. Up to 100 micron thick layers of polymer adhesives are typically used to laminate PEN and PET to glass carriers for sheet-to-sheet processing. The weight loss of these adhesives during device processing is typically greater than 1%, creating challenges for contamination due to outgassing of solvents. In addition, complete removal of the adhesive is challenged, so glass carriers are often not reused.

This application describes the use of a thin surface modification layer to form a moderate adhesion between a glass carrier and a polymer sheet to produce a controlled temporary bond that is very strong to preserve in TFT processing but weak enough to Disengagement is allowed. However, thermal, vacuum, solvent, and acidic and ultrasonic flat panel display (FPD) processes require robust bonding of thin polymer sheets to the carrier, but the various surface modifying layers of the surface modifying layer of the present invention discussed herein can This controlled joint is achieved for processing polymer flakes on a glass carrier. In addition, controlled bonding can allow the polymer sheet to be removed from the carrier without catastrophic damage to the polymer sheet or glass carrier, and in turn provides a reusable glass carrier.

Three transistor technologies are used in mass production of FPD backplane production: aSi bottom gate TFT, polycrystalline silicon (pSi) top gate TFT, and amorphous oxide (IGZO) bottom gate TFT . These The technology all requires high temperature processing steps> 300C. This requirement for substrates capable of high temperature processes, as well as requirements for chemical, mechanical, and vacuum compatibility, has become a major limitation on the industrialization of flexible displays on existing flexible substrates such as polymers. The general process starts with the cleaning of the polymer substrate, typically using ultrasonic or megasonic ultrasonic cleaning in an alkaline solution, followed by DI water cleaning. The device structure is fabricated in many subtractive cycles of material deposition and photolithography patterning followed by material etching. Metals, dielectrics and semiconductor materials are deposited by vacuum processes such as sputtering metal, transparent conductive oxides and oxide semiconductors; chemistry of amorphous silicon, silicon nitride and silicon dioxide at high temperatures Vapor deposition (CVD) deposition. Laser and flash annealing allow p-Si to crystallize without excessive substrate heating, but uniformity is challenged and performance is poor compared to glass substrates. The layers are patterned by photolithography patterning with a polymer resist and etching followed by resist stripping. Vacuum plasma (dry) etching process and acid wet etching process are used. In FPD processing, photoresist is typically stripped by a hot solvent, typically using ultrasonic or megasonic agitation.

Removing the thick layer of adhesive prevents the reusability of the carrier. For polymer adhesives suitable for FPD processing, they must have good chemical resistance in solvents, strong acids and strong bases. However, these same properties make removal challenging. Moreover, with layers up to 100 microns thick, the plasma process is not practical for removing the layers. The main challenge for the fabrication of organic thin film transistors is the build-up of a thin polymer sheet to a carrier.

This application describes methods for the controlled temporary bonding of polymer sheets to glass carriers for use in FPD processes, and describes reusable glass carriers for sheet to sheet processing of thin polymer substrates. The formation of the surface modification layer on the glass carrier creates a temporary joint with moderate adhesion between the thin polymer sheet and the carrier. Moderate adhesion is achieved by optimizing the contribution of Van der Waals and covalent attraction energy to the total adhesion energy, which is controlled by adjusting the polar and non-polar surface energy components of the sheet and the carrier. This moderate bond is strong enough to be preserved in FPD processing, including wet ultrasonic processes, vacuum processes, and thermal processes, and still allows the polymer sheet to remain disengaged from the carrier by the application of a sufficient peel force. Disengagement allows the removal of devices made on thin polymer sheets and the reuse of carriers, as the surface modification layer is <1 micron thick and easily removed in an oxygen plasma.

The advantage is obtained that a thin surface modification layer is used to create a moderate bond between the thin polymer sheet and the glass carrier.

(1) Compared to commercial adhesives, a reduction of approximately 100X in the amount of material used to join a thin polymer sheet to a carrier reduces outgassing and reduces the possibility of absorption and pollution of downstream processes.

(2) The surface modified layer of the highly cross-linked plasma polymer is non-volatile and insoluble, thereby reducing the probability of outgassing and process pollution.

(3) The surface modified layer is easy to be removed in an oxygen plasma or a downstream oxygen plasma at a high temperature.

(4) The glass carrier can be reused because the surface modification layer is thin and easy to remove.

PEN and PET are especially typical polymer substrates that can be used in roll form for electronic manufacturing. Compared to most polymers, it is relatively chemically inert, has low water absorption, low swelling, and temperature resistance. However, these properties are inferior to those of glass. For example, the highest non-thermally stable PEN The temperature is 155 ° C, while the maximum temperature of PET is only 120 ° C. These temperatures are low compared to> 600 ° C operating temperatures for display glasses suitable for pSi treatment. In contrast to 3.5 ppm of display glass, the thermal expansion of PEN is about 20 ppm. Moreover, after 30 minutes at 150 ° C, the shrinkage at temperature is about 0.1%, which far exceeds the relaxation and compaction of glass at significantly higher temperatures. These secondary physical properties of polymer substrates require process adaptation to deposit high-quality devices at high yields. For example, silicon dioxide, silicon nitride, and amorphous silicon deposition temperatures must be lowered to stay within limits suitable for polymer substrates.

The aforementioned physical properties of the polymers also make joining with rigid carriers for sheet-to-sheet processing a challenge. For example, the thermal expansion of polymer sheets is typically 6x greater than the thermal expansion of display glass. Although the upper temperature limit is small, the thermal stress is large enough to produce warpage and curvature, and cause delamination when using conventional bonding techniques. The use of high-expansion glass such as soda-lime or higher-expansion metal carriers can help manage the challenges of warpage, but these carriers are typically challenging with respect to contamination, compatibility, or roughness (heat transfer). The surface energy of PEN and PET is also significantly lower than that of glass. As shown in Table 16 below, Corning® Eagle XG® glass exhibits a surface energy of approximately 77mJ / m2 after cleaning using SC1 chemistry and standard cleaning techniques. See Example 16e. Without surface treatment, PEN and PET are non-polar, and the surface energy is 43-45mJ / m2 (43-45dyn / cm). See Table 15 below, which is from “Remote Atmospheric-Pressure Plasma Activation of the Surfaces of Polyethylene Terephthalate and Polyethylene Naphthalate”, E. Gonzalez, II, MD Barankin, PCGuschl and RFHicks, Langmuir 2008 24 (21), 12636 -12643 Of Table 2. Plasma cleaning (for example, by an oxygen plasma) greatly increases the surface energy to 55-65mJ / m2 (55-65dyn / cm, "plasma") by increasing the polarity component. In addition, UV ozone treatment or corona discharge can be used to clean polymers and temporarily increase their surface energy. Over time, however, the surface energy decreases back to its previous value ("aging").

In the case of these surface energies (about 55mJ / m2 to about 65mJ / m2) of the polymer bonding surface and about 77mJ / m2 of the glass carrier bonding surface, the polymer sheet does not sufficiently adhere to the glass carrier to allow Processing on a sheet, but if first set on a glass carrier and then heated to a moderate temperature, the polymer cannot be peeled from the glass carrier. Therefore, in order to initially bond PEN or PET to glass at room temperature, it has been found beneficial to modify the surface energy of the glass carrier to approximately match the surface energy of PEN or PET. In addition, it was found that the various surface modification layers of the above surface modification layer control the bonding energy so that the polymer layer can be used even after the organic-TFT processing cycle (including a vacuum annealing at 120 ° C for one hour and a post-baking step at 150 ° C for one minute). The glass carrier is peeled.

By selecting the appropriate surface modification layer to appropriately adjust the surface energy of the glass carrier, sufficient wetting strength and adhesive strength can be achieved to controllably bond a polymer such as PEN or PET to the glass carrier in one way. the way Suitable for organic-TFT processing (including vacuum annealing at 120 ° C for one hour and post-baking step at 150 ° C for one minute), while allowing the polymer to be removed from the carrier after processing. The polymer sheet can be successfully removed from the carrier, that is, the polymer sheet is controllably bonded to the carrier, even after the above processing, the OTFT on the polymer sheet and the mask used to generate it No significant difference in transistor geometry was observed between the OTFTs. The surface modification layer can be selected from various materials and processes exemplified throughout this specification. The polymer material may advantageously be plasma cleaned before joining (to increase the polar component of its surface energy in order to facilitate initial joining), but this is not necessary because the surface energy of the glass carrier can be greatly changed in order to achieve A suitable level for controlled engagement with the polymer in its current state (ie, as received, as cleaned, or as aged). Based on the above examples and their examples in Table 16 below, a surface energy range from about 36 mJ / m2 (Example 5g) to about 80 mJ / m2 (Example 5f) can be obtained on the glass carrier bonding surface.

Several of the above methods of surface modification are suitable for the adhesive bonding of polymer sheets and glass carriers. The surface modification includes forming from a carbon source, such as surface modification of plasma polymerization of a hydrocarbon gas. For example: Plasma polymer films deposited from fluorocarbon gas (Examples 5a and 5g); Plasma polymer films deposited from fluorocarbon gas and subsequently treated with nitrogen and hydrogen simultaneously (Example 5m); Plasma polymer film deposited by fluorine gas (Examples 6a-6j); Plasma polymer film deposited from hydrocarbon gas, optionally nitrogen and hydrogen (Examples 7a-g, 12j); deposited from various non-fluorine-containing gases and subsequently Plasma polymer films treated with nitrogen (Examples 9a-9j), where such surface energy is applicable to polymers in various states of cleanliness and / or aging; and deposition from various non-fluorine-containing gases and subsequent sequencing Ground Treatment with nitrogen followed by hydrogen (Examples 10a-10p), or treatment with dilute ammonia (Examples 8b, 8d), or sequentially with N2-O2 followed by N2 (Examples 11a, 11e), or N2-O2 (Example The plasma polymer films of 11f, 12c), all of which work particularly well with plasma cleaning PEN. Where a polymer other than PET or PEN is used, other surface treatments may be suitable, depending on the surface energy of the polymer just before bonding, and the surface energy that the polymer can be affected by the degree of cleaning and aging . It has been found that the surface energy of a glass carrier approximately matching the surface energy of a polymer sheet performs well in both initial bonding and controlled bonding, so that the polymer sheet can be easily processed in an organic-TFT type (including 120 ° C for one hour) Vacuum annealing and post-baking step at 150 ° C for one minute) followed by debonding.

In addition, other formulations of the surface modification layer are explored to achieve a surface energy within a surface energy range of a polymer sheet used to join a polymer sheet to a glass carrier as follows.

Surface modified layer formed from a mixture of gases

An example of using a plasma polymerized film to adjust the surface energy of the bonding surface and cover the surface hydroxyl groups on the bonding surface and / or control the type of polar bonding on the bonding surface is: the surface modification layer thin film includes a hydrocarbon (eg, methane) Deposition of a mixture of source gases. Deposition of the surface modification layer can occur at atmospheric pressure or reduced pressure, and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modification layer may be disposed on a bonding surface, a sheet, or both of the carrier. As noted above in connection with the examples in Table 3, plasma polymerization results in layers of highly crosslinked material. The control of reaction conditions and source gas can be used to control the thickness, density and chemical properties of the surface modification layer film, which can be specially used for the desired application Of functional groups. By controlling the properties of the film, including controlling the amount of hydroxyl groups on the surface to be covered, the surface energy of the bonding surface of the carrier can be adjusted. The surface energy can be adjusted to control the degree of bonding, that is, to prevent permanent covalent bonding between the sheet and the carrier during subsequent processing performed to place the film or structure on the sheet.

In the example in Table 16 below, various conditions were used to deposit a plasma polymerized film on a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate alkali-free display glass (commercially available from Corning Incorporated, Corning NY). Prior to film deposition, the vehicle is cleaned using SC1 and / or SC2 chemistry and standard cleaning techniques. The film is deposited in a triode electrode configuration mode in an STS multiplexed PECVD device (available from SPTS, Newport, UK), where the carrier is placed on a platform, and 380kHz RF energy of 50 watts is applied to the platform, A coil (shower head) is placed above the platform. 300 Watts of 13.5MHz RF energy is applied to the coil (shower head). The temperature of the platform is 200 ° C, and the flow rate of gas through the shower head is shown in Table 16. Shown (flow rate is calculated as standard cubic centimeters per minute-sccm). Therefore, for example, in the "Surface Modification Layer Deposition Process" column of Table 16, the notation of Example 16b is interpreted as follows: In a STS multiplexed PECVD equipment, at a platform temperature of 200 ° C, 200 sccm of H2, 50 sccm of CH4 and 50sccm of C2F6 flows through the shower head and enters the chamber with a pressure of 300mTorr; 300W of 13.5MHz RF energy is applied to the showerhead; 50W of 380kHz RF energy is applied to the carrier on which Platform; and the deposition time is 120 seconds. The notation of the remaining examples in the surface treatment column can be interpreted in a similar manner. Surface energy is obtained by using three different test liquids (in this case water (W), hexadecane (HD) and diiodine Methane (DIM) contact angle (CA) and Wu model were calculated in mJ / m2 (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D) are displayed, as well as the total energy (T). For these examples, the thickness of the surface modification layer is also shown in Angstroms "Th (A)".

Example 16e is a piece of bare Eagle XG® glass that has been cleaned using SC1 chemistry and standard cleaning techniques. Example 16e shows that the surface energy of the glass after cleaning is about 77 mJ / m ² .

Examples 16a to 16d show that a surface modification layer can be deposited on the glass surface to modify its surface energy so that the surface of the glass can be tailored to suit a particular bonding application. The example in Table 16 is an example of a one-step process for the deposition of a surface modification layer having a desired surface energy and a polar group, such as the examples in Tables 6 and 7.

Example 16a shows that the surface modification layer may be a plasma polymerized film deposited from a mixture of hydrogen and methane (hydrocarbon) gas. In these examples, the surface modification layer is deposited on a clean glass carrier. Therefore, the deposition of the surface modification layer shown reduces the surface energy from about 77 mJ / m ² to about 49 mJ / m ² , which is in the range of surface energy on a typical polymer bonding surface.

Example 16b shows that the surface modification layer can be a plasma polymerized film deposited from a mixture of hydrogen, methane (hydrocarbon), and a fluorine-containing gas (eg, C2F6, which is a fluorocarbon compound). In these examples, the surface modification layer is deposited on a clean glass substrate. Therefore, the deposition of the surface modification layer shown reduces the surface energy from about 77 mJ / m ² to about 37 mJ / m ² , which is approximately in the range of surface energy on a typical polymer bonding surface. The surface energy achieved in Example 16b was lower than the surface energy achieved in Example 16a, thus confirming that the addition of fluorine to the deposition gas can reduce the surface energy achieved by similar surface modification layer deposition conditions in other cases.

Example 16c shows that the surface modification layer can be a plasma polymerized film deposited from a mixture of hydrogen, methane (hydrocarbon), and a nitrogen-containing gas (eg, N2). In these examples, the surface modification layer is deposited on a clean glass carrier. Thus, the deposition of the surface modification layer shown reduces the surface energy from about 77 mJ / m ² to about 61 mJ / m ² , which is a typical polymerization that has been treated with an O 2 plasma (such as during the cleaning of a polymer sheet). Within the range of surface energy on the mating surface of the object. This surface energy is also within a range that achieves the suitability of joining a thin glass sheet to a carrier.

Example 16d shows that the surface modification layer may be a plasma polymerized film deposited from a mixture of methane (hydrocarbon) and a nitrogen-containing gas (eg, NH3). In these examples, the surface modification layer is deposited on a clean glass substrate. As a result, the deposition of the surface modification layer shown reduces the surface energy from about 77 mJ / m ² to about 57 mJ / m ² , which again falls within the range of surface energy on a typical polymer bonding surface. Furthermore, for some applications, this may be suitable for bonding a carrier to a thin glass sheet.

Compared to the surface energy achieved by Example 16a, the surface energy achieved by Examples 16c and 16d confirms that the addition of nitrogen (by N2 or by NH3) to the deposition gas can increase by similar deposition in other cases Surface energy achieved by gas.

The surface energy obtained by the surface modification layer of Example 16b is less than 50 mJ / m ² (considered suitable for controlled bonding of glass flakes and glass carriers), however, this surface modification layer is suitable for bonding polymers to surfaces Bonded to a glass bonding surface. In addition, it should be noted that the surface energy generated by the surface modification layer of Examples 16c and 16d (formed from plasma polymerization of hydrocarbons (methane), optionally hydrogen-containing gas (H2) and nitrogen-containing gas (N2 or ammonia)) More than about 50 mJ / m ² , and thus may be suitable for joining thin glass sheets to a glass carrier in some cases.

The sheet bonded to a carrier having a surface modification layer according to Examples 16a to 16d according to Table 16 was a substrate made from TEONEX® Q65 PEN (commercially available from DuPont) and having a thickness of 200 microns.

In the example of Table 16, although the bonding surface on which the surface modification layer is disposed is glass, this need not be the case. Instead, the bonding surface may be another suitable material having surface energy and properties similar to glass, such as silicon, polycrystalline silicon, single crystal silicon, ceramic, glass-ceramic, sapphire, or quartz.

Plasma polymerized hydrocarbon polymer membranes can be used in STS multiplexed CVD in triode mode from methane and hydrogen (Example 16a) and in optional fluorocarbons (Example 16b), optional nitrogen (Example 16c), or optional ammonia. (Example 16d) Deposited with addition. low Surface energies up to 37 mJ / M2 (Example 16b) and higher surface energies (about 61 mJ / m2, Example 16c) can be achieved using fluorocarbon or nitrogen addition. It is also possible to achieve a surface energy between the energy level of Example 16b and the energy level of Example 16c (ie, about 49mJ / m2 as in Example 16a, and about 57mJ / m2 as in Example 16d), so The ability to adjust the surface energy of the surface modification layer based on the deposition conditions including the deposition gas was demonstrated.

As a comparative example, a polymer film was placed on a bare glass carrier in SC1 clean form (Example 16e). However, the polymer sheet is not sufficiently bonded to the carrier to allow processing on the polymer sheet.

Moreover, it is necessary that wet strength and bonding strength be suitable for organic-TFT processing. The vastly different thermal expansion between the polymer film and the carrier is minimized by the choice of high expansion glass, and is best managed by reducing the rate of the heating and cooling steps. The need for a smooth and clean substrate surface with minimal water absorption during processing can be met by spin coating and curing a thin layer suitable for organic dielectrics. Both spin coating and curing planarize the surface and produce Barriers to moisture and other pollutants.

The surface modification layer process is used to bond PEN (TEONEX® Q65 200 micro-thick sheet from DuPont) to Corning® Eagle XG® glass carrier. Excellent bonding performance was found with the amorphous carbon layer deposited using the following conditions: 50CH4, 200H2, 300W 13.56MHz RF applied to the showerhead, 50W 380kHz RF applied to a 200 ° C platform, and 2 minute deposition time. The PEN was exposed to UV-ozone cleaner for 5 minutes before joining, as this was found to improve adhesion. Teflon applicator is used to apply PEN. An approximately 150 nm thick cycloaliphatic epoxy resin layer was spin-coated and cured on PEN to eliminate the surface Face defects. Organic gate insulator (OGI) is a photo-patternable cycloaliphatic epoxy resin.

The array of the bottom gate contacting the organic thin film transistor is formed by the following process. The 100nm Al gate metal was deposited by sputtering in AJA, patterned with Fuji 6512 resist lithography, and gate patterned by wet etching in A-type Al etchant. The photoresist was removed by 3 minutes in a PGMEA bath at room temperature followed by IPA / DI cleaning (NMP-based strippers are incompatible with the epoxy layer). A second epoxy gate insulator layer is spin-coated on the patterned gate and allowed to cure. A 100 nm thick Ag S / D metal was sputtered, patterned with Fuji 6512 lithography, and etched with a 1: 1 mixture of Transene TFS: pH 10 buffer. Etching becomes a challenge because Ag etch rate is fast, but the dissolution of etching products is slow. By etching for 5 s, the etching product was removed while spraying with DI water, and repeated four to five times to obtain excellent results. The wetting of the organic semiconductor (OSC) layer of the tetrathienoacene-DPP co-polymer (PTDPPTFT4) becomes a challenge. OSC adhesion was promoted by HMDS treatment in a YES oven at 120 ° C. The OSC polymer was dissolved in 6 parts of decalin: 4 parts of toluene at a concentration of 5 mg / mL. OSC was applied by spin-coating in a Laurel spin coater using manual dispensing (20 seconds rest, 500 rpm 30 seconds, 1000 rpm 60 seconds). The OSC film was soft-baked on a hot plate at 90 ° C. for 2 min, and vacuum annealed at 120 ° C. in a Salvis oven under rough vacuum for 1 hr to remove residual decalin. A short 5 second O2 plasma was used in Branson to improve adhesion. A third OGI layer was spin-coated on OSC, and exposed to light for 2.5 seconds, 1 minute at rest, and 150 minutes at 150 ° C for direct photopatterning. After 1 min inactivity, make active layer diagram in PGMEA The pallet was developed for 1 min, followed by IPA and DI cleaning. In Unaxis 790 RIE, dry etching using 30sccm O2 10sccm Ar 20sccm CHF3 50mT 200W 15s was used to pattern the active layer and expose the gate metal. The performance of 75 / 75um TFT's is summarized in the table shown in Figure 18, which shows the drain current versus gate voltage and performance of a typical transistor. The typical transistor has a 75 micron channel width, a 75 micron channel length, The bottom gate bottom contact organic thin film transistor fabricated on the PEN controllably bonded to the glass carrier as described above. PEN is susceptible to disengagement by using a blade to initiate cracking and subsequent peeling. The polymer sheet can be successfully removed from the carrier, even after the above treatment, as no obvious transistor geometry is seen between the OTFT on the polymer sheet and the OTFT on the mask used to generate it difference.

The above-mentioned process of forming an array of bottom-gate bottom-contact organic thin-film transistors was also successfully performed using a PEN sheet (TEONEX® Q65 200 micron thick sheet from DuPont), which is controllably bonded to Corning® A carrier made of Gorilla® glass (alkali-containing, chemically strengthenable cover glass available from Corning Incorporated, Corning, NY) and has a suitable surface modification layer selected from their surface modification layers described herein .

As described above, the polymer may itself be a substrate on which other devices are fabricated. Alternatively, the polymer may be a polymer surface on a composite substrate such as a glass / polymer composite. In this case, the polymer surface of the glass / polymer composite will face the carrier and will be bonded to it as described above, and the glass surface of the glass / polymer composite will be exposed as electrons or other structures can be made on it The surface. After the electronic or other structure is fabricated on the glass surface of the glass / polymer composite, the polymer surface of the composite can be peeled from the surface modification layer on the carrier. This embodiment may be advantageous because the glass layer in the glass / polymer composite becomes particularly thin, for example, having the following thickness: 50 microns, 40 microns, 30 microns, 20 microns, 10 microns or 5 microns. In this case, the polymer portion of the glass / polymer composite not only serves as a bonding surface for attaching the composite to the vehicle, it can also give the composite some disposal advantages when the composite is not on the vehicle.

in conclusion

It should be emphasized that the above-mentioned embodiments of the present invention, especially any "preferred" embodiments, are merely possible examples of implementation schemes, and are merely explained to achieve a clear understanding of the various principles of the present invention. Many variations and modifications may be made to the above-described embodiments of the present invention without substantially departing from the spirit and various principles of the present invention. All such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the scope of the accompanying patent application.

For example, although the surface modification layer 30 of many embodiments is shown and discussed as being formed on the carrier 10, it may be replaced or otherwise formed on the sheet 20. That is, as appropriate, the materials as described in the examples of Tables 3-12 and 16 may be applied to the carrier 10, the sheet 20, and both the faces of the carrier 10 and the sheet 20 to be joined together .

In addition, although some surface modification layers 30 are described as controlling the bonding strength so as to allow the sheet 20 to be removed from the carrier 10 even after treating the object 2 at a temperature of 400 ° C or 600 ° C, it is of course possible to complete the process more smoothly than the object 2 In certain tests, the objects were processed at lower temperatures, and the ability to remove the sheet 20 from the carrier 10 without damaging the sheet 20 or the carrier 10 was still achieved.

In addition, although the concept of controlled joining has been described herein for carriers and lamellae, in some cases these concepts apply to controlling the joining between thicker sheets of glass, ceramic, or glass-ceramic, where It may be necessary to detach the sheets (or portions thereof) from each other.

In addition, although the concept of controlled bonding herein has been described as applicable to glass carriers and glass flakes, the carrier may be made of other materials such as ceramic, glass ceramic, or metal. Similarly, the sheet that is controllably bonded to the carrier may be made of other materials such as ceramic or glass ceramic.

In addition, although the surface modification layers described above in Examples 3 and 5-12 are described as being formed by plasma polymerization, other techniques may be possible, for example, by thermal evaporation sputtering, bonding and bonding in the form of a gas. UV activation of surface-reactive substances, or wet chemical methods.

In addition, although the carbonaceous surface modification layer formed by the plasma polymerization of Examples 6-12 was formed using methane as a polymer-forming gas, other carbon-containing source materials may be possible. For example, the carbon-containing source may include at least one of the following: 1) a hydrocarbon (alkane, olefin, alkyne, or aromatic compound). Alkanes include but are not limited to: methane, ethane, propane and butane; alkenes include but are not limited to: ethylene, propylene and butene; alkynes include but are not limited to: acetylene, methylacetylene, ethylacetylene and dimethylacetylene Aromatic compounds include but are not limited to: benzene, toluene, xylene, ethylbenzene); 2) alcohols (including: methanol, ethanol, propanol); 3) aldehydes or ketones (including: formaldehyde, acetaldehyde and acetone); 4) amines (including: methylamine, dimethylamine, trimethylamine, and ethylamine); 5) organic acids (including: formic acid and acetic acid); 6) nitriles (including: acetonitrile); 7) CO; and 8) CO2. Alternatively, the carbon-containing source may include one or more of the following: 1) saturation Or unsaturated hydrocarbons, or 2) nitrogen or 3) oxygen-containing saturated or unsaturated hydrocarbons, 4) CO or CO2. Some commonly typical carbonaceous source materials include carbonaceous gases such as methane, ethane, propane, butane, ethylene, propylene, propyne, acetylene, MAPP, CO, and CO2.

In addition, although the polar groups used to treat the surface modification layer and increase the surface energy of the surface modification layer as in Examples 5 and 8-12, or as the surface modification layer itself in Examples 7, 16c, 16d The polar groups formed are nitrogen and oxygen, but other polar groups such as sulfur and / or phosphorus may be possible.

In addition, although N2 and NH3 are used as nitrogen-containing gas, other nitrogen-containing materials may be used. Such other nitrogen-containing materials such as hydrazine, N2O, NO, N2O4, methylamine, dimethylamine, trimethylamine and ethylamine, Acetonitrile.

In addition, although the oxygen-containing gases used are N2-O2 and O2, other oxygen-containing gases may be used, such as O3, H2O, methanol, ethanol, propanol, N2O, NO, and N2O4.

As can be seen from the examples discussed herein, the surface modification layers including their subsequent treatment surface modification layers can reach from about 1 nm (example 16b) or 2 nm (examples 3, 4) to about 10 nm (example 12c, 8.8 nm). thickness. In addition, thicker surface modification layers are also possible, as explained with respect to FIG. 15. However, when the thickness becomes greater than about 70 nm, the surface-modified layer begins to become translucent, which may be undesirable for applications that benefit from optical clarity.

The various concepts described above according to this application can be combined with one another in any and all different combinations. For example, various concepts can be combined according to the following aspects.

According to a first aspect, there is provided a method for controllably bonding a substrate to a carrier, the method comprising: obtaining a substrate having a polymer bonding surface having a first surface energy; and obtaining a substrate having a glass bonding surface A carrier, the glass bonding surface has a second surface energy; a surface modifying layer is deposited on the glass bonding surface so as to reduce the surface energy of the glass bonding surface; and the polymer bonding surface via the surface modifying layer Bonded to the glass bonding surface, wherein the substrate can be non-destructively disengaged from the carrier after being subjected to vacuum annealing for one hour in an environment having a temperature of 120 ° C.

According to a second aspect, the method of aspect 1 is provided, wherein the surface modification layer is deposited by one of the following: plasma polymerization of a carbon-containing gas; plasma polymerization of a hydrocarbon-containing gas; hydrocarbon-containing gas and fluorine Plasma polymerization of carbon compound gas; plasma polymerization of hydrocarbon-containing gas and hydrogen-containing gas; plasma polymerization of hydrocarbon-containing gas to form a layer, and then treating the layer with a nitrogen-containing gas; plasma polymerization of hydrocarbon-containing gas to form a layer Then, the layer is sequentially processed by two independent gases, one of which contains nitrogen and the other gas contains hydrogen; the plasma of the hydrocarbon-containing gas is polymerized to form a layer, and then the layer is sequentially processed by two independent gases, one of which The gas contains nitrogen and oxygen and the other gas contains nitrogen; Plasma polymerization of a hydrocarbon-containing gas to form a layer, and then treating the layer with a nitrogen-containing gas and an oxygen-containing gas; plasma polymerization of a hydrocarbon-containing gas, a nitrogen-containing gas, and a hydrogen-containing gas; a plasma of a hydrocarbon-containing gas and a hydrogen-containing gas Polymerize to form a layer, and then treat the layer with a nitrogen-containing gas; plasma polymerization of fluorocarbon gas; plasma polymerization of fluorocarbon gas and hydrogen gas; and plasma polymerization of fluorocarbon gas to form One layer, which is then treated simultaneously with a nitrogen-containing gas and a hydrogen-containing gas.

According to a third aspect, there is provided the method of aspect 1, wherein the surface modification layer is deposited by plasma polymerization of methane gas, ammonia gas, and hydrogen gas.

According to a fourth aspect, there is provided the method of aspect 2, wherein the carbon-containing gas includes at least one of a hydrocarbon, an alkane, an alkene, an alkyne, or an aromatic compound.

According to a fifth aspect, there is provided the method of aspect 2, wherein the carbon-containing gas includes at least one of methane, ethane, propane, butane, ethylene, propylene, propyne, acetylene, CO, and CO2.

According to a sixth aspect, there is provided a method of any one of aspects 2, 4, and 5, wherein when a hydrogen-containing gas is used, the hydrogen-containing gas contains H2, and wherein when a nitrogen-containing gas is used, the nitrogen-containing gas Contains at least one of ammonia, N2, hydrazine, N2O, NO, N2O4, methylamine, dimethylamine, trimethylamine, ethylamine, and acetonitrile.

According to a seventh aspect, there is provided a method of any one of aspects 2, 4-6, wherein when a hydrogen-containing gas is used, the hydrogen-containing gas contains H2, and wherein when an oxygen-containing gas is used, the oxygen-containing gas Contains at least one of O2, O3, H2O, methanol, ethanol, propanol, N2O, NO, and N2O4.

According to an eighth aspect, the method of any one of aspects 1-7 is provided, wherein the surface modification layer has a thickness of 1 nm to 70 nm.

According to a ninth aspect, the method of any one of aspects 1-7 is provided, wherein the surface modification layer has a thickness of 2 nm to 10 nm.

According to a tenth aspect, there is provided a method of any one of aspects 1-9, further comprising cleaning the polymer bonding surface to provide the first surface energy.

According to an eleventh aspect, there is provided the method of aspect 10, wherein the cleaning includes one of an oxygen plasma cleaning, a UV ozone treatment, and a corona discharge.

According to a twelfth aspect, the method of any one of aspects 1-11 is provided, wherein the substrate is a composite including a polymer and glass.

According to a thirteenth aspect, the method of any one of aspects 1-12 is provided, wherein the glass bonding surface has before the surface modification layer is deposited, 1 nm average surface roughness Ra.

According to a fourteenth aspect, the method of any one of aspects 1-13 is provided, wherein the substrate has 300 micron thickness.

According to a fifteenth aspect, the method of any one of aspects 1-14 is provided, wherein the carrier has a thickness of 200 micrometers to 3 mm.

According to a sixteenth aspect, there is provided an article including: a substrate having a polymer bonding surface; a carrier having a glass bonding surface; a plasma polymerized surface modification layer which releasably releases the polymer bonding surface Bonded to the glass bonding surface.

According to a seventeenth aspect, the object of aspect 16 is provided, wherein the surface modification layer has a thickness of 1 nm to 70 nm.

According to an eighteenth aspect, there is provided the object of aspect 16, wherein the surface modification layer has a thickness of 2 nm to 10 nm.

According to a nineteenth aspect, there is provided the object of any one of aspects 16-18, wherein the surface modification layer includes at least one of the following: plasma-polymerized hydrocarbons; and plasma-polymerized fluorocarbons.

According to the twentieth aspect, the object of any of aspects 16-19 is provided, wherein the substrate is a composite including a polymer and glass.

According to the twenty-first aspect, the object of any one of aspects 16-20 is provided, wherein the glass bonding surface has the surface modification layer without the surface modification layer disposed thereon. 1 nm average surface roughness Ra.

According to the twenty-second aspect, there is provided the object of any one of aspects 16-20, wherein the glass bonding surface has the surface modification layer without the surface modification layer disposed thereon. An average surface roughness Ra of 0.2 nm.

According to the twenty-third aspect, the object of any one of aspects 16-22 is provided, wherein the substrate has 300 micron thickness.

According to the twenty-fourth aspect, the object of any one of aspects 16-23 is provided, wherein the carrier has a thickness of 200 micrometers to 3 mm.

According to aspect A, a glass object is provided, comprising: a carrier having a carrier engaging surface; and a surface modifying layer disposed on the carrier engaging surface, wherein the surface modifying layer is configured to serve as the carrier When the bonding surface and the bonding surface of the glass sheet are bonded via the surface modification layer therebetween, after subjecting the object to a temperature cycle by: heating in a chamber at a rate of 9.2 ° C per minute from a room temperature cycle To 600 ° C, hold at 600 ° C for 10 minutes and then cool to 300 ° C at 1 ° C per minute, and then remove the object from the chamber and allow the object to cool to room temperature, the carrier and tablet The materials are not separated from each other when one is held and the other is subjected to gravity, there is no outgassing from the surface modification layer during the temperature cycle, and the sheet can be separated from the carrier without causing the The thinner one of the carrier and the sheet is broken into two or more pieces.

According to aspect B, a glass object is provided, comprising: a carrier having a carrier bonding surface; a sheet having a sheet bonding surface; a surface modification layer disposed on the carrier bonding surface and the sheet One of the bonding surfaces; the vehicle bonding surface and the sheet bonding surface are bonded via the surface modification layer therebetween, wherein the surface energy of bonding the sheet to the vehicle has the following characteristics, in that the After the object is subjected to temperature cycling by: cyclically heating from room temperature to 600 ° C at a rate of 9.2 ° C per minute in a chamber, maintaining at 600 ° C for 10 minutes, and then cooling to 300 ° C at 1 ° C per minute And the object is then removed from the chamber and the object is cooled to room temperature, the carrier and sheet are not separated from each other while one is held and the other is subjected to gravity during the temperature cycle There is no outgassing from the surface modification layer, and the sheet can be separated from the carrier without breaking the thinner one of the carrier and the sheet into two or more pieces.

According to aspect C, a glass object in any of aspects A or B is provided, wherein the surface modification layer has a thickness of 0.1 nm to 100 nm.

According to aspect D, a glass object in any one of aspects A or B is provided, wherein the surface modification layer has a thickness of 0.1 nm to 10 nm.

According to aspect E, a glass object in any of aspects A or B is provided, wherein the surface modification layer has a thickness of 0.1 nm to 2 nm.

According to any aspect of aspect F, a glass object of any one of aspects A to E or 1-24 is provided, wherein the carrier contains no alkali metal, aluminosilicate or borosilicate or Glass of aluminoborosilicate glass, each having 0.05wt.% Arsenic and antimony.

According to aspect G, a glass object in any of aspects A to F or 1-24 is provided, wherein each of the carrier and the sheet has a size of 100 mm x 100 mm or more.

Claims (12)

A method for controllably bonding a substrate to a carrier, the method comprising the steps of: obtaining a substrate having a polymer bonding surface, the polymer bonding surface having a first surface energy; and obtaining a glass A carrier of a bonding surface, the glass bonding surface has a second surface energy; a surface modification layer is deposited on the glass bonding surface so as to reduce the surface energy of the glass bonding surface; and via the surface modification layer Bonding the polymer bonding surface to the glass bonding surface, wherein the substrate can be non-destructively disengaged from the carrier after being subjected to vacuum annealing for one hour in an environment having a temperature of 120 ° C; and wherein the surface is modified Plasma layers are deposited by one of the following: a plasma polymerization of a carbon-containing gas; a plasma polymerization of a hydrocarbon-containing gas; a plasma polymerization of a hydrocarbon-containing gas and a fluorocarbon gas; a hydrocarbon-containing gas and a hydrogen-containing gas Plasma polymerization of a hydrocarbon-containing gas; a plasma polymerization of a hydrocarbon-containing gas to form a layer, and then treating the layer with a nitrogen-containing gas; a plasma polymerization of a hydrocarbon-containing gas to form a layer, and then The layer is sequentially processed by two independent gases, one of which contains nitrogen and the other gas contains hydrogen; a plasma containing a hydrocarbon gas is polymerized to form a layer, and then the layer is sequentially processed by two independent gases, one of which is a gas Contains nitrogen and oxygen and another gas contains nitrogen; a plasma containing a hydrocarbon gas polymerizes to form a layer, and then the layer is treated with a gas containing nitrogen and oxygen; a plasma containing a hydrocarbon gas, a nitrogen-containing gas, and a hydrogen-containing gas Polymerization; plasma polymerization of a hydrocarbon-containing gas and a hydrogen-containing gas to form a layer, and then treating the layer with a nitrogen-containing gas; plasma polymerization of a fluorocarbon gas; plasma polymerization of a fluorocarbon gas and a hydrogen gas And plasma polymerization of a fluorocarbon-containing gas to form a layer, and then treating the layer with a nitrogen-containing gas and a hydrogen-containing gas at the same time. The method according to claim 1, wherein the surface modification layer is deposited by plasma polymerization of methane gas, ammonia gas, and hydrogen gas. The method according to claim 1, wherein the surface modification layer has a thickness of 1 nm to 70 nm. The method of claim 1, further comprising the step of: cleaning the polymer bonding surface to provide the first surface energy. The method of claim 1, wherein the substrate is a composite comprising a polymer and a glass. The method as claimed in claim 1, wherein the glass bonding surface has before the deposition of the surface modification layer

One of 1 nm has an average surface roughness Ra. The method according to claim 1, wherein the substrate has

One thickness of 300 microns. An object includes: a substrate having a polymer bonding surface; a carrier having a glass bonding surface; a plasma polymerization surface modification layer for releasably bonding the polymer bonding surface to the glass bonding surface; And the plasma polymerized surface modified layer comprises at least one of the following: a plasma polymerized hydrocarbon; and a plasma polymerized fluorocarbon. The article according to claim 8, wherein the plasma polymerized surface modification layer has a thickness of 1 nm to 70 nm. The article of claim 8, wherein the substrate is a composite comprising a polymer and a glass. Article according to claim 8, wherein the glass bonding surface is provided without the plasma-polymerized surface modification layer disposed thereon

One of 1 nm has an average surface roughness Ra. Article according to claim 8, wherein the substrate has

One thickness of 300 microns.